Research Article

ChemCatChem doi.org/10.1002/cctc.202401690

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Ruthenium-Doped Copper Nanowires for Nitrite/Nitrate to

Ammonia Conversion and Their Integration in Zinc–Nitrite
Batteries
Tobias Rios-Studer,[a] Zhengfan Chen,[a] Christean Nickel,[a] Fan Feng,[a] Kevin Sowa,[a]
Ekemena O. Oseghe,[a] Sina Sadigh Akbari,[a] Sarra Rahali,[a] Leon Prädel,[b] Ingo Lieberwirth,[c]
Guangjin Zhang,[d, e, f] Dandan Gao,*[a] Rongji Liu,*[a] and Carsten Streb*[a]

The electrochemical reduction of nitrite (NO2 − ) and nitrate ammonia reduction, the electrode also shows high activity with
(NO3 − ) not only enables sustainable, circular routes to produce Faradaic efficiency of 88.4% (at −0.6 V versus RHE) and a yield
ammonia (NH3 ), but also eliminates pollutants in groundwa- rate of 62.5 mg h−1 cm−2 (at −1.0 V versus RHE). We show that the
ter. In this article, we report a facile synthesis of Ru-doped Cu electrode can easily be integrated into a Zn–nitrite battery, giv-
nanowires on Cu foam electrodes with low Ru (0.48 wt.%) load- ing a power density of 9.1 mW cm−2 , a NH3 yield rate of 1.88 mg
ing. The composite electrode shows high-performance in the h−1 cm−2 and a nitrite-to-ammonia Faradaic efficiency of 88.9%
NO2 − /NO3 − to NH3 electroreduction, giving NH3 Faradaic effi- at a current density of 20 mA cm−2 . The system combines three
ciency of up to 100% and NH3 yield rates up to 33.2 mg h−1 productive outputs, that is removal of NOx − pollutants, synthesis
cm−2 at −0.2 V versus RHE in NO2 − reduction. For the nitrate-to- of valuable NH3 and generation of “green” electricity.

1. Introduction tons produced annually. NH3 plays a crucial role in the produc-
tion of nitrogen fertilizers for agriculture and many chemicals
Ammonia (NH3 ) is one of the most essential and important for industry.[1–3] Additionally, NH3 is gaining increasing interest as
chemical feedstocks in modern society, with over 150 million carbon-free fuel for energy storage due to its high energy den-
sity (4.3 kWh kg−1 ).[4] To-date, the Haber–Bosch-process is the
dominant route in the synthesis of NH3 , where NH3 is formed
by the reaction of gaseous nitrogen (N2 ) with gaseous hydrogen
[a] T. Rios-Studer, Z. Chen, C. Nickel, F. Feng, K. Sowa, Dr. E. O. Oseghe, (H2 ) under high temperature and high pressure, which results in
Dr. S. S. Akbari, S. Rahali, Dr. D. Gao, Dr. R. Liu, Dr. C. Streb
a high energy demand and a significant impact on the global
Department of Chemistry, Johannes Gutenberg University Mainz,
Duesbergweg 10–14, Mainz 55128, Germany carbon footprint. The Haber-Bosch-process consumes about 1–
E-mail: [email protected] 2% of all energy worldwide and is responsible for more than
[email protected] 1%of the annual global CO2 emissions.[5,6] To solve this prob-
[email protected] lem, electrochemical synthesis of NH3 under ambient conditions
[b] L. Prädel offers an energy-efficient reaction pathway.[7,8] However, the
Department for Molecular Spectroscopy, Max Planck Institute for Polymer
direct reduction of nitrogen comes with challenges, such as the
Research, Ackermannweg 10, Mainz 55128, Germany
low aqueous solubility and high dissociation energy. Further-
[c] Dr. I. Lieberwirth
more, the potential needed to reduce nitrogen is in a region
Department of Physical Chemistry of Polymers, Max Planck Institute for
Polymer Research, Ackermannweg 10, Mainz 55128, Germany where the hydrogen evolution reaction (HER) occurs. An alter-
[d] G. Zhang
native to the reduction of nitrogen is the reduction of NOx –
Center of Materials Science and Optoelectronics Engineering, Chinese (nitrate (NO3 − ) and nitrite (NO2 − )), which is easily dissolved in
Academy of Sciences, Beijing 100049, PR China water and the dissociation energy of the N═O bond (204 kJ
[e] G. Zhang mol−1 ) is only about a quarter of the dissociation energy of the
CAS Key Laboratory of Green Process and Engineering, Institute of Process N2 triple bond (941 kJ mol−1 ).[9] NOx − is also a major water pollu-
Engineering, Chinese Academy of Sciences, Beijing 100190, PR China tant due to extensive fertiliser use and industrial processes, and
[f ] G. Zhang its accumulation in the environment leads to serious health and
Key Laboratory of Green and High-value Utilization of Salt Lake Resources,
ecological issues.[10] The urgent need to eliminate NOx − and pro-
Chinese Academy of Sciences, Beijing 100190, PR China
duce NH3 makes the NOx − reduction reaction (NOx RR) via an
Supporting information for this article is available on the WWW under
efficient electrocatalytic route particularly compelling.[1,11,12]
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Although electrocatalytic NOx RR has garnered increasing
© 2024 The Author(s). ChemCatChem published by Wiley-VCH GmbH. This is
an open access article under the terms of the Creative Commons Attribution
attention from researchers as a promising pathway for NH3
License, which permits use, distribution and reproduction in any medium, synthesis, the reaction kinetics and product selectivity in electro-
provided the original work is properly cited. chemical NOx RR are largely determined by the choice of catalyst.

