PERSPECTIVE

[Link]

Engineering 3D Printed Structures Towards

Electrochemically Driven Green Ammonia Synthesis:
A Perspective
Akshay Kumar K. Padinjareveetil, Juan V. Perales-Rondon, and Martin Pumera*

1. Introduction
Broadening scope of 3D printing technology is recently identified as a
potential strategy to mitigate concerns in the light of rising energy crisis and The consistent decline in the availabil-
ity of fossil fuels along with a rapidly
environmental imbalances. The importance of ammonia as a hydrogen carrier growing population has resulted in a se-
is well known and, in the context of 3D printing, designing and fabrication of vere energy crisis in most parts of the
electrode substrates for ammonia synthesis from nitrate sources will present world today. Several efforts have been
a twofold advantage toward addressing the energy crisis and also limiting the carried out by the global scientific com-
harmful effect of excessive nitrate from the environment. Studies in the munity to derive renewable and sus-
tainable energy sources to meet these
direction of employing 3D printed catalysts or reactors for ammonia
growing demands.[1–4] The synthesis of
production have been rarely reported. Thus, in this perspective article, the ammonia at an industrial scale is con-
possibilities of engineering several 3D printed electrocatalysts for nitrate sidered to be one of the most impact-
reduction to ammonia via various techniques are discussed and experimental ful discoveries of the last century[5] and
demonstrations to substantiate the potential of 3D printed electrocatalysts its importance is manifold with applica-
toward ammonia production are provided, for the first time. In addition, tions in agricultural sectors, pharmaceu-
ticals, textiles, refrigeration, and so on.
postfabrication treatments, modification, and patterned coating of 3D printed Being a “green” hydrogen-rich molecule,
substrates using active materials are also discussed along with the ammonia is known to be an impor-
possibilities of fabricating catalysts for ammonia synthesis via nitrogen tant next-generation energy carrier due
reduction reaction. Certain limitations and possible solutions of this printing to its high hydrogen content (17.65 wt%)
technology for ammonia production are discussed along with the future and high gravimetric energy density
(3 kWh kg−1 ), which assists in conve-
outlook. Such timely discussions will be interesting for researchers and
nient storage and transportation along
scientists for enhancing further possibilities toward broadening this field and with clean emissions.[6–11] Hence, its pro-
toward other catalytic applications. duction requires critical attention, es-
pecially for combatting the increasing
energy shortage. Owing to the environmental concerns, and high
A. K. K. Padinjareveetil, J. V. Perales-Rondon, M. Pumera set-up cost for ammonia production via traditional techniques
Future Energy and Innovation Laboratory such as the Haber–Bosch process, researchers are now focusing
Central European Institute of Technology
Brno University of Technology
on simple, efficient, and alternative approaches for ammonia syn-
Purkyňova 123, Brno 61200, Czech Republic thesis.
E-mail: [Link]@[Link] Interestingly, studies focusing on nitrate ions have recently
M. Pumera gained momentum as a new area of research where they
Department of Chemical and Biomolecular Engineering are known to be a potential source for ammonia production.
Yonsei University The electrochemical reduction of nitrate (NO3 − ) into ammo-
50 Yonsei-ro, Seodaemun-gu, Seoul South Korea, 03722
nia (NH3 ), abbreviated as NRA, involves an eight-electron and
M. Pumera
Faculty of Electrical Engineering and Computer Science nine-proton transfer reaction proceeding through multiple reac-
VSB – Technical University of Ostrava tion pathways/intermediate steps.[12,13] NRA has a reaction po-
17. listopadu 2172/15 Ostrava 70800, Czech Republic tential lower than hydrogen evolution reaction (HER). Further-
more, HER can be an interfering and competitive process during
The ORCID identification number(s) for the author(s) of this article
can be found under [Link] NRA, where electrons can be consumed for hydrogen generation,
© 2023 The Authors. Advanced Materials Technologies published by
which can significantly limit the Faradaic efficiency (FE) and se-
Wiley-VCH GmbH. This is an open access article under the terms of the lectivity of the reaction system. Hence, the fabrication of cata-
Creative Commons Attribution License, which permits use, distribution lysts becomes a key step in addressing the challenges associated
and reproduction in any medium, provided the original work is properly with NRA, by limiting the N≡N bond formation and competitive
cited. HER, aiding selective reduction, and delivering appreciable FE
DOI: 10.1002/admt.202202080 necessary for practical applications. Although several fabrication

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techniques for catalysts have already been reported,[14–17] the de- synthesis by exploiting the possible benefits of 3D printing tech-
mand for newer alternative strategies is increasing. nology.
From the fabrication point of view, traditional formative manu-
facturing techniques such as injection moulding, and subtractive 2. Nutshell on 3D Printing Technology
manufacturing techniques such as drilling, cutting, and milling,
although practiced, have several limitations.[18,19] For instance, A bottom-up technique, 3D printing classified under the cate-
complexity associated in device and electrode fabrication, along gory of automated manufacturing processes that has the poten-
with time consumption and high cost, has slowed the pace toward tial to fabricate desired 3D objects by depositing active mate-
fabricating state-of-the-art catalysts. Also, poor selectivity, stabil- rial in a layer-by-layer manner.[21,22,26] Right from its inception
ity, activity, and mass transfer limitations associated with the cat- in the 1980s, this field of study has made remarkable progress in
alysts limit their usage for catalytic applications directly. Thus, terms of providing complete autonomy for designing and print-
the need for simpler fabrication approaches that can easily mod- ing customized products.[27,28] Fundamental advantages of this
ulate the internal structure, and print complex geometries, has technology emanate from its features like immediate prototyp-
increased dramatically. Furthermore, the complexity associated ing ability, scalability, repeatability, flexibility in structural design,
with traditional techniques, along with high fabrication time, the the capacity of manufacturing complex designs, and minimal
need for skilled users, excessive resource wastage, and the need waste generation.[19,22] The technology today has come a long way
for advanced operational facilities for material fabrication has led from its initial usage of generating prototypes to a full-fledged
to further distress. 3D printing industry based across regions. The principles of 3D
Advancements like 3D printing technology (known as “addi- printing techniques have evolved with time based on the precur-
tive manufacturing” technique) have revolutionized the mate- sor materials used, setup cost, and targeted applications. The di-
rial fabrication technique, accounting for its rapid prototyping verse prospects associated with 3D printing make it a reliable
ability, and flexibility in designing and printing.[20–23] In addi- technique for fabricating various industrial tools and its popu-
tion, this innovative technique has the potential to deliver struc- larity can be measured in terms of its shrinking cost, increas-
tures with myriad geometries, better rigidity, tunable porosity, ing purchase rates, and its application has broadened to multi-
and size, thereby mitigating the multiple limitations associated ple domains such food,[29] biosensing,[27] biomedical,[25,30] health
with conventional fabrication techniques. Modifying designs us- emergency,[22] electrochemistry,[20,23,31–33] and beyond. Interest-
ing computer-assisted design (CAD) software is relatively sim- ingly, today it is also expanding to educational[34] and domestic
ple; therefore, materials can be easily formulated and examined circles.
on the basis of targeted products and experimental conditions. The printing process begins with modeling 3D struc-
Nanostructuring of these 3D printed structures in the microm- tures using CAD 3D modeling software, a 3D scanner, or
eter (μm) resolution can induce porosity and enhance the sur- photogrammetry.[22,23] After successful modeling of the design
face area, delivering nanometric features that can efficiently esca- (Figure 1A), it is converted to stereolithography file format (STL),
late and favor the catalytic reaction.[23–25] Engineering 3D printed which is the standard format file, followed by slicing using an-
structures can result in varied geometric morphologies, enhanc- other software. Postslicing, the final output is obtained in the
ing the chances of fabricating active catalyst structures for am- form of a G-code file that contains geometrical information of the
monia production. modeled design, commands, extrusion and bed temperature de-
Other advantages such as its user-friendly nature, rapid and tails, number and density of layers, and so on (Figure 1B). The G-
flexible customization, and possibility to formulate and fabricate code file can be later transferred to the 3D printer for final print-
complex structures using different catalytic materials, make 3D ing. While printing, the 2D layers of active/precursor material are
printing a highly desirable technology for NRA. Also, this would aligned on top of each other sequentially, resulting in the desired
be a breakthrough in the design of materials that can be easily in- 3D structure (Figure 1C). 3D printing techniques and precur-
tegrated into an electrolyzer, with a consequent easiness in scal- sor materials, such as metal filaments/powders, thermoplastics,
ability and manufacturing. In other words, the flexible nature of carbon based filaments, composites, and ceramics, offer multi-
3D printing technology favors rapid material production, facili- ple possibilities for a diverse range of applications. Certain tech-
tating the easy optimization of designs to obtain higher yields. niques associated with the technology are discussed below since
In short, this perspective article discusses the scope of devising a proper understanding of these printing strategies is indeed nec-
3D printed materials with enhanced activity, selectivity, and con- essary for designing application-specific devices/electrodes for
siderable yield for ammonia production. This accounts for the targeted applications.[20,35,36]
fact that proper formulation, engineering, and postfabrication
treatments of the 3D printed substrates could render active sites 2.1. Extrusion-Based Printing
capable of performing NRA, and consequently improve ammo-
nia production. Further, we discuss various strategies for design- Fused deposition modeling (FDM) or “fused filament fabri-
ing 3D printed electrocatalysts, an overview of the catalytic reac- cation” (FFF) involves the extrusion of active filaments down
tion mechanisms, experimentation using 3D printed electrocata- the printer nozzle to obtain a rigid 3D printed structure as
lysts toward ammonia production as a proof of concept, key chal- shown in Figure 2A.[25,31] This printing technique is in high
lenges, and a future outlook of this field. The above discussion is demand owing to its low cost and flexibility in using differ-
anticipated to provide researchers working in this area with rele- ent materials. Each filament has its specific extrusion temper-
vant ideas on designing newer electrode materials for ammonia ature capable of melting desired filaments down the printer

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Figure 1. Schematic representations of steps involved in designing and fabrication of 3D structures. A) designing, B) slicing of modeled structure, and
C) 3D printing.

Figure 2. Schematic representations of 3D printing techniques: A) fused deposition modeling, B) direct ink writing, C) stereolithography, and D) selective
laser sintering.

nozzle to the print bed platform. The precursor material in- Furthermore, another interesting extrusion-based technique
cludes graphene/polylactic acid (PLA) filaments (also known commonly used is direct ink writing (DIW, Figure 2B) where
as “black magic”),[25] carbon-black/PLA (protopasta), metal/PLA liquid-phase “ink” is dispensed out of the nozzle and deposited
filaments[37,38] (where metal = copper [Cu], bronze, stainless steel on the underlying printed layers to fabricate 3D structures.[39,40]
[SS], titanium [Ti], iron [Fe], aluminum [Al], etc.), PLA, acry- Typically, the inks are electrochemically active materials of
lonitrile butadiene styrene (ABS), customized filaments, and so interest in suspension or solution form. Ink formulation is a key
on. The directly printed materials are often subjected to post- aspect of this printing technique, where electroactive materials
fabrication protocols to make them conductive electrode/support along with additives, binders, solvents, and so on, are optimized
for desired applications. Interestingly, studies on 3D printed based on their rheological properties in order to develop an ideal
graphene/PLA filament[31] and metal/PLA filaments[37] have ink capable of extruding down the nozzle. This printing tech-
been reported recently, as ideal electrode substrate for catalytic nology has expanded in terms of printing various materials[41]
applications. that are difficult to practically realize using FDM techniques,

