Analytical and Bioanalytical Chemistry (2023) 415:2005–2023

https://doi.org/10.1007/s00216-022-04493-7

REVIEW

Recent progress of metal–organic frameworks as sensors in (bio)

analytical fields: towards real‑world applications
Alessio Zuliani1 · Noureddine Khiar1 · Carolina Carrillo‑Carrión1

Received: 21 October 2022 / Revised: 14 December 2022 / Accepted: 16 December 2022 / Published online: 4 January 2023
© The Author(s) 2023

Abstract
The deployment of metal–organic frameworks (MOFs) in a plethora of analytical and bioanalytical applications is a growing
research area. Their unique properties such as high but tunable porosity, well-defined channels or pores, and ease of post-
synthetic modification to incorporate additional functional units make them ideal candidates for sensing applications. This
is possible because the interaction of analytes with a MOF often results in a change in its structure, eventually leading to a
modification of the intrinsic physicochemical properties of the MOF which is then transduced into a measurable signal. The
high porosity allows for the adsorption of analytes very efficiently, while the tunable pore sizes/nature and/or installation of
specific recognition groups allow modulating the affinity towards different classes of compounds, which in turn lead to good
sensor sensitivity and selectivity, respectively. Some figures are given to illustrate the potential of MOF-based sensors in the
most relevant application fields, and future challenges and opportunities to their possible translation from academia (i.e.,
laboratory testing of MOF sensing properties) to industry (i.e., real-world analytical sensor devices) are critically discussed.

Keywords Metal–organic frameworks · Tunable properties · Analytical tools · Sensors · Contaminants · Bioanalysis

Introduction Although the well-known 3 “S” rule, i.e., sensitivity (the

slope of the calibration curve), selectivity (the ability to dis-
During the last years, the R&D in analytical chemistry has criminate a target analyte), and stability/reusability (changes
made great strides in designing sensors, i.e., analytic devices in accuracy in function of time/cycles of use), defines the
responding to the presence (qualitative sensors) and/or con- crucial characteristics to pursue when designing a sensor,
centration (quantitative sensors) of a specific target analyte, the most recent trends in the field are aimed at preparing
a family of compounds, or several analytes simultaneously analytical sensors also featuring the following [1]:
(multiplexed sensors), for central applications in industrial
process management, chemical risk detection, food qual- (i) Fast response. This is particularly important when
ity control, environmental analysis, and medical diagnosis. a quick decision needs to be made for health issues,
economic reasons, or environmental remediation. For
example, rapid analysis is necessary in contaminated
Published in the topical collection Analytical Nanoscience and sites, to instantly provide data for the assessment of
Nanotechnology with guest editors Ángel Ríos and Wolfgang J. the remediation activities. Rapid analysis is also
Parak. needed in pandemic situations, to monitor the spread
In honor of Prof. Miguel Valcárcel.
of the disease, such as in the case of the COVID-19
pandemic.
* Alessio Zuliani (ii) Portability. Portable sensors present a clear advan-
[email protected] tage, for example, in fighting the disposals of toxic
* Carolina Carrillo-Carrión reagents in sites difficultly monitored or in tiny
[email protected] environments. Another big area that is enormously
1 benefiting from the rapid evolution of miniaturized
Asymmetric Synthesis and Nanosystem Group (Art&Fun),
Institute for Chemical Research (IIQ), CSIC-University sensing systems is the medical field, as evidenced by
of Seville, 41092 Seville, Spain the increasing use of wearable sensing devices.

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Vol.:(0123456789)
2006 Zuliani A. et al.