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Scheme 1. Schematic illustration of the synthetic process of CuRu-xh/CF.

To date, a wide range of catalysts have been reported in recent Powder X-ray diffraction (pXRD) was used to confirm the for-
years such as noble metals,[13–15] transition metals,[16,17] metal mation of Cu(OH)2 during the electrochemical oxidation (Figure
alloys,[18–25] as well as metal oxides.[26–28] Among them, Cu-based S1). The pXRD patterns of pure CF, as well as the synthesized pure
materials have emerged as particularly attractive candidates for nanostructured CF (NCF, see experimental procedures in Sup-
NOx RR due to their low cost, weak hydrogen evolution tendency, porting Information) and CuRu-xh/CF, are compared in Figure 1a.
and high electrical conductivity.[17,19,29–33] However, the weak The pure CF as well as the synthesized electrodes exhibit three
adsorption of hydrogen (Had ) on bare Cu limits the hydrogena- distinct diffraction peaks at two theta values of 43.3°, 50.4°, and
tion rate of N-intermediates, resulting in low Faradaic efficiency 74.1°, which are attributed to the (111), (200) and (220) lattice
(FE) for NH3 production. To address this issue, noble metals planes of a face centred cubic (fcc) crystalline structure of Cu
such as Rh, Ru, Pt, and Au, known for their excellent hydro- (PDF#70–3039). However, no diffraction peaks associated with
gen adsorption–desorption properties, have been merged with metallic Ru were present in CuRu-xh/CF, which indicates that no
Cu substrates to enhance the hydrogenation ability of Cu-based crystalline Ru particles are present.[37]
catalysts at more positive potentials, significantly reducing the X-ray photoelectron spectroscopy (XPS) analyses reveal the
overpotential for the NOx RR.[25,34] It has been proposed that the presence of both Cu and Ru in CuRu-3 h/CF. The high-resolution
Cu site preferentially stabilizes nitrogen intermediate species, Cu 2p XPS spectrum of CuRu-3 h/CF is shown in Figure 1b. The
whereas the vicinal noble metals supply the activated H species spectrum shows strong peaks of Cu0 2p3/2 and Cu0 2p1/2 located
required for the surface hydrogenation to proceed. Additionally, at binding energies of 932.5 eV and 952.2 eV as well as weak
due to synergistic effects, 3d transition metals like Fe, Co, and peaks at higher binding energies of 934.1 eV and 954.2 eV asso-
Ni have also been used to modify Cu-based electrodes to create ciated with Cu2+ .[38] To distinguish the chemical states between
bimetallic composite materials with high NOX RR performance.[35] copper metal and oxides, we have also performed Cu Auger XPS
This report builds on pioneering work on the design of noble analysis. The Cu LMM Auger spectrum of CuRu-3 h/CF (Figure
metal (Ru and Rh)-doped nanostructured Cu catalysts.[25,34] Here, S2a, Supporting Information) shows the peaks associated with
we used a modified method for synthesizing a Cu foam (CF) Cu2+ , Cu+ and Cu0[39–41] indicating the partial surface oxidation of
based composite electrode, where Cu nanowires were grown on metallic Cu in CuRu-3 h/CF. Figure 1c displays the high-resolution
the CF surface, and Ru sites where then deposited on the Cu Ru 3d XPS spectrum of CuRu-3 h/CF. Similarly, the peaks could
nanowires. The resulting composite is referred to as CuRu-xh/CF, be deconvoluted into separated peaks for both Ru0 and Ru4+ .[42]
where x represents the duration of the galvanic replacement Besides, the high-resolution Ru 3p XPS spectrum (Figure S2b,
reaction. The catalyst shows high selectivity towards NH3 forma- Supporting Information) also shows the peaks associated with
tion and inertness toward HER, as well as a low NO2 − activation both Ru0 and Ru4+ ,[43] which could also indicate the partial
barrier reported for Ru catalysts.[34,36] The optimized electrode surface oxidation of metallic Ru in CuRu-3 h/CF.
CuRu-3 h/CF shows high performance for both, nitrite and nitrate The morphology of the different electrodes was investi-
reduction to ammonia, and integration into an aqueous zinc– gated using scanning electron microscopy (SEM). The surface
nitrite battery demonstrated the technological deployment of of the pure CF is smooth (Figure S3), whereas the images of
the system. Cu(OH)2 /CF (Figure S4) show a change of the morphology to a
uniform nanowire structure during the electrochemical oxida-
2. Results and Discussion tion, where the nanowires appear smooth and straight. After
galvanic replacement and annealing, the nanowires shown in
Scheme 1 shows the three-step synthetic process for CuRu-xh/CF the images of CuRu-xh/CF are no longer smooth and straight
(see details in the experimental procedures in Supporting Infor- and instead appear elongated and curved with many particles
mation). Briefly, the CF was firstly electrochemically oxidised agglomerated on the nanowires (Figure 1d,e and Figures S5–S7,
to Cu(OH)2 /CF, the obtained Cu(OH)2 /CF was then treated with Supporting Information). This structural change is also present
RuCl3 solution in a galvanic replacement reaction to obtain in NCF (Figure S8), which was prepared without the galvanic
Ru/Cu(OH)2 /CF. In the last step, the Ru/Cu(OH)2 /CF was annealed replacement reaction, indicating the aggregation of metallic
in a 10% H2 /Ar atmosphere to obtain CuRu-xh/CF. The electrodes Cu nanoparticles on the nanowires during the thermal reduc-
were used as-prepared without further pretreatment. tion of Cu(OH)2 . The comparison indicates that the structural

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Figure 1. Structural and elemental analyses of CuRu-xh/CF. (a) pXRD pattern of the synthesized electrodes. (b) High-resolution Cu 2p XPS spectrum.
(c) High-resolution Ru 3d XPS spectrum of CuRu-3 h/CF. (d and e) SEM images of CuRu-3 h/CF with different magnifications. (f ) SEM-EDX elemental
mapping of CuRu-3 h/CF.