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thus improving its scope for wider applications. Low cost, easy 2.4. 3D Printing versus Conventional Techniques
operation, and highly functional products are other advantages
of this technology.[18] 3D printing differs from the traditional manufacturing technique
such as “subtractive manufacturing,” where, in the case of the
latter, the expected final structures are carved out of a bulk ma-
terial via drilling, milling, sawing, broaching, and so on.[18,19,23]
The excess waste generated during preparation, immense time
2.2. Photopolymerization
consumption involved in designing complex structure, the re-
quirement of extensive human effort, expensive instrumental
Developed in the 1980s, this technique involves the selec-
setups, and the inability to alter the volumetric density of the
tive curing of liquid photopolymer (resin) sequentially using
building material are a few of the drawbacks associated with sub-
a specific light source to fabricate active structures. This tech-
tractive manufacturing.[22] Debates on the efficiency of 3D print-
nique can be further categorized into stereolithography (SLA,
ing and conventional techniques are ongoing. However, more
Figure 2C)[42] and digital light processing, where in the former,
than a replacement of established conventional techniques, 3D
a thin film of photopolymer resin is solidified using UV light
printing expects to enhance the existing ones for various appli-
to obtain a 3D printed structure while the latter uses a digital
cations. However, in the case of 3D printed substrates for cat-
light source.[43] Good accuracy and resolution, versatility, multi-
alytic applications, this technology has an upper hand over other
color, and multimaterial printing are added advantages of this
techniques, especially due to its ability to fabricate custom-made
technique.[18,19]
catalysts with versatile structures, different shapes, and geome-
try of the 3D printed electrodes, subjected to the experimental
condition.[20,23] For the NRA application, 3D printing can be an
advantageous option to fabricate the required 3D printed elec-
2.3. Powder Bed Fusion trodes, especially to design a substrate using active materials, al-
ready known for ammonia production. Such possible prototyp-
Selective laser sintering (SLS, Figure 2D)[22,44] uses thermal en- ing and modifications in 3D printing technology make it more
ergy or high-powered lasers to sinter finely powdered material advanced than other traditional printing techniques. 3D print-
together to procure a final solid structure. This method is highly ing industries are also expected to witness a massive hike in de-
advantageous as it can function without any external aid, has high signing and printing complete electrolyzer cells or catalytic reac-
accuracy, and constitutes a wide range of materials facilitating tors soon. The precursor materials employed are expected to pos-
the easy production of complex structures. However, its opera- sess high chemical resistance toward the electrolytes often used
tion requires better expertise and is also expensive in terms of for electrolysis, making this technology highly promising for de-
equipment and maintenance costs. signing reactor vessels. However, other advanced printing tech-
Selective laser melting (SLM), on the other hand, uses precur- niques, such as SLA, SLS, SLM, and so on, are expected to be ef-
sor materials like metal powders, which are heated until the melt- ficient technologies for fabricating better reactors for ammonia
ing point is achieved.[42,44] Upon heating, the metal powder par- production as well. Thus, by mitigating the issues of intensive
ticles become fused to procure the 3D printed structure , often energy or labor involved in traditional techniques, 3D printing
a conductive metal or metal alloy. Electron beam melting (EBM) can serve as an alternative that is capable of simultaneously 3D
is yet another quick 3D printing technique, where a computer- printing an electrolyzer cell comprising both active electrocata-
controlled electron gun is used to fabricate 3D structures from lysts and a reactor vessel. Finally, it is also worth highlighting the
active metal powder in high vacuum conditions.[19,45] Precious advantages of 3D printing in the field of electrolyzer development
metals and alloys are active materials employed for printing via in terms of less time consumption and ease of iteration of differ-
this technique. Low cost, faster printing with high build speed, ent cell designs for prototype optimization.
and reduced waste generation are some notable advantages of In general, prototype cell development processes involve a cy-
this technique.[18] cle of steps such as design, built, and testing in real conditions
In short, the above techniques can effectively aid in the design to evaluate performance and to identify the limitations and mod-
and fabrication of 3D substrates for a broad spectrum of appli- ify the subsequent designs until an optimized electrolyzer is ob-
cations. Furthermore, these 3D printed structures, upon appro- tained according to the requirements of the system under study.
priate tailoring or postprinting treatments,[46,47] can serve as con- The entire process can be enhanced through the use of 3D print-
ductive catalyst substrates and/or catalyst support for electrocat- ing technology as prototyping and simulation are simpler and
alytic applications. It is, however, the user’s choice regarding the more automated, allowing an optimal construction of devices in
type of material and printing technique that will be paramount a smaller number of iterations. In other words, it can bypass the
in designing substrates. Apart from that, further advancements excessive time taken for optimization.
in this technology can be advantageous in the designing and fab-
rication of reactor vessels, along with multiple components in
an electrolyzer cell. Thus, research in this direction can make
this technology efficient in devising a complete electrochemical 2.5. Summarized 3D Printing Techniques
setup by itself, thus reducing the production cost significantly. In
the following sections, multiple approaches toward designing 3D For a better understanding and appropriate technique selection,
printed substrates for ammonia production will be discussed. 3D printing techniques (discussed so far), associated precursor

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Figure 3. Representation of the reaction mechanism proposed for NRA. Top: The two main mechanisms that explain this reaction taking place at the
surface of a cathode electrode, namely, the adsorbed hydrogen reduction (left) and the electron reduction (right). The reaction mechanism has been
simplified to understand better. Bottom: Schematic of the step-by-step reaction mechanism (electron reduction) with a ball-type structure. Adapted with
permission.[68] Copyright 2021, Royal Society of Chemistry.

materials, advantages, and limitations associated with each tech- water bodies.[66,67] This method, interestingly, bypasses several
nique are presented in Table 1. limitations possessed by previous techniques for ammonia syn-
thesis, and also strategically eradicates the negative effect of ni-
3. Insights toward NRA and Benchmarking trate ions in the environment, making it a significant contributor
Protocol to the energy sector as well.

3.1. Significance of NRA

3.2. Reaction Mechanism
Haber–Bosch is a very well-established method known for large-
scale ammonia production,[55,56] but is an energy-intensive pro- The mechanism of NRA involves a complex eight-electron
cess that involves considerable emission of CO2 and harsh oper- transfer process that proceeds through a series of complex
ating conditions. The limitations of this method invite immedi- pathways.[12] Equation (1) explains the mechanism involved in
ate and alternative solutions for ammonia synthesis. One such the nitrate reduction reaction and the respective potential pro-
strategy involves the electrochemical nitrogen reduction reaction cured with respect to standard hydrogen electrode (SHE)
(NRR) which operates under mild conditions compared to the
Haber–Bosch.[57–60] However, the significantly high energy con- NO−3 + 9H+ + 8e− → NH3 + 3H2 O, E0 = −0.12 V vs SHE (1)
sumed during the breakage of N≡N , along with the competi-
tive HER, low FE, and selectivity, has compelled researchers to The mechanism of nitrate electroreduction[69–74] proceeds
come up with newer experimental approaches, although studies via direct electrocatalytic reduction, which includes two main
on NRR continue on a vast scale. NRA is one such emerging ap- pathways. The first one is regulated by the active adsorbed hydro-
proaches toward ammonia production which is being extensively gen atom (Hads ), called hydrogen adsorption reduction, and the
studied by researchers currently.[13,61–65] Discussions on the ad- second one comprises the electron reduction from the cathode,
vantages of these approaches over conventional techniques are known as the electron reduction pathway. These two main
provided in the Introduction. In the present section, we attempt pathways are illustrated in Figure 3, where the equations of both
to explain the reported reaction mechanism associated with the electrochemical processes are listed.[68] In the Hads mediated
NRA. Further examination has revealed that nitrogen (N2 ) con- pathway (Figure 3, top left), the water molecule is reductively
taining sources such as NO3 − ions are present in abundance as adsorbed on the electrode surface (Hads ). Furthermore, nitrate is
major water contaminants, especially in surface-to-ground-level reduced directly into NH3 by Hads species through a step-by-step

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Table 1. Summary of 3D printing techniques for devising 3D structures for catalytic applications.

3D printing Precursor materials Layer thickness Advantages Disadvantages Refs.

technique

FDM Carbon black/PLA, 50–300 μm • Cheap, scalable, rapid, and easy • Unoptimized extrusion temperature [19,42,48,49]
(Solid Graphene/PLA, prototyping can result in extruder clogging and
based) Carbon black/ABS, • Easy maintenance, controllable bad printing
Graphene/ABS, extrusion conditions and nonlaser • Time-consuming functionalization
PLA, ABS technique and modification approaches
Thermoplastic filaments, • Multiple postfabrication approaches for • Active materials restricted to filament
etc. enhancing printed surface form
• (E.g., solvent activation, chemical • Exposure to highly corrosive aqueous
activation, electrochemical activation, electrolytes can degrade the polymer
enzymatic, etc.) counterparts (e.g., PLA)
• Ideal substrate for functionalizing and
patterned coating approaches to modify
electrode surface
• Fabrication of electrochemical cells and
reaction wares
Metal/ PLA: 50–300 μm • Direct fabrication of metal substrates, a • High sintering temperature and [50,37]
Cu/PLA, Ti/PLA, Fe/PLA, possible replacement to costly time-consuming optimization
stainless steel, etc. conventional metal fabrication conditions
techniques • Solvent-based activation techniques
• Robust, low cost, higher thermal not ideal for polymer removal
conductivity, and active electrocatalytic
surfaces
• Resilience to bending
• Tunable porosity and properties upon
subjection to ideal postfabrication
treatments (e.g., sintering)
Multi-material printing: 50–300 μm • Combining multimaterial features to • Complex integration of multiple [19,51]
(composites of enhance the material property filaments in the printing protocol
Metal/PLA, • Possibilities of obtaining alloy like • Complex postfabrication protocols
Graphene/PLA structures • Size limitations
filaments, PLA, etc.) • Great possibilities for automatizing the • Unoptimized conditions increase
design and preparation of multiple chances of nozzle clogging
components for electrolyzer device
Customized 50–300 μm • High chance of customization of • Time consuming [19,52]
FDM printing (2D materials • Tedious optimization procedures
materials filaments, • Tunable properties and reduces the
nanomaterial/polymers possibilities of foreign impurities
composites, etc.) • Application-specific devices/catalyst
with loading subjected to user’s need
DIW Conductive extrudable inks 50–300 μm • Low cost, simple, easy processibility, • Restacking of active material [18,20,53]
(Solid (nanomaterials, glass, and varied choices • Unoptimized rheology aid in
based) metals, etc.) obeying • Tunable composition with multimaterial clogging and incomplete prints
ideal rheological fabrication facility • Poor mechanical properties and low
property resolution
SLA Photopolymer-based 1–50 μm • Easy, quick, and fine printing with • Time-consuming protocols [19,42]
(liquid materials accuracy and good resolution • Expensive precursors and lack of
based) • No need for support material conductive materials
• Much more complex integration for
electrode fabrication
SLS Metals, ceramics, 20–150 μm • Laser-based technique with high • High cost of instrumentation [18,19,42]
(Powder theromoplastics, low accuracy and broad range of material • Time consuming and limited
based) temperature metal alloys availability scalability
• No need for additional support material • Poor mechanical properties and
surface finishing
SLM Metal and/or metal alloy 20–150 μm • Highly conductive 3D structures • Limited precursor availability [19,42,54]
(Powder powders (stainless steel, • Decreased electrolyte resistance • Costly instrumentation setup
based) Ti-based, Ag-based, • Highly desirable for material • Time consuming
Cu-based) modification

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mechanism using a variety of intermediates such as NO2 − ads , results in a slightly green solution with maximum absorbance at
NOads , Nads , NHads , NH2ads , and so on.[68] the wavelength of 655 nm.[17] Nitrite, on the other hand, is deter-
On the other hand, in the electron reduction pathway mined by another colorimetric assay where the addition of appro-
(Figure 3, top right), a similar mechanism occurs without the priate reagents results in the formation of a complex red-colored
intermediation of Hads , but the direct cathodic reduction on the compound measured for its absorbance at 540 nm.[75,76] These
electrode surface.[68] Schematic representation of the electron compounds are determined to further calculate FE, considering
transfer mechanism taking place during the electron reduction the charge measured during the electrolytic experiment. FE, be-
pathway is given in Figure 3, bottom. Also, during this reaction ing a very important parameter to differentiate between several
pathway, two intermediate Nads recombine to form the most sta- catalytic materials, is frequently used to benchmark electrocat-
ble N2 . Based on theoretical calculations, the migration barrier alysts in this field. In addition, selectivity is also an important
of Nads (0.75 eV) is found to be higher than that of Hads (0.10 parameter in the screening of electrocatalysts and evaluating the
eV). This fact, along with the less feasibility of N–N bond forma- performance of a material toward ammonia production. Measur-
tion over the N–H bond, enhances the possibility of ammonia ing the nitrate concentration is necessary to calculate selectivity.
formation over the catalyst surface by the Hads . In short, the Hads - Similar to the quantification approach adopted in ammonia and
mediated pathway could greatly enhance ammonia production nitrite, nitrate concentration is measured using a colorimetric
via the adsorption of H on the electrode surface. In the electron- method using appropriate reagents, and the absorbance of nitrate
mediated pathway, NO3 − is initially reduced into NO2 − on the is directly measured at 220 nm (subtracting double of absorbance
electrode surface and then reduced into NOads . This intermediate at 275 nm previously).[75] All these methods are used to obtain the
can further result in the formation of either N2 or NH3 via mul- important parameters for understanding the role of the catalyst
tiple complex intermediates such as N2 Oads , HNOads , H2 NOads , and, ultimately, provide a rational strategy to unequivocally select
or NH2 OHads , wherein NH3 is procured as a final product. In the best catalytic material to enhance NRA.
both cases, the most possible stable products are N2 and NH3 .
However, their prevalence is mainly based on the electrolytic con- 4. Scope of 3D Printing Technology for Ammonia
ditions as well as the electrode material selected. For this rea- Production
son, the careful and rational selection of electrocatalysts should
be done in order to favor the mechanism toward NH3 forma- 3D printing technology has garnered significant recogni-
tion over N2 . In addition, although HER is usually perceived as a tion in recent years for its multidimensional possibilities,
competing reaction, its total suppression could hinder ammonia and escalating scientific advancement toward electrocatalytic
production because Hads is relevant for the reaction to proceed. applications.[20,24,31,32,77,78] However, 3D printed electrodes—an
Therefore, catalyst materials exhibiting balanced H and NO3 − ad- ever-expanding domain with great possibilities—have been sur-
sorption capabilities are desirable. prisingly overlooked for ammonia production although they
have been well explored for HER,[31,79] oxygen evolution reaction
(OER),[80,81] carbon dioxide reduction reactions (CO2 RR),[19,32]
3.3. Experimentation and Quantification and CO2 capture.[19] In short, the primary objective of this section
is to understand the feasibility of the available 3D printing tech-
To understand and further compare the performance of a catalyst nology to fabricate 3D printed structures for NRA efficiently. Ow-
toward ammonia production, a suitable benchmarking protocol ing to its immense multidisciplinary aspects, 3D printing tech-
should be followed. As a general approach, the first step consists nology can flourish in both industry and academia in the near
of conducting an electrolytic experiment followed by quantifying future, for diverse applications (Scheme 1).
the products generated during an electrolytic experiment. Thus, Geometry optimization is a very crucial parameter for fabricat-
the classical method to carry out NRA experiments is via am- ing ideal substrates as they can both facilitate as well as hinder the
perometry electrolytic experiments in specific experimental cells. evolution and detachment of gaseous products from the electrode
Typically, at a laboratory scale, two-compartment H-type three- surface.[19,82] For instance, a lack of proper geometric optimiza-
electrodes cells are employed. The electrocatalyst fabricated (here tion or poor design of the substrates can accumulate gaseous
3D printed electrodes) serves as a working electrode on the ca- products over the electrode surface, resulting in the passivation
thodic side along with the Ag/AgCl reference electrode while plat- of the active electrode and a significant drop in the catalytic re-
inum mesh or wire acts as a counter electrode assembled at the sponse. Interestingly, 3D printing technology can be beneficial
anodic side. for resolving the aforementioned concerns and is expected to be
Postelectrolysis, the quantification of products is carried out, promising for the fabrication of active functional electrocatalysts
where in general, the most common products determined in with better accuracy and enhanced performance.
the reaction are NH3 and nitrite (NO2 − ).[75] In addition, NO3 − Figure 4 shows 3D printed electrodes/devices of varying
content is also determined to track the ability of the electrocata- configurations employed for electrochemical applications.[51,84]
lyst to effectively reduce nitrate. Techniques other than UV–vis These differing complex structures/shapes can be mesh shaped,
spectroscopy have also been proposed in the literature to carry basket shaped, ribbon shaped, square shaped, circular electrodes
out these quantifications.[76] However, the colorimetric technique with void shapes and varying sizes, etc. Hence, similar adoption
has gained considerable popularity owing to its ease of usage, low and strict optimization can aid in fabricating 3D printed electro-
cost, higher accessibility for instrumentation, and accuracy. catalysts for NRA, thereby mitigating the limitations faced in fab-
Ammonia is quantified using indophenol blue method, where rication of active catalysts to an extent. Porosity and surface area
its presence is confirmed via quantification of a blue complex that of 3D structures are also critical aspects for ammonia production.