(iii) Easy and low-cost methods. The easiness and sim- on a more mature phase of research, including significant
plicity in the preparation of sensing materials (e.g., advances in MOF-based sensors. A MOF is basically the
one step synthesis, low-temperature, and low-pres- extended crystalline structure of metal-containing inorganic
sure conditions) are characteristics that facilitate building units (metal nodes) connected to multidentate
further large-scale production, also contributing organic building units (linkers) via coordination bonding.
to cutting costs. Low-cost sensors are especially The units of metal nodes, organic linkers, and sequentially
advantageous in low- and middle-income countries structural motifs yield an essentially infinite number of pos-
to increase their quality of life, as the recent COVID- sible combinations to form a MOF [3]. Indeed, more than
19 pandemic has made even more visible. 100,000 different structures of MOFs have been reported
(iv) Sustainable features. In the context of analytical sen- up to date, offering more possibilities of developing sensing
sors, the concept of sustainability means develop- materials than the ca. 600 structures reported for COFs [4].
ing both the sensing materials and the entire devices The main advantages of using MOFs for designing sens-
through environmentally friendly procedures (e.g., ing materials rise from their unique and highly tunable phys-
reducing waste production or lowering the ener- icochemical/structural (and hence functional) characteristics
getical consumption of the synthetic procedures), [5], including their regular porosity and tunable pore size,
by using sustainable sources of materials or green multivariate structures with multiple metals (either mono-,
methods for the preparation of the sensing materials, bi-, or tri-metallic systems) and/or organic linkers, to even
or by developing recyclable sensors (i.e., with a long employing conformationally flexible linkers and/or geomet-
lifespan, and with possible reuse of their individual rically versatile inorganic building units. In addition, MOFs
components). can be functionalized (both the external surface and internal
pore space) through post-synthetic modifications (PSM) to
The achievement of all these desired characteristics install new functionalities. More recently, the engineering
implies multidisciplinary strategies focused on innovating in of partially aperiodic frameworks, to purposefully introduce
the different components of a sensor, either in the sampling building-block vacancies and heterogeneities, is attracting
unit (for the capture of the analyte, and separation/filter- much interest to fully exploit the potential of MOF chem-
ing from the matrix interferents), in the recognition phase istry. All these features can (at least theoretically) address
(where the interaction of the analyte with the sensing ele- the need of developing new sensing materials featuring high
ment takes place and undergo a chemical change), or in the sensitivity, high selectivity, quick response time, enhanced
transducer (to convert the chemical change into a measurable stability, and reusability. If at first glance sensitivity appears
physical signal that can be optical, electrical, thermal, mass to be more related to modification of the surface chemistry
or acoustic); see Fig. 1. of MOFs, for example, by specific (bio)chemical interactions
More than 25 years of research on reticular chemistry, of the analyte with functional groups or opens metal sites
i.e., the chemistry of systems formed by molecular building (OMS) [6], and selectivity seems merely determined by pore
blocks regularly interconnected to form solid-state materials and aperture sizes, for example, by size exclusion of larger
in a designed and rational manner, have led to the prepara- molecules, the simultaneous combination of both surface
tion of a huge number of materials for multiple applications, chemistry and pore dimensions can synergistically enhance
including (bio)chemical sensing materials [2]. Among the sensitivity and selectivity [7], such as in the case of specific
reticular materials, metal–organic frameworks (MOFs) are interactions of a selected analyte with the functional groups

Fig. 1 Scheme of the main parts

of a sensor (sampling, recogni-
tion, and transducer), showing
that MOFs can play a functional
role in the different parts, either
as a sorbent material, as a sens-
ing/recognition material, and/or
as a transducing element