changes occur during the annealing process, not during the system using the as-prepared CF-based electrode as the work-
cation exchange process. However, it should be noted that ing electrode, Hg/HgO (1 M KOH) as the reference electrode
the duration of the galvanic replacement reaction affects the and the Pt wire as the counter electrode. All potentials reported
morphology. By comparing the different CuRu-xh/CF electrodes, in this study were converted to reversible hydrogen electrode
it can be observed that a shorter reaction time (CuRu-1 h/CF potentials (RHE).
and CuRu-3 h/CF) does not lead to significant changes in mor- To gain fundamental insight into the electrode reactivity,
phology. However, some particle aggregation is noticeable at we performed linear scan voltammetry (LSV) of the pure CF,
the ends of the nanowires (Figure 1d,e and Figures S5 and S6, NCF, and CuRu-xh/CF electrodes between 0.6 and −0.6 V versus
Supporting Information). If the galvanic replacement reaction RHE in the presence and absence of 0.1 M NaNO2 . As shown in
time was extended to 5 h, the nanowires were no longer uni- Figure 2a, the current density for all electrodes increased over a
formly present on the surface, and instead were agglomerated wide range of potentials in the presence of NO2 − , compared to
(Figure S7). SEM energy dispersive X-ray spectroscopy (SEM-EDX, the LSV performed without NO2 − , which indicates the apparent
Figure 1f and Figure S9, Supporting Information) shows that reduction of NO2 − for all these electrodes. The reduction peak at
Ru is uniformly distributed on the Cu surface. The loading of ∼0.4 V can be attributed to the reduction of Cu2+ to Cu+ .[44,45]
Ru determined by inductively coupled plasma optical emission Further comparison indicates that the presence of nanowire
spectroscopy (ICP-OES) for CuRu-xh/CF was 0.25 wt.% (x = 1), structure of the synthesized electrodes resulted in a higher cat-
0.48 wt.% (x = 3) and 0.92 wt.% (x = 5) respectively (Figure alytic activity compared to pure CF that was further increased in
S10, Supporting Information). This indicates prolonged gal- the presence of Ru (CuRu-xh/CF). CuRu-3 h/CF shows the high-
vanic replacement time can be used to control the Ru loading est catalytic activity and the current density reaches 570 mA/cm2
amount. Furthermore, we have also performed transmission at a potential of −0.6 V versus RHE. Additionally, CuRu-xh/CF
electron microscopy (TEM) and high-resolution TEM (HRTEM) to shows a lower onset potential for NO2 − reduction at 0.25 V ver-
get more detailed information about the CuRu-3 h/CF electrode sus RHE, compared to pure CF (−0.05 V versus RHE). We further
(Figure S11, Supporting Information). The images of the surface performed the Tafel slope analysis of different electrodes toward
layer of the electrode show a polymorphic structure. The lattice NO2 RR (Figure S12, Supporting Information). It is shown that the
spacing was determined as 0.30 nm which corresponds to Tafel slope of NCF (152 mV dec−1 ) significantly decreased com-
the lattice spacing of Cu2 O (110) (Figure S11d,e), which further pared with that of CF (207 mV dec−1 ) due to the formation of
indicates partial surface oxidation of CuRu-3 h/CF electrode. nanowires on the surface of NCF. While the doping of Ru on the
The NO2 RR performance was tested in an H-cell filled with NCF (CuRu-xh/CF electrodes) further increased the Tafel slopes
1 M aqueous KOH as electrolyte, the two cell compartments that could be due to the different reaction mechanisms caused
were separated by a Nafion 117 membrane. A three-electrode by the interaction between Ru and Cu. However, due to the