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as an immediate solution to this. However, with progress in the

technology, this is expected to be used in designing functional
electrocatalysts and reactors among others. Furthermore, the fol-
lowing sections and critical discussions provide a broader under-
standing of the feasibility of 3D printing technology for ammonia
production.

4.1. Fused Deposition Modeling

Extrusion-based FDM printing is considered one of the funda-

mental strategies for 3D printing electrodes/devices. In the FDM
technique, active materials, typically filaments, are extruded out
of the hot end of the nozzle to obtain a 3D printed structure
(detailed in Section 2).[25] At laboratory scale, Original Prusa
i3 MK3S+ 3D printer with a nozzle thickness of 0.4/0.6 mm
Scheme 1. Multidimensional applications of 3D printed structures toward
is employed, which can extrude various filaments of car-
ammonia production.
bon/polymer, metal/polymer, and customized 2D material fila-
ments, via FDM technique (Figure 5A). The choice of filaments
is often application-specific and undergoes specific postprinting
treatments to improve the properties of the printed structures.
Although several established works using 3D printed electrode
substrates via the FDM technique for various electrocatalytic ap-
plications have been reported,[20,31,87] ammonia production using
3D printed electrodes is a relatively unexplored domain.
In FDM, the filament materials constitute insulating polymer
components along with conductive active fillers. Postprinting,
the 3D printed substrates are further subjected to certain modi-
fication techniques to remove the nonconductive PLA/ABS poly-
mer components and eventually expose more catalytically active
sites over the electrode surface.[33,88] In addition, sputtering, coat-
ings, and patterning can result in modifying the electrode sur-
faces for desired catalytic applications as explained in detail in
Section 5.

Figure 4. 3D printed electrodes and electrochemical cells of various size

and geometry. A) Selective laser melting 3D printed stainless steel gauze- 4.1.1. 3D Printed Carbon/Polymer Electrodes
shaped and fused deposition modeling 3D printed polylactic acid based
electrochemical cells. Reproduced with permission.[83] Copyright 2017,
Wiley-VCH. B) Helical-shaped 3D printed steel electrode. Reproduced with Carbon materials are interesting catalytic materials owing to their
permission.[84] Copyright 2015, Wiley-VCH. C) Square-shaped 3D printed good electrical conductivity, high surface area, and chemical sta-
copper electrode. D–F) 3D carbon electrodes of various shape and size. bility. Interestingly, modifications[89–91] via heteroatom doping,
C–F) Adapted with permission under the term of CC-BY license.[19] Copy- size, morphology and vacancy engineering, crystal facet regula-
right 2023, The Authors, Advanced Materials Interfaces published by tion, and so on can also render carbon materials active for cat-
Wiley-VCH. G) Square shaped electrode. Adapted with permission.[85] alytic applications as well. Multiple studies have been put forth
Copyright 2019, Wiley-VCH.
regarding modifications and surface engineering strategies over
carbon-based substrates for efficient ammonia production.[92,93]
The advancements in technology can render enhanced surface These studies show that suitably modified carbon/graphene sub-
area for ammonia production via techniques such as sintering, strates are ideal for ammonia production and the scope of
solvent activation, chemical activation, and patterning, a detailed availing carbon/graphene filaments in the context of 3D print-
evaluation of which shall be provided in the subsequent sections. ing ensures a huge advancement in the field of 3D print-
Electrochemical studies on 3D printed electrodes in various ing technology for ammonia production. In short, fabricating
electrolyte systems are available in the literature.[25,86,24] Although 3D printed carbon-based macro/microstructures using carbon-
the degradation of polymers such as PLA in acidic and alkaline based filaments presents new possibilities in devising electrocat-
electrolytes is known, a timely improvement in the fabrication alysts and/or substrates for catalytic applications. Graphene/PLA
of newer metal/polymer and carbon/polymer composites may filament (Figure 5B)[33,94] and carbon-black/PLA ( Figure 5C)
help to overcome this. Masking 3D printed substrates to mitigate are two types of commercial 3D printable filament material
degradation toward harsh electrolyte conditions could be other that are used for printing carbon electrode substrates. Several
possible strategies.[19] Employing customized filament fabrica- works have demonstrated the possibility of easy modification of
tion techniques or other metal 3D printing techniques can serve these activated 3D printed carbon surfaces for enhanced catalytic

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Figure 5. A) Prusa FDM 3D printer capable of extruding filaments to 3D structures. B) Spool of graphene/PLA filament. C) Spool of carbon black/PLA
filament. D) Commercial 3D printable filaments of i) copper, ii) titanium, iii) aluminum, iv) stainless steel, and v) bronze.

properties.[25,85] Speculating that although direct 3D printed car- at −1.21 V; Figure 6G) of ALD-coated 3D carbon substrate
bon electrodes may not deliver very high performance like the (300 cycles) catalyst showed a clear dominance over the pristine
conventionally well-known catalyst, they can serve as good sub- 3D printed carbon substrate. Furthermore, it was observed that
strate material for ammonia production. the FE and yield progressively increased with increasing ALD
For instance, in a study by our group, 3D printed carbon cycles (Figure 6H), thus displaying the potential of ALD-coated
substrates were evaluated for NRA.[95] The two filament sub- MnOx layers to modify the surface chemistry of 3D printed car-
strates of 0D carbon black (Protopasta), and 1D carbon nanotubes bon frameworks for catalytic applications such as NRA.
(graphene/PLA) were evaluated systematically. Figure 6A shows Thus, it can be assured that these commercially available or
linear sweep voltammetry (LSV) profile of 0D carbon black and customized carbon substrates will be a benchmark for the 3D
1D carbon nanotubes in electrolyte solution of Na2 SO4 (with and printing industry, specifically for ammonia production. Multiple
without nitrate), conducted at scan rate of 5 mV s−1 . It was ob- studies recommend the modification of 3D printed electrodes via
served that 0D was inactive, while 1D exhibited nitrate reduc- electrodeposition[25] and patterned coating of active material[96]
tion ability, upon preliminary analysis. Second, electrolysis mea- in order to achieve better performance. This is explained in Sec-
surements of the 3D printed carbon 1D catalyst at multiple po- tion 5 with a major focus on ammonia production. Therefore,
tentials were done, and the quantitative measurements revealed exploiting 3D printed carbon surfaces via appropriate modifica-
that the electrocatalysts showed an increasing yield rate of from tion techniques and optimization can make them ideal electrocat-
6.8 to 364.5 μg h−1 cm−2 and more than 50% FE at potentials alysts for ammonia production and open up further application
beyond −1.21 V versus RHE (Figure 6B). Cyclic stability assess- possibilities.
ments at −1.21 V showed a roughly constant performance of 3D
printed 1D carbon catalyst in terms of both FE and yield rate
(Figure 6C), thereby aiding in devising a cost-effective 3D printed 4.1.2. 3D Printed Metal/Polymer Electrodes
carbon catalyst for NRA application. Furthermore, the role of
metal oxide impurities (TiO2 and Fe3 O4 ), carbon defects (basal With the progress in technology, newer, cost-effective, and scal-
plane, edge plane), and active sites in 3D printed 1D carbon cat- able techniques with high build speed have also been devised
alyst was further elucidated in the study. The studies affirmed to fabricate 3D printed metal structures.[19] For instance, FDM
that a synergistic effect of intrinsic surface features of defective can be used to extrude metal/PLA filaments, which is also a pos-
carbon nanotubes and metallic impurities can enhance the NRA sible replacement for SLA/SLM. However, there is still a long
performance (Figure 6D). Because commercially procured car- way to go. The 3D printing hubs have given immense possibil-
bon filaments may have varying inherent impurities (TiO2 and ity to procure various metal/polymer filaments of Cu, Ti, Al, SS,
Fe3 O4 ) that could influence catalytic activities, the researchers and bronze, leaving users with extensive choices for fabricating
have further employed uniform deposition of manganese oxides application-specific catalysts (Figure 5D).
(MnOx) over 3D printed carbon substrates via atomic layer depo- Cu/PLA: Among the FDM printable metal/polymer filaments,
sition (ALD) technique to procure functionalized carbon frame- Cu/PLA is a well-known commercial filament used for 3D print-
works. LSV was initially employed for a preliminary analysis, ing Cu substrates.[37,38] Interestingly, from the catalysis point of
wherein the ALD-coated layer exhibited a better nitrate reduc- view and previous reports, among transition metals, Cu (CuO or
tion ability over the pristine 3D carbon substrate (Figure 6E). Cu2 O) is considered to be a highly desirable material for ammo-
Quantification of products postelectrolysis shows that the yield nia production owing to its high catalytic activity, selectivity, and
rate (435.9 μg h−1 cm−2 at −1.21 V; Figure 6F) and FE (64.8% high FE. Also, the fact that Cu 3D printed metal electrodes have

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Figure 6. A) LSV profile of 0D and 1D 3D-printed carbon substrates in 0.5 m Na2 SO4 electrolyte and 0.1 m KNO3 /0.5 m Na2 SO4 mixed electrolyte.
B) NH3 yield rate and FE of 3D printed 1D carbon framework at multiple potentials. C) Durability assessments of tests of 3D printed 1D carbon
framework at −1.21 V. D) Schematic representation of enhanced activity of 1D 3D-printed carbon framework. Electrochemical performance of 1D carbon
framework and MnOx ALD-coated 1D carbon framework: E) LSV curve, F) yield rate, G) FE, and H) effect of varying ALD-coated MnOx thickness over
1D carbon framework for NRA activity. A–H) Reproduced with permission.[95] Copyright 2023, Elsevier.