13
Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2007

placed in the internal surface of the MOFs or intentionally new MOF-based sensing materials as well as on new effi-
created vacancy defects. Concerning the response time, this cient, sustainable, and scalable synthetic strategies.
depends mainly on the rate of diffusion of the analyte to Several excellent reviews related to the potential of MOFs
the interacting site, thus connected to the MOF particle size for different (bio)sensing applications have been published
and pore dimensions of the MOFs [8]. Bearing this in mind, over the last couple of years, but each is approached from
nanosized MOFs, which have higher surface-to-volume a different perspective. While some reviews discuss very
ratios in comparison with micrometer-sized MOFs, show specific types of MOFs or composites (such as carbon dots@
faster diffusion rates and therefore faster response to ana- MOFs [15] or lanthanide MOFs [16]), others are focused
lytes, being usually preferred to ensure rapid analyte uptake on specific sensor types (e.g., electrochemical [17–20] or
and equilibration with higher sensitivity. Nanosized MOFs luminescent [21]), specific analytes (e.g., food contaminants
are also selected for sensing applications in the biomedical [22], gases [23, 24], neurotransmitters [25], biomarkers for
field, since smaller particles are more efficiently internal- cancer [26]), or specific applications fields (e.g., biomedical,
ized in cells. On the other hand, the long-term stability in food) [27, 28]. In contrast, this review presents an overview
operation/detection conditions and, therefore, the reusability of the potential of MOFs for real-world sensing applica-
of MOFs, is a critical issue that still requires much improve- tions, highlighting recent trends in the most relevant (bio)
ment. Many studies have focused on improving the kinetic analytical fields based on figures and emphasizing current
and/or thermodynamic stability of MOFs by introducing limitations and challenges that must be faced. Therefore, the
hydrophobic substituents, by changing the MOF constitu- review is organized into three sections. First, the key proper-
ents to increase the strength of metal–linker bonds [9], or ties of MOFs to be used as sensing materials are introduced.
by selecting inner clusters (e.g., Zr6-cluster) with the ability Second, a section summarizes the use of MOFs as sens-
of reversibly rearrange upon removal or addition of μ3-OH ing materials in different application fields, including food
groups, without any changes in the connecting carboxylates control, environmental analysis, and biomedical purposes,
[10]. reporting some representative analytes. In a final section,
Nevertheless, despite the tremendous progress that the challenges and prospects of the nearest future of MOF
has been made to date in the design of MOF-based sens- sensors are critically discussed, and some patents are also
ing materials, the development of sensors with industrial reported to illustrate the growing interest of MOFs as sen-
relevance and application in real applications still requires sors in the field of industry.
intense research to solve the main current limitations.
Firstly, the selectivity is normally poor. Many MOF-sens-
ing approaches entail a loss of signal (i.e., fluorescence or Key features of MOFs for sensing
phosphorescence intensity) in response to the interaction/
adsorption of the analyte; these “turn-off” sensors can also As previously mentioned, the key characteristics of MOF-
be affected by other interference which also results in sig- based sensors are sensitivity, selectivity, response time,
nal loss, ultimately resulting in increased LOD. Moreover, stability, and reusability, as well as incorporating appropri-
some MOFs still suffer from the drawback of relatively poor ate signal transduction capabilities (e.g., optical, electrical/
stability under working conditions. electrochemical, photoelectrochemical, mechanical, ther-
Besides, some limitations related to the production of mal, mass, magnetic, acoustic). Moreover, in some sens-
MOFs at an industrial level should be considered. Cur- ing schemes and with the future perspective of developing
rently, the synthesis of many MOFs is expensive, mainly portable sensors, the construction of analytical sensing
due to the cost of organic linkers. Moreover, the process- devices involves the fabrication of films of MOFs (which
ability of MOFs is hampered by the powdery nature of are normally primarily obtained as powders) either through
these materials, considering also the health issues related the deposition or coating of substrates with MOF crystals.
with the processing of nanoparticles, since many MOFs are Bearing all this in mind, it seems clear that the preparation
in the nanoscale dimension. Unfortunately, there is very of the MOF for each specific sensing application must follow
limited data (especially in real-life conditions) regarding a “design-for-purpose” approach to ultimately achieve the
the health risks related to nanomaterials [11]. Addition- desired sensor performances.
ally, the synthesis of MOFs under the principles of green
and sustainable chemistry is scarcely considered today, and Selectivity and sensitivity
only a few studies have carried out life cycle assessments
of MOFs [12–14]. The two main strategies to enhance the selectivity of MOF-
Therefore, the development of MOF-based sensors with sensing materials are size exclusion (i.e., molecular siev-
future application potential in real scenarios remains an open ing by pores) and physical–chemical interactions. The
challenge, and it requires more research efforts focused on MOF porosity can be varied through composition, that is

13
2008 Zuliani A. et al.