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Figure 2. Electrocatalytic NO2 RR performance of different electrodes in 1 M KOH solution. (a) LSV curves of pure CF, NCF, and CuRu-xh/CF in the presence
and absence of NO2 − . (b) NH3 FE and (c) NH3 yield rate of pure CF, NCF, and CuRu-3 h/CF. The error bars represent the standard deviations of three
independent measurements. (d) Nitrite-to-NH3 FE and yield rate of CuRu-3 h/CF at 0.1 V versus RHE, detected by indophenol blue method and 1 H NMR
spectroscopy. (e) Cycling stability tests of CuRu-3 h/CF at 0.1 V versus RHE. (f ) NO2 − removal using CuRu-3 h/CF with an initial nitrite-N concentration of
365 ppm at a potential of −0.2 V versus RHE. (g) NH3 yield of CuRu-3 h/CF with NO2 − at 0.1 V versus RHE, without NO2 − at 0.1 V versus RHE and without
potential in the presence of NO2 − . (h) 1 H NMR spectra of the electrolyte before and after electrocatalysis using 14 NO2 − and 15 NO2 − as nitrogen source. (i)
ECSA analysis of NCF and CuRu-xh/CF.

potential coexistence of both HER and NO2 RR, and the complex The corresponding NH3 yield rates are shown in Figure 2c. It
multistep NO2 RR process, it is not easy to investigate the kinetics is visible that CuRu-3 h/CF also shows the highest yield rate
of NO2 RR by using simple Tafel slope analysis. at all applied potentials with a maximum yield rate of 33.2 mg
Thereafter, chronoamperometry tests were performed at h−1 cm−2 at a potential of −0.2 V versus RHE, which is about
potentials between 0.2 and −0.2 V versus RHE to determine NH3 four times higher than that of pure CF. It should be noted that
selectivity of the NO2 RR using pure CF, NCFand CuRu-3 h/CF NCF shows a notably higher yield rate than pure CF, suggest-
as catalysts (Figure S13, Supporting Information). We used the ing that the Cu nanowire structure in NCF enhances catalytic
indophenol blue method (IBM) with UV–vis absorption spec- activity compared to the smooth surface of pure CF, most likely
troscopy as well as 1 H NMR spectroscopy to confirm and quantify due to the increased specific surface area. We also compared
the NH3 production at different potentials (Figure S14, Support- the calculated FE and yield rate of NH3 measured by IBM and
ing Information).[46] The resulting potential dependent NH3 FE is NMR spectroscopy. As shown in Figure 2d, the results of the
shown in Figure 2b. It can be seen that the FE of CuRu-3 h/CF two different methods are consistent. Next, we tested the long-
is the highest at all applied potentials and reaches ∼100% even term stability of the CuRu-3 h/CF catalyst using eight consecutive
at a positive potential of 0.1 V versus RHE. It is notable that 30-min electrolysis cycles at 0.1 V versus RHE (Figure S15, Sup-
the nanostructured NCF does not result in a higher FE than porting Information). The NH3 yield rate and FE of each cycle are
pure CF, indicating the presence of Ru in CuRu-3 h/CF is the shown in Figure 2e. It is shown that the NH3 yield rate and FE
cause of the notably higher selectivity towards NH3 formation. were essentially maintained over 8 cycles, indicating the CuRu-