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been studied as catalysts for energy conversion applications[37] typing of electrodes with varying geometry, porosity, and employ-
substantiates the high possibilities of their use as electrocatalysts ing specific activation techniques to these printed platforms can
for ammonia production as well. Cu as a precursor material is make the 3D printed Fe substrates active for NRA applications.
also known to be cheap and nontoxic along with exhibiting good
electrochemical activity toward reduction reactions, high sensi-
tivity, and lower overpotential for reductive electron transfer.[38] 4.1.3. Experimental Demonstration
In Cu/PLA metal filaments, Cu fillers provide good strength and
high conductivity to the printed electrodes while PLA ensures To validate the possibility of ammonia production via 3D printed
structural integrity to filaments both before and after printing. electrodes, an experimental demonstration is carried out by au-
However, postprinting treatment of these 3D printed metal thors with their expertise in 3D printing devices/electrodes and
electrodes is conducted to improve the conductivity of electrodes ammonia electrocatalysis. A detailed study on 3D printed Cu elec-
for enhanced catalytic activity. For instance, sintering 3D printed trodes for NRA is beyond the scope of this article, as the authors
Cu electrodes increases the contact between Cu metal particles to expect to show only a working model in this new domain, as no
eventually realize a conductive Cu metal electrocatalyst.[38] This studies have been reported in this field, to date.
approach can also aid in controlling the morphology of the metal Original Prusa i3 MK3S+ 3D printer (Figure 7A), with
electrode substrate. For instance, in a recent study, 3D printed a nozzle thickness of 0.6 mm (nozzle temperature [Tnozzle ]
Cu electrodes were sintered at various temperatures, and their = 230 °C, print bed temperature [Tbed ] = 60 °C) was em-
elemental states at different temperatures were examined using ployed for 3D printing of Cu/PLA filaments. Commercial
X-ray photoelectron spectroscopy (XPS).[38] From such observa- Cu/PLA filament (Figure 7B) was procured from the Virtual
tions, it is expected that researchers proceeding toward electro- Foundry, USA, which was used for 3D printing Cu electro-
catalyst fabrication would need to optimize the sintering condi- catalyst substrates via FDM (Figure 7C). Sintering of the 3D
tions because variations in conditions such as temperature could printed Cu/PLA electrode substrate was further carried out
modulate the composition of the Cu in printed electrodes. In- at following temperature ramp: 0–300 °C at 5 °C min−1 ;
deed, such optimization can provide a viable strategy to fabricate 300–1010 °C at 3 °C min−1 , 1010–1060 °C at 1 °C min−1 . Finally,
and activate 3D printed metal electrodes that could be integrated the Cu electrodes were held at 1060 °C for 60 min and the oven
into electrolyzers for enhanced NRA. Overall, research focusing was allowed to cool down to room temperature (Figure 7D). This
on these metal 3D printed parts for ammonia production would protocol was carried out to reduce the nonconductive PLA coun-
be highly beneficial for the 3D metal printing industries and fu- terpart in printed structures and eventually expose more conduc-
ture electrochemical applications. tive Cu active sites. Postactivation, the 3D printed electrodes were
Ti/PLA: Transition metals such as Ti are interesting, owing to employed for NRA and quantification studies (Figure 7E).
its cost-effectiveness, robustness, abundant availability, and be- Initially, the electrocatalytic activity of the 3D printed Cu elec-
ing a poor HER catalyst. In addition, its electrochemical potential trodes toward NRA was evaluated using the LSV technique. The
stability window is quite large, making Ti highly selective for ni- experiment was carried out in a three-electrode setup wherein,
trate anion reduction. In a study by Jaramillo and co-workers,[97] a 3D printed Cu electrode served as the working electrode,
electrolyte engineering was carried out using Ti electrodes for the Ag/AgCl as the reference electrode, and platinum as the counter
efficient NRA. The effect of various electrochemical conditions electrode. The LSV was performed in 1 m KOH electrolyte sys-
on selectivity and electrochemical activity at Ti cathode for am- tems both with and without NO3 − at a scan rate of 20 mV s−1 .
monia production was examined using this study. The catalyst Analysis of the LSV curves revealed that the 3D printed Cu elec-
was successful in delivering 82% FE (−1 V vs RHE) and a partial trode was successful in reducing nitrate ions in the electrolyte at
current density to ammonia was also recorded at around −22 mA low onset potential.
cm−2 (nitrate concentration of 0.4 m; pH ≈ 0.77). Today, 3D print- Furthermore, the electrocatalysts displayed a very high cur-
ing technology allows the advanced facility of 3D printing Ti elec- rent density in electrolyte systems containing NO3 − (jmax = 56
trodes via FDM using Ti/PLA filaments. Commercial filaments mA cm−2 ), while the catalyst delivered high onset potential and
for extrusion are available from sources like The Virtual Foundry. low current density in electrolyte solutions without NO3 −
Employing postfabrication strategies such as sintering would re- (Figure 8A). Hence, from the preliminary analysis, it becomes
sult in the successful elimination of the possible nonconductive well evident that 3D printing Cu electrode substrate and subse-
PLA from 3D printed Ti/PLA structures. This approach can re- quent activation treatment results in devising newer conductive
sult in constituting more than 90% Ti metal counterpart, making active substrate for NRA applications. Further, NRA experimen-
them suitable prototypes for catalysis such as NRA. Tuning the tation was performed on 3D printed electrocatalysts in an H-type
geometry, size, and porosity of 3D Ti printed structures can avail cell at −0.92 V versus RHE. This is done to evaluate if the 3D
easy access to fabricate active Ti catalysts for NRA. printed electrocatalysts are ideal for delivering FE of a reason-
Fe/PLA: Fe-based catalytically active centers are long known to able amount upon electrolysis. The electrolysis experiment was
be capable of ammonia production, such as in the Haber–Bosch carried out for 1 h at room temperature with continuous mag-
process.[98] In a very recent study by Wu et al.,[17] Fe single atom netic stirring at 100 rpm.
catalyst was used for NRA and showcased interesting results. In Postelectrolysis, the analyte samples from the cathodic side
the context of 3D printing, we find that this technology gives the were taken and quantified for ammonia as shown in Figure 8B,
possibility of fabricating 3D printed Fe substrates via extrusion- using the standard colorimetric method. Interestingly, the
based printing of Fe/PLA filaments[99] at around 185–195 °C and electrocatalysts delivered about more than 85% of FE and high
bed temperature of around 50 °C. The possibility for rapid proto- yield rate. Thus, this experimental demonstration validates the

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Figure 7. Schematic representation of designing and fabrication of 3D printed Cu electrocatalysts for ammonia production.

Figure 8. A) LSV profile of 3D printed Cu metal electrode. B) Calculated FE and yield rate.

potential of 3D printing technology toward ammonia production. tivated using optimized technique and further studied for electro-
Engineering of these catalysts and ideal optimization conditions chemical applications. Thus, advancements in 3D printing tech-
can deliver FE and yield, beyond the one reported above. Fur- nology have given users the freedom to create their own 3D print-
thermore, researchers and scientists are expected to explore able filaments of 2D transition metal dichalcogenides (TMDs).
the possibilities of this technology to fabricate multiple other TMDs such as MoS2 [100,101] with suitable modifications, are
electrocatalysts for ammonia production in the near future. found to be ideal for ammonia conversion as well. Thus, the
aforementioned observation gives a clear pathway to fabricate
4.1.4. Customized Filament Fabrication MoS2 /carbon filaments that are either modified or engineered,
and later 3D printed and activated to fabricate a 3D printed MoS2
Besides commercially available carbon and metal-based fila- electrocatalysts for NRA.
ments, the advanced research today provides the possibility of Literature also shows that TMDs other than MoS2 are also be-
on-demand filament fabrication using various active materials, ing noticeably used as catalysts for ammonia production. Hence,
2D materials, and nanomaterial composites, based on the user’s appropriate optimizations and the adaptation of previous stud-
choice.[19] For instance, in a recent work published by our group, ies can result in designing and fabricating various 3D printed
filaments of 2D material were fabricated using a slurry contain- substrates/ catalysts other than MoS2 .[102] Since filament fabri-
ing MoS2 , graphite, activated charcoal, and multiwalled carbon cation using graphene and TMDs is already shown to be suc-
nanotubes.[52] The slurry prepared from the above mixture was cessful, we expect that this approach can be expanded toward de-
dried at room temperature and fed into a filament extruder (Felfil signing several similar electrocatalysts using other active materi-
Evo, Italy, Figure 9A) to obtain MoS2 /C/PLA filament. The resul- als such as MXenes[103] MAX phases,[104] MOFs,[105] COFs, other
tant filament was successfully FDM 3D printed to electrodes, ac- layered materials,[106] and so on. Such customized fabrication of

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Figure 9. A) Filament fabricator offering customizable filaments. B) Multimaterial FDM 3D printer and components. (A) and (B) Adapted with permission
under the term of CC-BY license.[19] Copyright 2023, The Authors, Advanced Materials Interfaces published by Wiley-VCH. C) and D) Printer components
from different perspective.

filaments with the desired composition is expected to provide a tive materials, an alloy of 3D printed Cu–Ni hybrid catalyst can
huge advancement in the preparation of electrode materials for be fabricated using the MM FDM printing technique to procure
ammonia production. Also, it would truly be a landmark case if 3D printed bifunctional catalysts. Furthermore, subjecting these
such customized filaments can be used for practical applications 3D printed hybrid systems toward post-fabrication treatments is
and provide users with extensive choices. speculated to enhance the performance of the fabricated catalyst.
Furthermore, fabricating filaments using metal particles and Such 3D printed hybrid electrode systems can be highly innova-
polymers is highly beneficial in achieving active 3D printed sub- tive for catalytic applications such as NRA.
strates for various applications via FDM. For instance, in an arti- 3D printing technology finds wide applications not only in
cle by Hwang et al., Cu and Fe particles were mixed with ABS the designing and fabrication of catalytic material for vari-
thermoplastic to fabricate corresponding metal/polymer com- ous energy applications[23,24,111] such as water splitting,[112] CO2
posite filaments.[107] Based on the loading of metal particles in the reduction,[32,113] and artificial photosynthesis,[114] but also in the
fabricated filaments (i.e., Cu/ABS and Fe/ABS), tensile strength fabrication of electrolyzers[51] (electrolytic cells) that can be used
and thermal conductivity were analyzed along with the optimiza- for practical applications. Components of an electrolyzer device
tion of parameters such as temperature and fill density. The in- include electrodes and current collectors based on the intended
vestigation showcases the importance of both metals and poly- application. Advancements in 3D printing technology have en-
mers in filaments for enhancing conductivity and structural in- hanced the prospects of this industry, especially with more pre-
tegrity, respectively. However, postfabrication approaches can re- cursor materials being added continuously to print hubs. Also,
solve the conductivity issues without compromising the property significant advancements are taking place in the integration of
of the active metal based material. Proper optimization of com- both insulating and conducting parts into the electrolyzers. In
position will lead to the fabrication of an ideal 3D printed metal other words, the possibilities of manufacturing the casing and
substrate, which in turn can serve as an active electrocatalyst for internal components of electrolyzers with complex shapes and
NRA. architecture are infinite using 3D printing approach such as MM
FDM.
As a general approach, the electrocatalysts developed are ex-
4.1.5. Multimaterial Printing and Catalytic Reactors tensively tested in a standard three-electrode cell. However, the
behavior of the electrocatalyst in terms of efficiency and stability
Multimaterial (MM) FDM 3D printing is another interesting is completely different when transferred to an electrolyzer (two-
printing technique that allows the users to sequentially extrude electrode cell) under real conditions. For this reason, the testing
multiple filaments of entirely different compositions simulta- of developed electrocatalysts under actual working conditions is
neously (Figure 9B–D).[51,108,109] This can be considered a ma- mandatory. In principle, MM FDM technology offers a promising
jor revolution in the field of 3D printing, as earlier 3D print- breakthrough in cell design due to decentralized manufacturing,
ers were capable of extruding only one filament at a time. MM and customization possibilities for designing cost-effective and
FDM 3D printing can be interesting for a wide range of applica- highly complex structures with minimal waste generation dur-
tions, especially for catalysis, anticipating a synergistic effect of ing the manufacturing process.
materials in these 3D printed hybrid electrode systems. Studies Thus, over time, this technology is expected to advance toward
on Cu–Ni alloys for enhanced ammonia production are already designing a complete electrolyzer cell that requires less labor,
reported.[16] Also, there are reports available on using metal poly- is cost-effective, efficient, and ideal for catalytic applications
mer filaments of Ni for FDM printing.[110] Thus, in the context such as NRA. However, one of the drawbacks that need to be
of 3D printing by taking advantage of the filaments of both ac- addressed is the integrity of the cell under operation. Owing to