judiciously selecting the metal ions and organic linkers (e.g., with ZIF-8 [37]. Furthermore, ultra-high surface areas and
node and linker sizes and geometries, linker appendages overall dimension of MOFs can determine better sensing
and their directional orientation), which allows not only to performances, especially in the case of nanosized MOFs
change the pore and aperture sizes but also its hydrophilic- due to their higher surface-to-volume ratio, which translates
hydrophobic character to increase the affinity towards the into higher sensitivity as well as faster response because of
target analyte. While many MOFs are microporous materi- the shorter diffusion paths. MIL-96(Al) nanoparticles (ca.
als (having pores of < 2 nm), depending on the molecular 200 nm diameter), for example, showed high sensitivity
dimensions of the target analytes MOFs with large pores, towards water detection [38]. More recently, the creation
either mesopores (2–50 nm) or even macropores (> 50 nm) of defects within the MOF structure (i.e., open metal sites)
are required. Pore sizes in MOFs can be enlarged by increas- has also been proposed as a strategy to promote preferred
ing the separation between metal nodes using long organic analyte binding for selective detection. Sensitivity can be
linkers. However, this method fails with very long linkers also enhanced by signal amplification approaches, exploiting
since interpenetrated networks with small pore sizes are usu- specific guest molecules or inorganic metal particles grafted,
ally formed. Strategies to overcome this effect include the supported, or encapsulated on/in the MOFs, such as DNA,
use of sterically hindered linkers [29], the use of sacrifi- metal nanoparticles, carbon dots, and carbon nanotubes [39,
cial templates [30], or the replacement of node-coordinated 40]. For example, the modification of Cu-MOFs with DNA
molecules (e.g., solvents) with other ligands [31]. Concern- chains resulted in enhanced sensitivity towards Pb2+ [40] or
ing the role of physical–chemical interactions as strategy to miRNA detection [41].
modulate the selectivity, as well as to increase the sensitiv- As highlighted in Table 1, the different approaches for
ity, the incorporation of functional groups (e.g., amines, car- boosting the selectivity and the sensitivity present divergent
boxylic acids, hydroxyls) within the framework is commonly advantages and disadvantages, which should be taken into
used to favor the binding with the target analyte through account in the design of the sensors depending on the final
hydrogen bonding, electrostatic interactions, electron donor/ application; for example, highly selective but expensive sen-
acceptor interactions, or covalent bonds formation. These sors may be justified in the specific case of biomedical use.
groups can be incorporated in the MOFs during the synthe-
sis (by using organic linker containing already those groups), Stability
or through post-synthetic modification (PSM) approaches
by modifications on the linkers [32] or on open metal sites The stability of MOFs derives from different factors such
(OMS, known also as coordinatively unsaturated sites (CUS) as the type, geometries, and properties of the linkers and
or occasionally also as open coordination sites (OCS) [6]) of the metal nodes, the strength of the coordination bonds,
[33]. For example, TMU-60 was synthesized using ligands and the MOF topology, as well as the particle sizes of the
with amino groups to form electron-rich pores capable of MOFs (nanoMOFs are normally less stable than micro-
detecting different (electron-poor) metal ions such as Pb2+, sized MOFs or bulk MOFs). Among all, the strength of the
Hg2+, Cu2+, Cd2+, Cr2+, Ni2+, and Cr3 [34]; while Mg- M-linker has been pointed out as the most determining fac-
MOF-74 films with open metal sites were post-synthetically tor of the stability of MOFs, and more importantly, it can
modified with ethylenediamine and used as sensing materi- be designed to be strong enough not to break under specific
als for the detection of CO2 and benzene [35]. More complex sensing conditions. Theoretically, Pearson’s hard/soft acid/
functional moieties can be also incorporated, such as biolog- base principle (HSAB) can be used to predict and assume
ical recognition elements (i.e., antibodies, enzymes, DNA the stability of M-linker. Thus, in order to prepare highly
strands), forming the so-called biosensors that are capable stable MOFs, metal ions with high valence states (e.g.,
fr endowing the MOFs with a higher level of selectivity or Ti(IV), Zr(IV), Al(III), Fe(III) and Cr(III)), considered as
even specificity towards some analytes. hard acids, should interact with hard bases ligands (e.g., car-
When it comes to sensitivity, although it depends to some boxylate ligands), while soft bases ligands (e.g., imidazolate,
extent on the method of signal transduction, the strength of pyrazolate, triazolate) should interact with soft metal ions
the analyte binding to the MOF will have a strong influence; (e.g., Zn(II), Cu(II), Mn(II)) [42]. For example, Zr-based
thus, stronger binding will lead to lower detection limits. MOFs synthesized using tetracarboxylate ligands possessed
The strength of the analyte-MOF can be adjusted by also such high stability and durability that were employed as sta-
playing with the size of the pores, the hydrophilic-hydro- tionary phase in HPLC [43]. In addition, ligand rigidifica-
philic nature of the pores, the presence of specific functional tion has been demonstrated to be an efficient approach for
organic groups, or the functionalization with biomolecules. enhancing the stability of MOFs. For instance, ligands with
For example, small pores will adsorb gas or vapor analytes high rigidity, such as tetratopic ligands in Zr-based MOFs,
more strongly than large ones, resulting in an enhanced sen- have a high energy barrier and tend to keep their conforma-
sitivity [36], such as in the case of the detection of H2S tion, stabilizing the structure of MOFs [44]. Improvements

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Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2009