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3 h/CF has a high stability for the NO2 RR. Post-catalytic analysis face area (ECSA) and the charge-transfer resistance (Rct ) at the
of CuRu-3 h/CF gave us further information regarding the struc- electrode/electrolyte interface, as both parameters are crucial for
tural stability. The pXRD patterns show that there is no change the reactivity of heterogeneous electrocatalysts. Electrochemical
in structure and the same diffraction peaks are present after double-layer capacitance (Cdl ) tests were performed to deter-
the reaction (Figure S16, Supporting Information). Cu LMM Auger mine the ECSA of the synthesized CF-based electrodes (Figures
XPS analysis of Cu shows a decrease of Cu2+ and increase of S22 and S23, Supporting Information). Figure 2i shows the Cdl
Cu+ after the reaction (Figure S2a,c, Supporting Information), of the electrodes, the resulting ECSA is shown in Figure S24,
indicating the partial surface reduction during NO2 RR. The high- Supporting Information. It is noted that CuRu-3 h/CF shows the
resolution Ru 3p XPS spectrum after the reaction does not show highest ECSA among all the electrodes. The result shows that the
any Ru signal (Figure S2d, Supporting Information). However, addition of Ru first leads to an increase in ECSA compared to
ICP-OES was used to verify the presence of Ru, and the load- NCF, but longer reaction time in CuRu-5 h/CF leads to a decrease
ing amount of Ru after reaction was ∼0.29 wt.%, indicating some in ECSA, which may be attributed to the agglomeration of the Cu
leakage of Ru during reaction. Encouragingly, the leaking of Ru nanowires as observed from the SEM images. Further, an electro-
did not reduce much of the activity of the CuRu-3 h/CF electrode. chemical impedance study (EIS) was performed to determine the
SEM images (Figure S17, Supporting Information) of CuRu-3 h/CF Rct of the electrodes (Figure S25, Supporting Information). It is
after NO2 RR indicate that the surface structure changed from notable that CuRu-3 h/CF features more than ten times lower Rct
nanowires to nanosheets during the reaction. SEM-EDX analyses than that of NCF, which enables efficient and fast electron trans-
show that Ru is still uniformly distributed on the surface after the fer at the solid–electrolyte interface, whereas all the CuRu-xh/CF
reaction (Figures S18 and S19, Supporting Information). However, electrodes have similar Rct values (Table S1, Supporting Informa-
we note that this surface restructuring of CuRu-3 h/CF does not tion). These specific characteristics grant CuRu-3 h/CF its superior
have a significant effect on the NO2 RR activity of this material. activity for NO2 RR.
To investigate the NO2 − removal capabilities of CuRu-3 h/CF, Furthermore, we also investigated the performance of CuRu-
a batch conversion test was performed at −0.2 V versus RHE with 3 h/CF in NO3 RR. First, we performed LSV between 0.6 V and
a nitrite-N concentration of 365 ppm (Figure 2f). NO2 − quantifica- −1.2 V versus RHE in the presence and absence of NO3 − (Figure
tion was determined using N-(1-naphthyl)ethylene diamine spec- S26, Supporting Information). The current density increases with
trophotometric method (Figure S20, Supporting Information).[47] more negative potentials in the presence of NO3 − , indicat-
Even at this low nitrite concentration, the nitrite-to-ammonia FE ing the efficient reduction of NO3 − . Next, we performed CA