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the layer-by-layer based printing technology, there is a possibility which was about 7.5 times the value procured from 3D carbon.
of liquid leakage with the consequent change in experimental The SAC also displayed a high activity and stability during the
conditions, making it difficult for direct application in the reactor NRA process. Furthermore, electrocatalytic performance of other
design. However, these limitations are expected to be addressed metal sites was evaluated by changing the central elements and
by researchers over time. Nevertheless, at the onset, it appears spatial geometries of 3D printed SACs. In principle, the tech-
to be a very beneficial technique due to its ease of usage and nique has opened up enormous possibilities for fabricating large-
multiple possibilities in the designing and testing of new cell scale commercial production of SACs for a sustainable produc-
configurations in short time periods. tion of fuels and chemicals and a broad spectrum of other appli-
cations.
3D printable inks of 2D materials for DIW[120,121] have gained
4.2. Direct Ink Writing attention for designing electrodes; however, using such elec-
trodes for ammonia production remains unexplored. For in-
Designing 3D printed substrates using all types of precursor stance, there are reports on DIW of 3D MXene substrates,[122]
materials may not be feasible with the FDM-based technique; yet employing these 3D printed substrates as electrocatalysts for
hence, there is a need for better and improved alternatives such NRA has hitherto not been subject to experimentation. Techni-
as DIW. DIW is a well-known 3D printing technique that works cally, MXene dispersions are prepared in both aqueous and non-
on the principle of extruding a formulated ink dispersion of the aqueous systems, provided that the rheological properties are op-
active material out of the nozzle to obtain a final 3D printed timized prior to 3D printing. Understanding the fluidic proper-
structure.[22,40] This printing technique permits the user to 3D ties is an important task because the lack of proper optimizations
print any desirable material as long as the formulated precur- can lead to deviation in the ink flow and result in bad printing.
sor inks follow rheological behavior that is ideal for extrusion. In addition, there are a couple of studies on Cu-modified MX-
Shear thinning and the viscoelastic properties of the ink also ene that have emerged recently for NRA, wherein in one of the
help retain the shape and continue to provide sufficient fluidity, works by Li et al., Cu molecular catalyst (copper phthalocyanine,
and interlayer adhesion, resulting in an ideal 3D printed elec- CuPc) was anchored to the Ti3 C2 Tx MXene surface to obtain a
trocatalyst. 2D materials, such as graphene,[115] TMDs,[101] and CuPc@MXene catalyst. The catalyst delivered very high ammo-
MXenes[116,117] with modifications and improvements, are known nia selectivity of 94.0% and a nitrate conversion rate of 90.5%.[123]
to serve as ideal catalysts/support material for ammonia produc- The above works expand the possibilities of modification of MX-
tion. ene surfaces using various other transition metals for ammonia
Like 2D materials, the scope of single-atom catalysts (SAC)[119] production. Using this approach, similar MXene slurries can be
is also advancing in recent times, especially in the light of catalytic formulated for the DIW of 3D printed MXene electrocatalysts
applications. SAC constitute isolated single metal atoms (active for NRA. Also, 3D printing of MOF-based catalysts was recently
sites), anchored by support materials, with cost-effective, tunable reported via DIW using aqueous Fe-based MOF/silicon carbide
catalytic sites, and high catalytic selectivity being added advan- composite inks[124] enhancing its possibility as an electrocatalyst
tages. Complex wet chemistry synthesis approaches and costly for NRA. In short, formulating slurries of 2D material compos-
precursors aggravate the overall cost of fabrication of SAC. Ac- ites or nanoparticles will be interesting for DIW as the extru-
counting for these critical material fabrication aspects, in a re- sion of such composite materials may be more challenging via
cent study, 3D printed SAC was proposed by Xie et al.,[118] to the FDM approach. However, fabricating multicomponent 3D
fabricate cost-effective target materials and mitigating the com- printed substrates using 2D materials will be a good foundation
plexity associated with the wet chemistry process. Transition for ambitious projects in the future, especially for NRA.
metal precursors along with natural polymers such as gelatin 3D printed Cu substrate for NRA via FDM is already dis-
and gelatin methacryloyl (GelMA) was employed to formulate cussed in the previous section. Interestingly, metallic micro- or
the extrudable ink for fabrication of 3D printed SAC catalysts. nanoparticles that are sintered at high temperatures are found
Postprinting, the sample was freeze-dried, followed by pyrolysis to serve as dispersions for DIW. For example, in a study by Lim
of dried samples to anchor active metal atoms onto the et al.,[125] Cu particles were mixed with Pluronic F127 to obtain
gelatin/GelMA-derived carbon. Employing the above synthesis a self-standing ink that was 3D printed successfully. This was
approach, the researchers were successful to procure isolated Fe followed by postprinting treatments to deliver efficient and con-
sites with Fe(acac)3 (Tris(acetylacetonato)iron(III)) serving as Fe ductive substrates. Taking advantage of the principle adopted in
single atom precursor. The synthesis was also extended to other fabricating Cu electrodes via DIW, the possibility of 3D printing
metal acetylacetonates, such as Pt(acac)2 , Ni(acac)2, Zn(acac)2 , other metal nano/microparticles beyond Cu can be explored.
Co(acac)2 , Cu(acac)2 , and multiple others to procure PtSAC, Noticeably, the 3D printed electrode material prepared via DIW
NiSAC, ZnSAC, CoSAC, and CuSAC, respectively. In addition, may also need to be treated using additional methods to activate
the research provides an experimental demonstration of these 3D and expose their catalytically active surfaces as in the case of
printed Fe SACs (Fe3DSAC) for NRA as an approach to exhibit FDM. Furthermore, gold- (Au)[126] and silver- (Ag)[127] based
the potential of this technology toward fabrication of active elec- electrodes were also studied for NRA. Fabricating 3D printed
trocatalysts. The electrochemical performance was evaluated in structures using these active materials via DIW can enable
an Ar-saturated 0.10 m KOH aqueous solution with 10 × 10−3 m robust and conductive platforms for catalytic applications as in a
NO3 − . It was observed that Fe3DSAC showed a higher ammonia study reported by Zhu et al.[128] In short, the above work can be
production over 3D carbon material. Also, the yield for Fe3DSAC referred to and/or adapted for designing 3D printed substrates
at −0.6 V versus RHE was procured around ≈4.55 μmol cm−2 h−1 of Ag, Au, multiple alloy composites, and so on. Thus, designing

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3D printed electrocatalysts using a wide variety of materials allow the user to devise an active electrocatalyst for large-scale
via DIW for ammonia production shall be a novel venture that applications.
guarantees wide-scale application in the future.
5. Postfabrication Treatments and Modification
4.3. Other Printing Approaches 3D printed electrocatalysts/substrates can be considered a fore-
runner to next-generation energy applications in terms of de-
Metal 3D printing technology provides a rapid prototyping plat- vising electrode materials that are scalable and can be easily
form to fabricate robust and conductive 3D metal electrode extended toward large-scale production. FDM 3D printing of
substrates.[84,129,130] Integrating the design flexibility rendered by graphene/PLA and metal/PLA filaments are well known for the
3D printing technology with the mechanical properties of re- fabrication of catalyst/substrate for a broad spectrum of appli-
spective metals to fabricate electrocatalysts, substrates, and re- cations. Although PLA in these substrates provides structural
actors are interesting material fabrication approaches. In previ- integrity to the printed structure, the conductivity of substrates
ous sections, the ability of metal FDM 3D printing was discussed is severely hampered by these nonconductive polymer counter-
as a potential possibility of the recent advancements to design parts. Thus, postfabrication approaches are introduced to limit
metal 3D printed catalysts. However, multiple other 3D printing the amount of polymers in the printed structures, with the objec-
technologies[19,54,131] are conventionally known for designing ro- tive of increasing the conductivity of the printed substrates, es-
bust, conductive, and active metal 3D printed catalysts, and cat- pecially for catalysis applications.[20,47,94] Solvent,[31] thermal,[88]
alytic reactors. In principle, in this technology of 3D printing, electrochemical,[46] enzyme activation,[133] among others, are
high power laser sources are typically used for binding the pow- some of the techniques employed to get rid of nonconductive PLA
dered metal particles and then systematically printed to procure in carbon substrates or customized substrates.
the final conductive 3D printed structures. Among these, SLS and In a broader context, especially for the FDM technique,
SLM are the potential techniques that can be employed in design- solvent activation using DMF,[25,31] acetone,[94] NaBH4 ,[49]
ing 3D structures with the help of metal powders or metal-based and NaOH,[134] are commonly employed for activating car-
precursor materials. bon/polymer, graphene/polymer electrode substrates, with sev-
SLS-based metal 3D printing technology has been recently eral other solvents being studied periodically. Electrochemical
used by a group of researchers to fabricate self-catalytic reactors treatment is another possible strategy that has been suggested by
(SCR) for CO2 RR applications using various active metal com- researchers to improve the conductivity of 3D printed substrates.
ponents of Fe, cobalt (Co), and Ni.[77] Hence, understanding the In a study by Browne et al.,[86] an interesting approach of material
potential of 3D printing technology for the fabrication of metal enhancement was proposed via sequential solvent activation of
3D printed parts is regarded to be highly promising for devising graphene/PLA electrodes in DMF, followed by electrochemical
active 3D printed substrates for NRA applications. SLM 3D print- activation in phosphate-buffer solution, resulting in 3D printed
ing techniques have also been employed to fabricate 3D printed electrodes with enhanced performance. These catalytic carbon
conductive electrode substrates, where the precursor materials surfaces can also be modified or surface-engineered with metal
are either metal or metal alloys of Cu, Ti, Al, and so on. nanoparticles to fabricate electrocatalysts that are efficient for
3D printed metal electrodes can be printed efficiently using ammonia production.
both SLM and direct metal laser sintering (DMLS) techniques, Sintering is another strategy employed for metal/PLA
where metal powder particles are sintered using a laser source electrodes,[37] such as Cu/PLA and Fe/PLA, wherein exposure
and fused in an inert gas-filled chamber.[132] During the process, of 3D printed substrates to high temperature can result in the
metal powder is added over the sintered layer and the above pro- removal of nonconductive PLA counterparts, delivering metal
cedure is repeated until the final component is printed based on substrates with enhanced and exposed metal active sites.[37,38]
the predesigned 3D modeled data file. While only a single metal Modification of 3D printed substrates using appropriate
powder is used with the SLM technique, multiple metal alloys strategies can render to electrocatalysts for various catalytic
with varying melting points are used to 3D print structures using applications.[135] Electrodeposition,[25] ALD,[85] patterned coating
DMLS. This approach can be used to 3D print metal substrates techniques,[31,96] functionalization of active molecular materials,
using single or multiple metallic components that would render and so on, are a few among a host of other techniques known to
the user the ability to design electrodes with different composi- fabricate active 3D printed structures for ammonia production.
tions and customize an electrocatalyst for ammonia production. Electrodeposition is a well-known and widely adopted tech-
The list of precursor materials available for metal 3D printing nique employed to deposit a layer of active material from a
ranges from Cu, Ni, Ti, Al, etc., and their alloys, to precious met- corresponding precursor metal salt solution over the activated
als such as Au, Ag, and metal powders. Based on discussions car- 3D printed substrates (Figure 10A). This approach can be used
ried out in this paper, it can be observed that these metal precur- to electroplate 3D printed structures with a Cu and Ni layer,[25]
sors can be 3D printed as active materials toward NRA. However, or any similar salt of transition metal[81,136] provided they are
we do not expect the alloy to be efficient by default for ammo- active metal centers for ammonia production. Cu and Ni are
nia production but anticipate that metal printing via SLS, SLM, well known as active electrocatalysts for ammonia production.
EBM, and DMLS will be advantageous in fabricating electrode Thus, techniques such as chronoamperometry can be employed
materials with excellent mechanical and conductive properties, using a Cu- and/or Ni-based salt solution at defined time inter-
making it ideal for NRA. In short, improvements, modifications, vals for the electrodeposition of Cu/Ni over carbon[25] or metal
and optimizations of these 3D printed alloy parts over time will substrates.[83] TMDs like MoS2 and WS2 are promising materials

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nanoparticles, metal oxides, and so on, to be active for ammo-

nia production. For instance, in a study, MoS2 was spray-coated
over 3D printed carbon-based (graphene/PLA) electrode sur-
faces, and evaluated for HER.[96] The approach aided in abundant
and ideal coverage of electrode surfaces by MoS2 sheets. Further-
more, in another interesting study from our groups, dip-coating
(Figure 10F) of 2D materials such as MXenes and TMDs of
MoS2 , MoSe2 , WS2 , and WSe2 , were coated over DMF-activated
3D printed graphene/ PLA electrode.[31] Postdrying, the electrode
was evaluated for HER application in 0.5 m H2 SO4 electrolyte so-
lution, showcasing improved electrocatalytic activity of 3D elec-
trode substrate. Thus, techniques such as dip-coating can be em-
ployed as a facile and cost-effective approach of electrode modifi-
cation over conventional techniques.
Sputtering an active material can also be highly beneficial for
designing 3D printed electrocatalysts. For instance, in a study,
NRA was carried out over modified Au electrodes.[126] Modifica-
tions via sputtering of Au on 3D printed carbon electrodes and
post-treatments also have been reported to improve the surface
properties of electrode substrates. This can be extended to Ag or
similar transition metals, which could be ideally sputtered over
3D printed electrode surfaces to fabricate newer electrodes for
NRA. Thus, there is an immense possibility of improving the
Figure 10. Modification of 3D printed electrocatalysts via A) electrodepo- substrate surface for NRA in multiple ways. The major task lies in
sition, B,C) ALD, D) spray-coating, E) spin-coating, and F) dip-coating. deciding the ideal modification approach for each catalytic mate-
rial followed by its optimization. Hence, the 3D printing of active
material substrates is expected to show high possibilities for the
for ammonia production. Because electrodeposition of these ma- design of ideal electrocatalysts that are efficient, active, and highly
terials is already reported,[137] we assume that these modified 3D selective for NRA.
printed electrocatalysts could be highly efficient for NRA as well.
Furthermore, techniques such as ALD deliver a feasible, 6. 3D Printed Substrates for Nitrogen Reduction
homogeneous (Figure 10B), and conformal deposition of ac- Reaction
tive layers, sequentially without compromising the 3D topogra-
phy. A stepwise demonstration is given in Figure 10C. These Haber–Bosch process is the conventionally well-known indus-
are advanced deposition techniques with high reproducibility trial process for ammonia production. Owing to the limita-
that are ideal for depositing material of tunable thickness over tions of this technique, as mentioned in the previous section,
complex structures such as 3D printed electrodes.[138] For in- there have been constant efforts among researchers for find-
stance, in a study, 2D materials such as MoS2 are shown to be ing alternatives. Among them, electrochemical NRR for ammo-
coated efficiently over 3D printed titanium electrodes for catalytic nia production[59,140,141] has gained massive scientific interest in
applications.[50] This technique is ideal for depositing active ma- the recent past. NRR continues to be a well investigated do-
terial over carbon-based substrates as well.[138] Although limita- main, although recent studies consider NRA to be more effi-
tions from electrodeposition can be mitigated by adopting better cient than NRR. Thus, a discussion on the possibilities of de-
techniques such as ALD, they are expensive and require expert signing 3D printed electrocatalysts for NRR can be interesting
guidance, especially during coating over 3D printed electrodes. to the researchers working in this area. NRR offers the possibil-
ALD also has a wide range of metal/metal oxide precursor mate- ity for large-scale applications owing to the abundant availabil-
rials that can be explored for obtaining a better electrode surface, ity of nitrogen source in the atmosphere.[140,142,143] In addition,
ideal for NRA. the clean and sustainable mode of NH3 production with less
Patterned coatings of active material dispersions over 3D energy-intensive working conditions and low or even zero CO2
printed substrates are an interesting, rapid, and cost-effective emissions makes this technique unique and preferable over the
electrode modification approach to devise electrocatalysts. This Haber–Bosch process.
approach has attracted significant attention in recent years due Thus, the fundamental focus would be on developing ideal
to the low complexity of the instrumentation and minimal com- electrocatalysts with high activity and stability that can efficiently
plications involved in ink formulation.[31,139] Techniques such as carry out ammonia synthesis under ambient conditions. Further-
spray-coating (Figure 10D),[96] spin-coating (Figure 10E), and dip- more, it must also be capable of mitigating selectivity toward
coating[31] are commonly known approaches to fabricate sub- HER and favor ammonia production. 3D printed electrocatalysts
strates that are cheaper and less toxic, enabling successful coat- for NRR are also relatively new and unexplored like NRA. The
ing over the desired 3D printed substrates. These techniques mechanism can be procured from the literature as detailing is be-
give users the freedom to develop a wide range of 3D printed yond the scope of the article.[59,144,145] Although several catalysts
material catalysts by patterning 2D materials, their composites, for NRR, and the possibility of fabricating catalysts using these