Table 1 Advantages and

disadvantages of the main
Cost-
Strategy Simplicity Sensitivity Selectivity
strategies for enhancing efficiency
selectivity and sensitivity Tuning pore and aperture size
Tuning hydrophilic /hydrophobic
character
Functionalization with organic
groups (e.g., -NH2, -COOH,
-SO3H)
Functionalization with
biomolecules (e.g., antibody,
DNA, RNA, enzymes)
Multiplexed sensors (e.g.,
multicolour MOFs-sensors)
Metal NP-MOFs composites
Engineering defects (open metal
sites)
Nanosized MOFs

Legend: low; medium; high

on the MOF stability can also be achieved by PSM. This molecules (e.g., modulators used in the synthesis) inside
is the case of a highly stable PCN-777 luminescent sensor the pores of the MOF can slow the diffusion of the analytes.
for protein detection prepared by the post-synthetic addition This is why the activation of MOFs for the efficient removal
of ligands enriched with carboxylic groups, forming strong of such potential guest molecules, which is usually done
bonds between Zr4+ and -COO− [45]. by heat and/or vacuum treatment, is so important. On the
other hand, since most of the analytes are physisorbed, the
Rapid response time and reusability reusability of the MOFs can be achieved by vacuum treat-
ment aided by heating, such as in the case of KAUST-8 used
A fast response after interaction with the target analyte and as sensing material for SO2 and regenerated by heating at
the possibility of using the MOFs for different cycles depend 105 °C in vacuum [48]. Reusability is clearly not considered
mainly on the thermodynamics and kinetics of adsorption. for MOFs sensing probes designed for single use (i.e., when
More in detail, the rate of diffusion of the analytes to the the materials go through irreversible reactions).
interacting part of the MOFs (either within the internal pores
or the external surface) is determined mainly by (i) intrinsic Signal transduction strategy
properties of the analyte, e.g., molecular dimension, flex-
ibility, polarity; (ii) properties of the MOF such as the size, Although, in principle, any MOF property that changes upon
geometry and nature of the pores, MOF particle size (since interaction with the analyte could be measured as a sens-
diffusion times increase as the square of diffusion distance), ing signal, most MOF sensors reported to date are based
MOF morphology (e.g., 2D nanosheets MOFs lead generally on either optical transduction schemes (i.e., luminescent,
to superior sensing properties because of enhanced diffusion colorimetric, or plasmonic) or electrochemical. Note that the
and accessibility of analytes to the recognition sites), and the incorporation of nanoparticles (NPs) within the framework,
“breathing” effect of the MOF; and (iii) the medium (sol- for example, luminescent quantum dots or plasmonic Au
vent) when the sensor is used in solution, or the thickness of NPs, is another approach to form MOF-based composites
the MOFs films when used as a layer onto a solid support. having multifunctionalities for improved signal transduction
For example, a thin film of MFU-4-based sensor for deute- mechanisms.
rium detection showed a fast response time of only a few
milliseconds [46]. Similarly, NTU-9 nanosheets showed fast (i) Luminescent sensors. In luminescence sensors, the
response through Fe3+ detection thanks to high dispersive MOF works as both recognition material and trans-
nature and highly accessible active sites [47]. In addition, ducer; thus, the photoluminescent properties of the
the presence of coordinated solvent molecules or other guest MOFs must be finely tuned in order to have detect-

13
2010 Zuliani A. et al.