reached 92%. After 2 h of electrolysis, only 9% of the initial nitrite measurements at potentials between −0.1 and −1.0 V versus
concentration (i.e., 33 ppm remained in the solution. Note that RHE (Figure S27, Supporting Information). The NH3 production
the sum concentrations of nitrite-N and ammonia-N through- was confirmed and quantified using the IBM, and the resulting
out the measurement remain constant and are consistent with nitrate-to-ammonia FE and yield rate are displayed in Figure S28,
the initial nitrite-N concentration, indicating the high NO2 − to Supporting Information. Highest FE (88.4%) was detected at a
NH3 conversion selectivity. Even at a positive potential of 0.1 V potential of −0.6 V versus RHE; the highest yield rate (62.5 mg
versus RHE, the CuRu-3 h/CF still shows efficient conversion of h−1 cm−2 ) was observed at −1.0 V versus RHE. The above results
NO2 − to NH3 . The FE reached as high as 92% after 2 h electroly- show that CuRu-3 h/CF has high performance for the conversion
sis and remained above 80% after 6 h, with only 5% of the initial of NOx − to NH3 , which is comparable to the related CF-based
nitrite (with a nitrite-N concentration of 19 ppm) remaining in the catalysts (Tables S2 and S3, Supporting Information).
solution at the end (Figure S21). For a practical application, we designed a zinc–nitrite battery
To confirm the origin of the nitrogen atoms incorporated in using CuRu-3 h/CF as cathode and zinc foil as anode (Figure 3a).
the synthesized NH3 , several control experiments were under- The battery maintains a constant OCP of 1.13 V for at least 6 h
taken. First, we note that virtually no NH3 is detected when (Figure 3b). Figure 3c shows the charge-discharge LSV curves of
0.1 M aqueous NO2 − solutions were kept at the open circuit the CuRu-3 h/CF based zinc–nitrite battery. The discharge curve
potential (OCP). Also, when a potential of 0.1 V versus RHE was shows an increasing output current density with more nega-
applied, no significant NH3 formation was detected unless NO2 − tive cathodic potential, and the power density reaches 9.1 mW
was present in the solution (Figure 2g). These results indicate cm−2 . The time dependent discharge curves of the battery at
that NH3 originated from the reduction of NO2 − . Also, isotope current densities from 2 to 30 mA cm−2 , displayed in Figure 3d,
labelling experiments were carried out for NO2 RR in the presence indicate a good long-term electrochemical stability. Figure 3e
of 14 NO2 − or 15 NO2 − followed by product identification and quan- displays the NH3 yield and corresponding FE during discharge
tifications via 1 H NMR. As shown in Figure 2h, the characteristic with various output current densities. The CuRu-3 h/CF based
splitting of the 1 H resonance into 3 symmetric signals when using zinc–nitrite battery achieves a NH3 yield rate of 1.88 mg h−1 cm−2
14
NO2 − and the corresponding splitting into 2 symmetric signals and a FE of 88.9% at a current density of 20 mA cm−2 . Lastly,
when using 15 NO2 − reveal the presence of 14 NH4 + and 15 NH4 + the CuRu-3 h/CF based zinc–nitrite battery was used to power
in the NMR spectra. The above results verify that NH3 originates an electronic timer for at least 18 h (Figure 3f). In summary,
from NO2 − reduction. the Zn-nitrite battery achieves three tasks: sustainable energy
To understand the origin of the notable NO2 RR performance supply, NH3 electrosynthesis and removal of NO2 − pollutant in
of CuRu-3 h/CF, we measured the electrochemically active sur- wastewater.[48,49]