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active materials via 3D printing are both well known, the inter- 6.3. 2D Materials
disciplinary domains of 3D printing electrocatalysts for ammo-
nia synthesis via NRR are still not explored well. In the following Studies on combining 2D materials to fabricate electrocatalysts
discussion, we focus on developing a bridge between existing re- for ammonia production are known to be relatively new, one
ports on the possible active materials known for NRR and the fea- among them being the recent studies on loading 1T′-MoS2 with
sibility of using these materials toward fabrication of 3D printed Ti3 C2 MXene.[155] The possibility of ideal ink formulation via
electrodes/devices via various techniques. DIW can also result in developing 3D printed MoS2 /MXene elec-
trocatalysts for desired catalytic applications such as for NRR.
These novel approaches of designing self-standing, robust, and
6.1. Carbon Substrates active 3D printed electrocatalyst substrates can bring an impact-
ful improvement in this field.
Advantages of carbon substrates are very well discussed in Sec- Though the major part of this article focuses on the possibil-
tion 4.1.1 along with several reports on carbon/graphene sub- ity of utilizing 3D printed electrodes for NRA, we also claim that
strates for NRR applications.[146,147] For instance, Zhang et al.[93] the technique of 3D printing electrocatalysts has not been hith-
put forth a detailed discussion on multiple defect engineering erto introduced to NRR as well. Thus, a large possibility exists for
strategies over carbon-based substrates for efficient ammonia designing electrocatalysts for NRR via several other techniques,
production. Also, Majumder et al.[148] discuss the possibility of given the fact that 3D printing shows enormous prospects of fab-
modifying graphene electrocatalysts for enhanced ammonia pro- ricating substrates similar to the ones that have been already re-
duction from nitrogen. Therefore, adapting the possibilities of ported for NRR. Also, the mechanism shared by these two re-
using carbon material from the above works into the realm of actions (NRA and NRR) to give the same product (ammonia)
3D printing technology can lead to the fabrication of 3D printed has a big difference, and their adaptability to serve as a cata-
carbon substrates via FDM (black magic/protopasta/customized lyst via 3D printing technology is subject to repeated improve-
carbon-based filaments, etc.) for ammonia synthesis. ment, considering the geometry, porosity, and size with respect
to the experimental conditions, systematic optimization, and tun-
ing/optimizing the postfabrication approaches. However, consid-
6.2. Metal Electrocatalysts ering the reports on the limitations of NRR over NRA, the major
focus was shifted to 3D printing electrodes for NRA. Neverthe-
Cu,[149] Ti,[150] Ni,[151] Au,[152] and Ag[153] have been explored for less, there is still scope for improvement in designing electrocat-
NRR application as well. In the domain of 3D printing, employ- alysts of active material using FDM, DIW, SLA, or SLM among
ing the respective metal/PLA filaments of corresponding active others for NRR.
material (Cu, Ti, Ni, etc.) and/or modification of 3D printed sub-
strates via sputtering (Ag, Au), electrodeposition (Ag, Au, Ni, Cu, 7. Challenges and Solutions
etc.), coatings of active material (Ni, Cu, etc.) over substrates,
would help in designing ideal and efficient 3D printed electro- The prospect of 3D printed substrates for NRA is relatively
catalysts. In principle, this approach would help in designing new and, thus, the expected uptake in this area can be a
3D printed electrocatalysts for NRR applications at a large scale, bit slow; however, once the abilities of this technology toward
in minimal time, and cost-effective manner. Advancements in NRA are fully realized, it will represent a promising leap in
3D printing technology, such as customized filament fabrication the design of electrodes/devices. FDM-based electrode and de-
(Section 4.1.4), MM 3D printing techniques (Section 4.1.5), and vice fabrication using graphene/PLA, carbon black/PLA, car-
other known 3D printing techniques, would also help in design- bon black/ABS, customized 2D material/PLA, and so on, are
ing ideal electrocatalysts for ammonia production via nitrogen well known. However, extruded 3D printed structures may not
reduction. The postfabrication techniques and electrode modifi- be ideal for direct catalysis applications owing to the presence
cations discussed in Section 5 are also advantageous for the fab- of nonconductive constituents (PLA, ABS, etc.), requiring post-
rication of conductive 3D printed electrodes with high selectivity fabrication treatments.[47,94] Although several techniques have
and efficiency for NRR, as well as for high-yield ammonia pro- been proposed,[19,20] very strict optimization measures are rec-
duction. ommended because overexposure to postfabrication treatments
Furthermore, molybdenum (Mo) and Fe are considered to be such as solvents, and physical and/or chemical treatments can
theoretically feasible electrocatalysts for NRR. In a work by Zeng result in excess loss of polymer from printed parts. This even-
et al.,[154] nitrogen-doped MoS2 nanoflowers were studied as elec- tually affects the strength of 3D printed structures, resulting in
trocatalysts under ambient conditions. It was observed that the the weakening and breakage of the printed structures. Neverthe-
catalyst delivered high FE (9.14%) at −0.3 V versus RHE in 0.1 m less, an initial exploration of this technique for the fabrication of
Na2 SO4 and provided NH3 yield of 69.82 μg h−1 mgcat −1 . In our 3D printed catalyst can be relatively time-consuming, where the
previous discussion about the FDM 3D printing technique, the user will initially need to fabricate multiple prototypes with varied
work on MoS2 3D printed substrates conducted by our group was compositions of active material, fillers, polymers, additives, and
mentioned.[52] The possibility of modifying these electrode sur- so on (e.g., customized filaments). Optimization also extends to
faces via nitrogen doping or similar method is also known to be the filament extrusion quality, extrusion temperature, and repro-
technically feasible. Thus, we propose the possibility of designing ducibility. Postoptimization of the ideal filament composition can
nitrogen-doped 3D printed MoS2 substrates via extrusion-based aid in employing these 3D printed structures as electrocatalysts
technique that are speculated to be ideal for NRR. for NRA applications.

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Temperature is another vital factor for the extrusion of fila- technology can be an asset in the fabrication and engineering of
ments, wherein the extrusion temperature will vary from fila- 3D printed electrodes that serve as active electrocatalysts for am-
ment to filament. Sometimes high temperatures can result in the monia production. Several precursors materials have emerged in
oxidation of metal nanoparticles or filament composites, affect- recent years that can be extruded/sintered/formulated success-
ing the conductivity severely. A possible remedy would be to de- fully to procure 3D printed electrodes and devices. These precur-
sign a special chamber that would be capable of providing inert sors include carbon materials, 2D materials (graphene, MXene,
atmospheric conditions via constant purging of Ar/N2 gas during TMDs, MOFs, etc.), metal/metal oxides, nano/microparticles,
printing.[19] In addition, sintering 3D printed metal electrodes and many more. Interestingly, 3D printing techniques today pro-
such as Cu/PLA, Fe/PLA, and Ti/PLA, at elevated/unoptimized vide the flexibility of printing self-supported catalyst substrates,
temperatures can result in the degradation or deformed shape of SACs, for catalysis and possibly resolve several issues encoun-
the printed electrodes. This could be mitigated by using covering tered by traditional printing techniques. We summarize that al-
materials and molds that help to preserve the shape of the elec- though several active materials are reportedly known to be ideal
trode post thermal treatment. As a feasible strategy, experiments for ammonia production, 3D printing technology confers the
like thermogravimetric analysis could be initially employed to freedom to 3D-print these active materials for catalytic applica-
track the degradation of polymers from the printed structure. tions like NRA. The technology of 3D printing was developed four
With such systematic understanding, the user can easily opti- decades ago; however, it has taken a considerable length of time to
mize the required temperature for activating the printed elec- expand and flourish as a domain across multiple industries and
trode substrate without losing the shape of the printed structures. sciences. This technique today has become exponentially cheaper
DIW using certain active materials can result in clogging of the as the cost of printers, precursor materials, and other accessories
nozzle; however, the rheological properties of inks should be con- consistently declines. Although 3D printing electrodes for cat-
stantly assessed for better printability. Proper optimization of ink alytic applications are primarily studied as a proof-of-concept,
fluidity can also prevent bad printing or incomplete printed struc- over time this technology is expected to potentially expand to
tures. large-scale manufacturing terrains, using structures that are less
Electrode modification via various techniques was discussed expensive and with large outputs. This process of escalating from
in detail in the previous section. However, certain challenges are small-scale laboratory operations to a large-scale industrial setup
also associated with the modification of the electrocatalyst sur- can be challenging and requires critical and creative resolutions
face using conventional techniques, which has to be taken care in its design.
of for efficient catalyst fabrication. For instance, although elec- 3D printing is known to have great potential in terms of de-
trodeposition techniques are cheap, quick, and provide a wide signing reactors for catalytic systems as it holds a dual advantage
range of choices for metal or metal oxides, the semiuniform de- of having a catalyst component as well as the ability to moderate
position of material over the 3D printed structure can serve as a the flow of reactants. This article, however, has focused on using
major limitation to this technique.[19] The techniques employed 3D printing technology for the fabrication of functional catalysts,
for electrodeposition are expected to be well optimized, prior to catalytic reactors, and similar systems for ammonia production.
its coating over fabricated 3D electrode material. Significant advancements have been witnessed in recent years
Every technique has its pros and cons. Therefore, finding the in fabricating 3D printed devices, with a major focus on catal-
ideal technique based on the experimental setup/targeted appli- ysis applications. Thus, the fabrication of active electrocatalysts
cations has to be carefully executed to fabricate ideal electrocata- that could be integrated into the electrolytic system, along with
lysts/reactors/devices for applications such as ammonia produc- the manufacturing of both framework and internal part of the
tion. Strategies to improve ammonia production have evolved electrolyzer, can be considered to be significant advancements in
over time and have come a long way from conventional tech- the field of NRA. This would also be an impactful technology in
niques like Haber–Bosch and NRR to recent ones like NRA. De- the future for diversifying ammonia production. In short, with
signing ideal electrocatalysts or catalytic reactors has been the ammonia production being a vital application, further advance-
primary goal of all these techniques, where the catalyst exhibits ments are expected in this direction and 3D printing would be
high activity, selectivity, efficiency, and stability during the reac- a breakthrough in designing novel electrocatalyst structures that
tion. 3D printing for ammonia production is a relatively new ap- are more cost-effective, energy-efficient, and also mitigate the en-
proach toward designing electrodes or electrolyzers; therefore, it vironmental concerns.
is guaranteed to take a considerable amount of time and research
to develop effective strategies for fabricating efficient catalysts for
NRA. Acknowledgements
M.P. acknowledges the financial support of Grant Agency of the Czech Re-
8. Conclusion and Future Perspective public (EXPRO: 19-26896X). A.K.K.P. acknowledges the grant CEITEC-K-
21-7059, realized within the project Quality Internal Grants of BUT (KInG
Catalysts can play a significant role in resolving several ongoing BUT), Reg. No. CZ.02.2.69/0.0/0.0/19_073/0016948 and financed from
crises arising due to the declining availability of fossil fuels and the OP RDE .
the exhaustion of resources with the increasing population. The
conversion of nitrate into ammonia has unfolded the scope of an
alternative sustainable pathway for ammonia synthesis and, thus,
the design of ideal electrocatalysts for this process has become a
Conflict of Interest
major task. This perspective article discusses how 3D printing The authors declare no conflict of interest.