able signals (i.e., not too quenched). The photolu- pound due to intermolecular interactions. MOFs
minescence of MOFs can arise from (a) the lumi- with tunable colorimetric responses can be obtained
nescence properties of organic linkers (normally through careful design, either using transition metal
extended π-conjugation systems with rigid struc- ions or chromophore ligands. upon the introduc-
tures), such as in MOFs containing pyrene, anthra- tion of analytes. Alternatively, chromophores can
cene, and similar compounds as building units; (b) be loaded into the internal pores or attached to the
metal-based emissions, such as in lanthanide-based MOF surface. Compared with individual metal ions
MOFs; (c) metal–to–ligand charge transfer (MLCT), or chromophores as colorimetric probes, the use of
such as those occurring in Cu(I) or Ag(I) based colorimetric MOFs has several advantages, such
MOFs; (d) ligand–to–metal charge transfer (LMCT), as superior stability due to the protection provided
for example, in Zn(II)/Cd(II) and carboxylate ligands by the framework to the chromogenic reaction, and
based MOFs; (e) ligand–to–ligand charge transfer enhancing detection sensitivity and selectivity thanks
(LLCT), known as antennae effect, which involves to the intrinsic porosity, open metal sites, and Lewis
the indirect excitation of the metal such as in the acid/base sites, which can be adjusted on purpose.
case of MOFs with absorbing ligands (e.g., π- and (iii) Electrochemical sensors. These sensors offer the pos-
σ-bonded antenna ligands) and emitting lanthanide sibility of detecting in a simple and fast way analytes
ions; or (f) fluorophores loaded as guest molecules that can be easily oxidized or reduced, by means of
in the MOF pores, such as guest-centered emission changes in the measured current, electric potential,
and guest-sensitization. From the perspective of the or other electrical signals. Since electrochemical
metal-type MOF, the vast majority of luminescent reactions can only occur on the electrode surface,
MOFs can be classified into two groups: lanthanide- the deposition or immobilization of the MOFs on
based MOFs (Ln-MOFs) and transition metal-based the electrode surface is required. The preparation
MOFs [49] Ln-MOFs are very useful for sensing pur- of MOFs with electrocatalytic activity involves the
poses due to their unique luminescent properties such introduction of the redox-active sites in the metal
as long lifetime, sharp emissions, and high quantum nodes or organic ligands, such as the incorporation
yields in the visible and near-infrared (NIR) regions. of active metal sites with nitrogen-containing ligands
Notably, the possibility of working in the NIR region (e.g., porphyrin- and bipyridine-based ligands) or the
makes Ln-MOFs compatible for in vitro (cells) and functionalization of ligands with electron-donating or
in vivo (animals) sensing applications, avoiding the electron-withdrawing groups. In addition, the excel-
typical cell and tissue autofluorescence in the blue- lent electrocatalytic performance reported for some
green region. Besides, binary and ternary co-doped MOF-based structures arises from their high porosity
Ln-MOFs can be easily prepared, and these mixed (which result in rapid mass transport during elec-
Ln-MOFs can generate simultaneous emission of dif- trochemical reaction, improved adsorption capacity,
ferent Ln ions using one single excitation wavelength, and reduction of the activation energy of the inter-
resulting thus in MOF sensors with improved sensi- mediates), and the selective interaction of the analyte
tivity and selectivity [50]. Among the luminescent with the catalytic sites in the MOF (which improves
transition metal-based MOFs, Zn- and Cd-MOFs the selectivity of the electrochemical response).
are the most commonly reported since d10 metal ions However, due to the fact that the majority of MOFs
have several coordination numbers and geometries are insulating, the MOFs are subjected to high-
and exhibit luminescent properties when bound to temperature annealing to transform non-conductive
functional ligands. In contrast to Ln ions, transition or low-conductive MOFs to conductive materials
metals generally do not have intrinsic luminescence, for achieving a good electrocatalytic response; the
but they modulate the MOF emission by participating MOFs are thus used as sacrificial templates since the
in LMCT or MLCT processes. Whereas LMCT is unique structures and intrinsic active sites in MOFs
often reported in Zn- and Cd-MOFs, MLCT is more are destroyed during the thermal treatment. Three
frequently found in Cu- and Ag-MOFs [51]. main strategies are proposed to improve the electro-
(ii) Colorimetric sensors. These sensors have attracted catalytic activities of MOFs in their pristine form
increasing attention due to their simple and rapid [8]: preparing conductive or electrochemically active
signal readout with the naked eye or using smart- MOFs, MOFs supported on conductive substrates,
phones, which allows for in situ sensing applications and MOFs hybridized with active materials. It has
[52]. In a colorimetric sensor, an optical shift in the also been shown that nanoMOFs and ultrathin 2D
visible absorption band of the sensor is produced MOF nanosheets present a significantly higher elec-
after adsorption/interaction with a specific com- trochemical activity, which is related to the presence