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Figure 3. Zinc–nitrite battery test. (a) Schematic illustration of the zinc–nitrite battery with Zn anode and CuRu-3 h/CF cathode. (b) Open-circuit voltage of
the zinc–nitrite battery. (c) Discharge polarisation curve and corresponding power density curve of the zinc–nitrite battery. (d) Discharging curves at
different current densities. (e) NH3 FE and yield rate of the zinc–nitrite battery. (f ) Photograph of an electronic timer powered by our CuRu-3 h/CF based
zinc–nitrite battery.

3. Conclusion Zhang and Carsten Streb acknowledge the International CAS

Partnership Project (039GJHZ2022029GC). Rongji Liu, Dandan
In summary, we report the facile synthesis of a Ru-doped Cu Gao, and Carsten Streb gratefully acknowledge financial sup-
nanowires electrode for highly efficient NOx – to –NH3 reduc- port by Johannes Gutenberg University Mainz, the Top-Level
tion with high activity (with FE near 100% and a yield rate of Research Initiative SusInnoScience, and the Gutenberg Research
33.2 mg h−1 cm−2 at a potential of −0.2 V versus RHE) and high College. The authors acknowledge Dr. Mihail Mondeshki for NMR
stability. Integration of the electrode into a Zn-nitrite battery measurements and discussion.
demonstrated its operational capacity for combined sustainable Open access funding enabled and organized by Projekt
electricity production, NH3 electrosynthesis, and NO2 − pollu- DEAL.
tant removal. The reported approach provides us a hint for
designing high-performance transition metal-based catalysts for
sustainable NH3 synthesis. Data Availability Statement

Supporting Information The data that support the findings of this study are openly avail-
able in zenodo.org at https://doi.org/10.5281/zenodo.13881049,
Experimental and analytical data are available as Supporting reference number 13881049.
Information. The raw data reported in this manuscript is available
at zenodo.org via https://doi.org/10.5281/zenodo.13881049. Keywords: Ammonia synthesis • Electrocatalysis • Nitrate
reduction • Nitrite reduction • Zn-nitrite batteries

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