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Keywords [28] C. Barnatt, 3D Printing: The Next Industrial Revolution, Explain-

[Link], 2013.
3D printing, ammonia synthesis, catalysis, electrochemical nitrate reduc- [29] J. Sun, Z. Peng, W. Zhou, J. Y. H. Fuh, G. S. Hong, A. Chiu, Proc.
tion, electrochemistry, nitrogen reduction reactions, patterned coatings Manuf. 2015, 1, 308.
[30] V. V. T. Padil, K. P. Akshay Kumar, S. Murugesan, R. Torres-Mendieta,
Received: January 9, 2023 S. Wacławek, J. Y. Cheong, M. Černík, R. S. Varma, Green Chem. 2022,
Revised: March 24, 2023 24, 3081.
Published online: May 23, 2023 [31] K. P. Akshay Kumar, K. Ghosh, O. Alduhaish, M. Pumera, Elec-
trochem. Commun. 2021, 122, 106890.
[32] E. Vaněčková, M. Bouša, V. Shestivska, J. Kubišta, P. Moreno-
García, P. Broekmann, M. Rahaman, M. Zlámal, J. Heyda, M.
Bernauer, T. Sebechlebská, V. Kolivoška, ChemElectroChem 2021, 8,
[1] S. C. Peter, ACS Energy Lett. 2018, 3, 1557. 2137.
[2] L. Pokrajac, A. Abbas, W. Chrzanowski, G. M. Dias, B. J. Eggleton, S. [33] C. W. Foster, M. P. Down, Y. Zhang, X. Ji, S. J. Rowley-Neale, G. C.
Maguire, E. Maine, T. Malloy, J. Nathwani, L. Nazar, A. Sips, J. Sone, Smith, P. J. Kelly, C. E. Banks, Sci. Rep. 2017, 7, 42233.
A. Van Den Berg, P. S. Weiss, S. Mitra, ACS Nano 2021, 15, 18608. [34] C. W. Pinger, M. K. Geiger, D. M. Spence, J. Chem. Educ. 2020, 97,
[3] A. Venkateshaiah, J. Y. Cheong, S. H. Shin, K. P. Akshaykumar, T. G. 112.
Yun, J. Bae, S. Wacławek, M. Černík, S. Agarwal, A. Greiner, V. V. T. [35] N. Shahrubudin, T. C. Lee, R. Ramlan, Proc. Manuf. 2019, 35, 1286.
Padil, I. D. Kim, R. S. Varma, Green Chem. 2020, 22, 1198. [36] S. C. Ligon, R. Liska, J. Stampfl, M. Gurr, R. Mülhaupt, Chem. Rev.
[4] T. R. Karl, K. E. Trenberth, Science 2003, 302, 1719. 2017, 117, 10212.
[5] D. R. MacFarlane, P. V. Cherepanov, J. Choi, B. H. R. Suryanto, R. Y. [37] C. Iffelsberger, D. Rojas, M. Pumera, J. Phys. Chem. C 2022, 126,
Hodgetts, J. M. Bakker, F. M. Ferrero Vallana, A. N. Simonov, Joule 9016.
2020, 4, 1186. [38] E. Redondo, M. Pumera, Appl. Mater. Today 2021, 25, 101253.
[6] A. Valera-Medina, F. Amer-Hatem, A. K. Azad, I. C. Dedoussi, M. [39] J. A. Lewis, Adv. Funct. Mater. 2006, 16, 2193.
De Joannon, R. X. Fernandes, P. Glarborg, H. Hashemi, X. He, S. [40] S. Tagliaferri, A. Panagiotopoulos, C. Mattevi, Mater. Adv. 2021, 2,
Mashruk, J. McGowan, C. Mounaim-Rouselle, A. Ortiz-Prado, A. 540.
Ortiz-Valera, I. Rossetti, B. Shu, M. Yehia, H. Xiao, M. Costa, Energy [41] A. Shahzad, I. Lazoglu, Composites, Part B 2021, 225, 109249.
Fuels 2021, 35, 6964. [42] C. Parra-Cabrera, C. Achille, S. Kuhn, R. Ameloot, Chem. Soc. Rev.
[7] G. Jeerh, M. Zhang, S. Tao, J. Mater. Chem. A 2021, 9, 727. 2018, 47, 209.
[8] S. Ornes, Proc. Natl. Acad. Sci. USA 2021, 118, e2119584118. [43] formlabs, SLA vs. DLP: Guide to Resin 3D Printers, https:
[9] R. Schlögl, Angew. Chem., Int. Ed. 2003, 42, 2004. //[Link]/eu/blog/resin-3d-printer-comparison-sla-vs-dlp/,
[10] J. Guo, P. Chen, Chem 2017, 3, 709. (accessed: July 2022).
[11] L. Li, C. Tang, B. Xia, H. Jin, Y. Zheng, S. Z. Qiao, ACS Catal. 2019, [44] E. O. Olakanmi, R. F. Cochrane, K. W. Dalgarno, Prog. Mater. Sci.
9, 2902. 2015, 74, 401.
[12] X. Lu, H. Song, J. Cai, S. Lu, Electrochem. Commun. 2021, 129, [45] Nick Loth, ALL3DP, Electron Beam Melting (EBM) – 3D Printing
107094. Simply Explained, [Link]
[13] G. F. Chen, Y. Yuan, H. Jiang, S. Y. Ren, L. X. Ding, L. Ma, T. Wu, J. ebm-3d-printing-simply-explained/. accessed October, 2022
Lu, H. Wang, Nat. Energy 2020, 5, 605. [46] P. L. dos Santos, V. Katic, H. C. Loureiro, M. F. dos Santos, D. P. dos
[14] J. Qin, K. Wu, L. Chen, X. Wang, Q. Zhao, B. Liu, Z. Ye, J. Mater. Santos, A. L. B. Formiga, J. A. Bonacin, Sens. Actuators, B 2019, 281,
Chem. A 2022, 10, 3963. 837.
[15] Z. Gao, Y. Lai, Y. Tao, L. Xiao, L. Zhang, F. Luo, ACS Cent. Sci. 2021, [47] D. P. Rocha, R. G. Rocha, S. V. F. Castro, M. A. G. Trindade, R. A.
7, 1066. A. Munoz, E. M. Richter, L. Angnes, Electrochem. Sci. Adv. 2022, 2,
[16] Y. Wang, A. Xu, Z. Wang, L. Huang, J. Li, F. Li, J. Wicks, M. Luo, D. e2100136.
H. Nam, C. S. Tan, Y. Ding, J. Wu, Y. Lum, C. T. Dinh, D. Sinton, G. [48] G. I. J. Salentijn, P. E. Oomen, M. Grajewski, E. Verpoorte, Anal.
Zheng, E. H. Sargent, J. Am. Chem. Soc. 2020, 142, 5702. Chem. 2017, 89, 7053.
[17] Z. Y. Wu, M. Karamad, X. Yong, Q. Huang, D. A. Cullen, P. Zhu, C. [49] E. Redondo, J. Muñoz, M. Pumera, Carbon 2021, 175, 413.
Xia, Q. Xiao, M. Shakouri, F. Y. Chen, J. Y. (Timothy) Kim, Y. Xia, K. [50] V. Urbanová, J. Plutnar, M. Pumera, Appl. Mater. Today 2021, 24,
Heck, Y. Hu, M. S. Wong, Q. Li, I. Gates, S. Siahrostami, H. Wang, 101131.
Nat. Commun. 2021, 12, 2870. [51] A. Ambrosi, M. Pumera, ACS Sustainable Chem. Eng. 2018, 6, 16968.
[18] A. Ambrosi, R. R. S. Shi, R. D. Webster, J. Mater. Chem. A 2020, 8, [52] K. Ghosh, S. Ng, C. Iffelsberger, M. Pumera, Appl. Mater. Today 2022,
21902. 26, 101301.
[19] A. K. K. Padinjareveetil, M. Pumera, Adv. Mater. Interfaces 2023, 10, [53] B. Y. Ahn, E. B. Duoss, M. J. Motala, X. Guo, S. Il Park, Y. Xiong,
2201734. J. Yoon, R. G. Nuzzo, J. A. Rogers, J. A. Lewis, Science 2009, 323,
[20] M. P. Browne, E. Redondo, M. Pumera, Chem. Rev. 2020, 120, 2783. 1590.
[21] M. R. Hartings, Z. Ahmed, Nat. Rev. Chem. 2019, 3, 305. [54] J. Zhu, P. Wu, Y. Chao, J. Yu, W. Zhu, Z. Liu, C. Xu, Chem. Eng. J. 2022,
[22] K. P. A. Kumar, M. Pumera, Adv. Funct. Mater. 2021, 31, 2100450. 433, 134341.
[23] A. Ambrosi, M. Pumera, Chem. Soc. Rev. 2016, 45, 2740. [55] H. Liu, Ammon. Synth. Catal. 2013, 1.
[24] C. Y. Lee, A. C. Taylor, A. Nattestad, S. Beirne, G. G. Wallace, Joule [56] J. Humphreys, R. Lan, S. Tao, Adv. Energy Sustainability Res. 2021, 2,
2019, 3, 1835. 2000043.
[25] K. P. A. Kumar, K. Ghosh, O. Alduhaish, M. Pumera, Electrochem. [57] L. Zhang, X. Ji, X. Ren, Y. Ma, X. Shi, Z. Tian, A. M. Asiri, L. Chen, B.
Commun. 2020, 120, 106827. Tang, X. Sun, Adv. Mater. 2018, 30, 1800191.
[26] X. Tian, J. Jin, S. Yuan, C. K. Chua, S. B. Tor, K. Zhou, Adv. Energy [58] D. Liu, M. Chen, X. Du, H. Ai, K. H. Lo, S. Wang, S. Chen,
Mater. 2017, 7, 1700127. G. Xing, X. Wang, H. Pan, Adv. Funct. Mater. 2021, 31,
[27] J. Muñoz, M. Pumera, TrAC, Trends Anal. Chem. 2020, 128, 115933. 2008983.

Adv. Mater. Technol. 2023, 8, 2202080 2202080 (19 of 22) © 2023 The Authors. Advanced Materials Technologies published by Wiley-VCH GmbH
 2365709x, 2023, 13, Downloaded from [Link] by Cochrane Peru, Wiley Online Library on [19/01/2025]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[Link] [Link]

[59] S. L. Foster, S. I. P. Bakovic, R. D. Duda, S. Maheshwari, R. D. Milton, [93] L. H. Zhang, F. Yu, N. R. Shiju, ACS Sustainable Chem. Eng. 2021, 9,
S. D. Minteer, M. J. Janik, J. N. Renner, L. F. Greenlee, Nat. Catal. 7687.
2018, 1, 490. [94] R. Gusmão, M. P. Browne, Z. Sofer, M. Pumera, Electrochem. Com-
[60] J. Hou, M. Yang, J. Zhang, Nanoscale 2020, 12, 6900. mun. 2019, 102, 83.
[61] Y. Wang, W. Zhou, R. Jia, Y. Yu, B. Zhang, Angew. Chem., Int. Ed. 2020, [95] W. Gao, J. V. Perales-Rondon, J. Michalička, M. Pumera, Appl. Catal.,
59, 5350. B 2023, 330, 122632.
[62] J. Martínez, A. Ortiz, I. Ortiz, Appl. Catal., B 2017, 207, 42. [96] R. Gusmão, Z. Sofer, P. Marvan, M. Pumera, Nanoscale 2019, 11,
[63] W. Duan, G. Li, Z. Lei, T. Zhu, Y. Xue, C. Wei, C. Feng, Water Res. 9888.
2019, 161, 126. [97] J. M. McEnaney, S. J. Blair, A. C. Nielander, J. A. Schwalbe, D. M.
[64] J. Wang, C. Cai, Y. Wang, X. Yang, D. Wu, Y. Zhu, M. Li, M. Gu, M. Koshy, M. Cargnello, T. F. Jaramillo, ACS Sustainable Chem. Eng.
Shao, ACS Catal. 2021, 11, 15135. 2020, 8, 2672.
[65] P. H. van Langevelde, I. Katsounaros, M. T. M. Koper, Joule 2021, 5, [98] T. Kandemir, M. E. Schuster, A. Senyshyn, M. Behrens, R. Schlögl,
290. Angew. Chem., Int. Ed. 2013, 52, 12723.
[66] M. Duca, M. T. M. Koper, Energy Environ. Sci. 2012, 5, 9726. [99] Elegant3D, Iron PLA filament Proto-Pasta magnetic iron 1.75 mm
[67] A. Scheidleder, J. Grath, G. Winkler, U. Stark, C. Koreimann, C. 0.5 kg, [Link]
Gmeiner, P. Gravesen, J. Leonard, M. Elvira, S. Nixon, J. Casillas, [Link]. accessed July, 2022
T. J. Lack, N. Thyssen, “Groundwater quality and quantity in Eu- [100] L. Yang, W. Zhu, Appl. Surf. Sci. 2022, 596, 153624.
rope”@eng, Bernan Associates, U.S.A 1999, 1. [101] J. Li, Y. Zhang, C. Liu, L. Zheng, E. Petit, K. Qi, Y. Zhang, H. Wu, W.
[68] Y. Wang, C. Wang, M. Li, Y. Yu, B. Zhang, Chem. Soc. Rev. 2021, 50, Wang, A. Tiberj, X. Wang, M. Chhowalla, L. Lajaunie, R. Yu, D. Voiry,
6720. Adv. Funct. Mater. 2022, 32, 2108316.
[69] A. C. A. De Vooys, R. A. Van Santen, J. A. R. Van Veen, J. Mol. Catal. [102] J. P. Hughes, P. L. Dos Santos, M. P. Down, C. W. Foster, J. A.
A: Chem. 2000, 154, 203. Bonacin, E. M. Keefe, S. J. Rowley-Neale, C. E. Banks, Sustainable
[70] A. R. Cook, N. Dimitrijevic, B. W. Dreyfus, D. Meisel, L. A. Curtiss, Energy Fuels 2019, 4, 302.
D. M. Camaioni, J. Phys. Chem. A 2001, 105, 3658. [103] Y. Z. Zhang, Y. Wang, Q. Jiang, J. K. El-Demellawi, H. Kim, H. N.
[71] Y. Li, Y. K. Go, H. Ooka, D. He, F. Jin, S. H. Kim, R. Nakamura, Angew. Alshareef, Adv. Mater. 2020, 32, 1908486.
Chem., Int. Ed. 2020, 59, 9744. [104] K. P. Akshay Kumar, O. Alduhaish, M. Pumera, Electrochem. Com-
[72] R. Jia, Y. Wang, C. Wang, Y. Ling, Y. Yu, B. Zhang, ACS Catal. 2020, mun. 2021, 125, 106977.
10, 3533. [105] S. Mallakpour, E. Azadi, C. M. Hussain, New J. Chem. 2021, 45,
[73] A. C. A. de Vooys, M. T. M. Koper, R. A. Van Santen, J. A. R. Van Veen, 13247.
Electrochim. Acta 2001, 46, 923. [106] S. Wert, C. Iffelsberger, A. K. K Padinjareveetil, M. Pumera, ACS Appl.
[74] T. Yoshioka, K. Iwase, S. Nakanishi, K. Hashimoto, K. Kamiya, J. Phys. Electron. Mater. 2023, 5, 928.
Chem. C 2016, 120, 15729. [107] S. Hwang, E. I. Reyes, K. sik Moon, R. C. Rumpf, N. S. Kim, J. Elec-
[75] Y. Wang, Y. Yu, R. Jia, C. Zhang, B. Zhang, Natl. Sci. Rev. 2019, 6, 730. tron. Mater. 2015, 44, 771.
[76] J. Crawford, H. Yin, A. Du, A. P. O’Mullane, Angew. Chem. Int. Ed. [108] R. Kelly, Multi-material 3D Printer: Types & Printing Guide, https:
2022, 134, e202201604. //[Link]/2/multi-material-3d-printing-an-overview/, 2022. ac-
[77] Q. Wei, H. Li, G. Liu, Y. He, Y. Wang, Y. E. Tan, D. Wang, X. Peng, G. cessed February, 2023
Yang, N. Tsubaki, Nat. Commun. 2020, 11, 4098. [109] A. Ambrosi, R. D. Webster, M. Pumera, Appl. Mater. Today 2020, 18,
[78] X. Zhou, C. J. Liu, Adv. Funct. Mater. 2017, 27, 1701134. 100530.
[79] C. Iffelsberger, S. Ng, M. Pumera, Appl. Mater. Today 2020, 20, [110] E. Mackiewicz, T. Wejrzanowski, B. Adamczyk-Cieślak, G. J. Oliver,
100654. Materials 2022, 15, 1360.
[80] Y. Ying, M. P. Browne, M. Pumera, Sustainable Energy Fuels 2020, 4, [111] S. Mooraj, Z. Qi, C. Zhu, J. Ren, S. Peng, L. Liu, S. Zhang, S. Feng,
3732. F. Kong, Y. Liu, E. B. Duoss, S. Baker, W. Chen, Nano Res. 2021, 14,
[81] P. L. dos Santos, S. J. Rowley-Neale, A. G. M. Ferrari, J. A. Bonacin, 2105.
C. E. Banks, ChemElectroChem 2019, 6, 5633. [112] S. Liu, R. Liu, D. Gao, I. Trentin, C. Streb, Chem. Commun. 2020, 56,
[82] M. P. Browne, A. Mills, J. Mater. Chem. A 2018, 6, 14162. 8476.
[83] A. Ambrosi, M. Pumera, Adv. Funct. Mater. 2018, 28, 1700655. [113] D. Corral, J. T. Feaster, S. Sobhani, J. R. Deotte, D. U. Lee, A. A. Wong,
[84] A. Ambrosi, J. G. S. Moo, M. Pumera, Adv. Funct. Mater. 2016, 26, J. Hamilton, V. A. Beck, A. Sarkar, C. Hahn, T. F. Jaramillo, S. E. Baker,
698. E. B. Duoss, Energy Environ. Sci. 2021, 14, 3064.
[85] M. P. Browne, J. Plutnar, A. M. Pourrahimi, Z. Sofer, M. Pumera, [114] L. Chen, X. Tang, P. Xie, J. Xu, Z. Chen, Z. Cai, P. He, H. Zhou, D.
Adv. Energy Mater. 2019, 9, 1900994. Zhang, T. Fan, Chem. Mater. 2018, 30, 799.
[86] M. P. Browne, F. Novotný, Z. Sofer, M. Pumera, ACS Appl. Mater. [115] F. Lei, W. Xu, J. Yu, K. Li, J. Xie, P. Hao, G. Cui, B. Tang, Chem. Eng.
Interfaces 2018, 10, 40294. J. 2021, 426, 131317.
[87] M. H. Omar, K. A. Razak, M. N. Ab Wahab, H. H. Hamzah, RSC Adv. [116] T. Hu, M. Wang, C. Guo, C. M. Li, J. Mater. Chem. A 2022, 10, 8923.
2021, 11, 16557. [117] J. Wang, T. Feng, J. Chen, J.-H. He, X. Fang, Research 2022, 2022,
[88] F. Novotný, V. Urbanová, J. Plutnar, M. Pumera, ACS Appl. Mater. 9837012.
Interfaces 2019, 11, 35371. [118] F. Xie, X. Cui, X. Zhi, D. Yao, B. Johannessen, T. Lin, J. Tang, T. B. F.
[89] Y. Zheng, Y. Jiao, S. Z. Qiao, Adv. Mater. 2015, 27, 5372. Woodfield, L. Gu, S.-Z. Qiao, Nat. Synth. 2023, 2, 129.
[90] K. P. A. Kumar, O. Alduhaish, S. F. Adil, M. Pumera, Adv. Mater. In- [119] X. Yang, A. Wang, B. Qiao, J. Li, J. Liu, T. Zhang, Acc. Chem. Res.
terfaces 2022, 9, 2102317. 2013, 46, 1740.
[91] J. Zhu, S. Mu, Adv. Funct. Mater. 2020, 30, 2001097. [120] R. Yang, J. Zhou, C. Yang, L. Qiu, H. Cheng, Adv. Mater. Technol.
[92] Z. Chen, J. Chen, G. Barcaro, T. M. Budnyak, A. Rokicińska, R. Dron- 2020, 5, 1901066.
skowski, S. Budnyk, P. Kuśtrowski, S. Monti, A. Slabon, Catal. Sci. [121] K. Hassan, M. J. Nine, T. T. Tung, N. Stanley, P. L. Yap, H. Rastin, L.
Technol. 2022, 12, 3582. Yu, D. Losic, Nanoscale 2020, 12, 19007.

Adv. Mater. Technol. 2023, 8, 2202080 2202080 (20 of 22) © 2023 The Authors. Advanced Materials Technologies published by Wiley-VCH GmbH
 2365709x, 2023, 13, Downloaded from [Link] by Cochrane Peru, Wiley Online Library on [19/01/2025]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[Link] [Link]

[122] C. Zhang, L. McKeon, M. P. Kremer, S.-H. Park, O. Ronan, A. Seral- [137] C. Iffelsberger, M. Pumera, J. Mater. Chem. A 2021, 9, 22072.
Ascaso, S. Barwich, C. Ó. Coileáin, N. McEvoy, H. C. Nerl, B. Ana- [138] W. Gao, J. Michalička, M. Pumera, Small 2022, 18, 2105572.
sori, J. N. Coleman, Y. Gogotsi, V. Nicolosi, Nat. Commun. 2019, 10, [139] R. M. Pasquarelli, D. S. Ginley, R. O’hayre, Chem. Soc. Rev. 2011, 40,
1795. 5406.
[123] L. X. Li, W. J. Sun, H. Y. Zhang, J. L. Wei, S. X. Wang, J. H. He, N. J. [140] X. Guo, H. Du, F. Qu, J. Li, J. Mater. Chem. A 2019, 7, 3531.
Li, Q. F. Xu, D. Y. Chen, H. Li, J. M. Lu, J. Mater. Chem. A 2021, 9, [141] A. R. Singh, B. A. Rohr, J. A. Schwalbe, M. Cargnello, K. Chan, T. F.
21771. Jaramillo, I. Chorkendorff, J. K. Nørskov, ACS Catal. 2017, 7, 706.
[124] A. D. Salazar-Aguilar, A. Quintanilla, S. M. Vega-Díaz, J. A. Casas, P. [142] Y. Ren, C. Yu, X. Tan, H. Huang, Q. Wei, J. Qiu, Energy Environ. Sci.
Miranzo, M. I. Osendi, M. Belmonte, Open Ceram. 2021, 5, 100047. 2021, 14, 1176.
[125] G. J. H. Lim, Z. Lyu, X. Zhang, J. J. Koh, Y. Zhang, C. He, S. Adams, [143] X. W. Lv, C. C. Weng, Z. Y. Yuan, ChemSusChem 2020, 13, 3061.
J. Wang, J. Ding, J. Mater. Chem. A 2020, 8, 9058. [144] J. Wang, S. Chen, Z. Li, G. Li, X. Liu, ChemElectroChem 2020, 7, 1067.
[126] M. S. El-Deab, Electrochim. Acta 2004, 49, 1639. [145] D. Wang, L. M. Azofra, M. Harb, L. Cavallo, X. Zhang, B. H. R.
[127] Z. Liu, C. Wang, C. Chen, C. Li, C. Guo, Electrochem. Commun. 2021, Suryanto, D. R. MacFarlane, ChemSusChem 2018, 11, 3416.
131, 107121. [146] Y. Liu, Y. Su, X. Quan, X. Fan, S. Chen, H. Yu, H. Zhao, Y. Zhang, J.
[128] C. Zhu, Z. Qi, V. A. Beck, M. Luneau, J. Lattimer, W. Chen, M. A. Zhao, ACS Catal. 2018, 8, 1186.
Worsley, J. Ye, E. B. Duoss, C. M. Spadaccini, C. M. Friend, J. Biener, [147] J. Deng, C. Liu, Chem 2018, 4, 1773.
Sci. Adv. 2018, 4, eaas9459. [148] M. Majumder, H. Saini, I. Dědek, A. Schneemann, N. R. Chodankar,
[129] T. Duda, L. V. Raghavan, IFAC-PapersOnLine 2016, 49, 103. V. Ramarao, M. S. Santosh, A. K. Nanjundan, Š. Kment, D.
[130] T. S. Cheng, M. Z. M. Nasir, A. Ambrosi, M. Pumera, Appl. Mater. Dubal, M. Otyepka, R. Zbořil, K. Jayaramulu, ACS Nano 2021, 15,
Today 2017, 9, 212. 17275.
[131] Formlabs, 3D Printing Technology Comparison: FDM vs. SLA vs. [149] Y. X. Lin, S. N. Zhang, Z. H. Xue, J. J. Zhang, H. Su, T. J. Zhao, G.
SLS, [Link] Y. Zhai, X. H. Li, M. Antonietti, J. S. Chen, Nat. Commun. 2019, 10,
the-right-3d-printing-technology/, accessed July, 2022. 4380.
[132] Sculpteo, 3D Printing with DMLS and SLM Technologies, https: [150] H. Hirakawa, M. Hashimoto, Y. Shiraishi, T. Hirai, J. Am. Chem. Soc.
//[Link]/en/materials/dmls-material/#:∼:text=DMLS. 2017, 139, 10929.
accessed July, 2022 [151] S. X. Wang, H. Maimaiti, B. Xu, Y. Guo, P. S. Zhai, H. Z. Zhang, J.
[133] C. L. Manzanares-Palenzuela, S. Hermanova, Z. Sofer, M. Pumera, Phys. Chem. C 2019, 123, 31119.
Nanoscale 2019, 11, 12124. [152] H. Ma, Z. Chen, Z. Wang, Nanoscale 2021, 13, 1717.
[134] D. M. Wirth, M. J. Sheaff, J. V. Waldman, M. P. Symcox, H. D. White- [153] W. Li, K. Li, Y. Ye, S. Zhang, Y. Liu, G. Wang, C. Liang, H. Zhang, H.
head, J. D. Sharp, J. R. Doerfler, A. A. Lamar, G. Leblanc, Anal. Chem. Zhao, Commun. Chem. 2021, 4, 10.
2019, 91, 5553. [154] L. Zeng, S. Chen, J. Van Der Zalm, X. Li, A. Chen, Chem. Commun.
[135] J. Muñoz, M. Pumera, ChemElectroChem 2020, 7, 3404. 2019, 55, 7386.
[136] X. Su, X. Li, C. Y. A. Ong, T. S. Herng, Y. Wang, E. Peng, J. Ding, Adv. [155] X. Chen, S. Zhang, X. Qian, Z. Liang, Y. Xue, X. Zhang, J. Tian, Y.
Sci. 2019, 6, 1801670. Han, M. Shao, Appl. Catal., B 2022, 310, 121277.

Akshay Kumar K. Padinjareveetil is a doctoral student in the Future Energy and Innovation Lab at
CEITEC, Brno, Czech Republic. His research focuses on designing and fabrication of devices and
electrode materials for electrocatalysis, energy storage, environmental remediation, and biomedical
applications. Previously, he completed his postgraduation in chemistry from the Cochin University of
Science and Technology, India, in 2018.

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Juan V. Perales-Rondon received his B.S. in Chemistry from University of Los Andes (Venezuela) and
his Ph.D. in Electrochemistry from the University of Alicante (Spain), working in electrocatalysis, in
understanding the mechanism of formic acid oxidation on Pt electrodes. His research experience
ranges from fundamental electrocatalysis, spectroelectrochemical studies for electrocatalysis as well
as the use of couple technique for energy and analytical applications. Recently, he has directed his
research toward the development of electrodes for nitrate to ammonia conversion, as well as the study
of the reaction at a fundamental level to understand the origin of the catalyst activity.

Martin Pumera is a Chief Investigator of Future Energy & Innovation Lab at CEITEC, Brno, Czech Re-
public, and the Director of the Center for Advanced Functional Nanorobots and a Distinguished Pro-
fessor of Chemistry at the University of Chemistry and Technology, Prague. He received his Ph.D. in
2001 from Charles University, Czech Republic. He became a tenured group leader at National Institute
for Materials Science (NIMS), Japan, in 2006 and joined Nanyang Technological University, Singa-
pore, as a professor in 2010. His research interests include 2D nanomaterials, 3D printing, electro-
chemistry, and micro/nanomachines. He is a “Highly Cited Researcher” by Clarivate Analytics since
2017.

Adv. Mater. Technol. 2023, 8, 2202080 2202080 (22 of 22) © 2023 The Authors. Advanced Materials Technologies published by Wiley-VCH GmbH