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Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2011

of more active sites exposed or easily accessible, onto the support, self-assembly of MOFs to form monolayer
together with the improved diffusion of the analyte further deposited on a support, or by incorporation of MOFs
to the catalytic sites. into gel or polymeric matrices. In the first case, the film for-
mation can be accomplished by reacting the linkers and the
It is worth noting that in electrochemical sensing, MOFs metal precursor directly on the surface, which is often pre-
are typically deposited on glassy carbon electrodes (GCEs) viously modified with a self-assembled monolayer or with
or other substrates to promote integration of MOFs with small MOF crystals to facilitate the nucleation process. The
portable electrochemical devices; therefore, the development presence of functional groups on the surface can also favor
of efficient methods for the fabrication of these MOF-based the nucleation of MOFs to a crystallographic direction or
films is very importance in these sensing schemes. lead to coordination geometries distinct to those normally
obtained by standard synthesis. This is the case of a recently
Fabrication of MOF films reported work in which a film of Zr-based MOF was pre-
pared by vapor-assisted conversion and oriented along the
The integration of the MOFs onto surfaces and devices is [111] crystal axis, thanks to the modulation of the surface
required for some MOF-based sensors (i.e., solid-state sens- modifiers, the droplet volume, and the reaction time [57].
ing applications), in which the signal transduction method The other approach for the preparation of MOF films consists
requires a physical interface between the MOF and the in preparing MOF particles (preferably small particles) and
device support. This is, for example, the case in electro- sequentially depositing them on a surface by different tech-
chemical sensing. It should be noted that the properties of niques. For example, NH2-MIL-88B was deposited by spin
the MOF films such as the crystal size and thickness affect coating on a silicon wafer for the preparation of colorimetric
their electron-transfer kinetics and adsorption ability, and sensors for various volatile organic compounds (VOCs) [58].
thus achieving a precise control of all these parameters is
crucial to achieve desired film properties such as variable
thickness ranging from nanometers to a few micrometers Overview of the applications of MOFs
and low roughness. as sensors in different fields
MOFs films are usually prepared through two main strate-
gies [53–56]: (i) by direct synthesis of MOFs on the support, The research on MOF-based sensors has generated numer-
via dip coating, film coating, interfacial synthesis, evapora- ous innovative outcomes, as evidenced by the exponential
tion method, electrochemical approaches, etc., or (ii) by dep- increase in publications and patents during the last years
osition of already-synthesized MOFs by simple evaporation in this area (Fig. 2A, B). Considering the types of MOFs

Fig. 2 A Publications
(2007–2022) and B patents
(2008–2022, early publica-
tion date) per year from WOS
searches with the topic “metal–
organic framework (or MOF)
sensor, detection, quantification,
analysis.” Taken on the 13th of
October 2022. C Tree map of
the main families of MOFs used
in sensing applications from
WOS searches taken on the 7th
of December 2022. ZIF, zeolitic
imidazolate framework; MIL,
Materials Institute Lavoisier;
UiO, University of Oslo;
HKUST, Hong Kong University
of Science and Technology;
TCPP, tetrakis(4-carboxy-
phenyl)porphyrin; IRMOF,
isoreticular metal–organic
framework; NU, Northwestern
University

13
2012 Zuliani A. et al.

reported in the publications, it is observed that they belong Regardless of the final application, the success of the
mainly to the families of lanthanide MOFs (Ln-MOF), ZIF, utilization of MOF-based sensors depends strongly on the
MIL, UiO, and HKUST, and to a lesser extent to TCPP- capacity of delivering valid analysis compared to traditional
based MOFs, IRMOF and NU (Fig. 2C). Regarding the analytical techniques. Up to date, those include classical tech-
fields of application of the publications during the last two niques such as high-performance liquid chromatography–
decades, it is observed that they mainly belong to envi- mass spectrometry (HPLC–MS), inductively coupled plasma
ronmental, food control, and biomedical areas, with sig- mass spectrometry (ICP-MS), and gas chromatography–
nificantly distinct proportions of each one (Fig. 3A). If in mass spectrometry (GC–MS) [59]. Other analyses specific
the early 2000s the focus on environmental analysis was for biomarkers and pathogens include polymerase chain
more consistent (green segment of the pie graph in Fig. 3B), reaction (PCR) [60], enzyme-linked immunosorbent assay
during the last two years, the research on sensors for food (ELISA), lateral flow immunoassay, flow-through immuno-
control has gained more attention, while the percentage of assay, or surface plasma resonance (SPR). Capillary elec-
publications related to the biomedical area (ca. one-third trophoresis–mass spectrometry (CE-MS) and NMR are also
of the annual publications) remained fairly the same since widely used considering the complexity of many biomedi-
2003. Notably, in the last 2 years, there has been a growth cal analytes [61]. Volatile organic compounds (VOCs) are
of interest in virus diagnosis, with a special focus on the instead analyzed by the same GC and LC techniques often
subcategory of the SARS-CoV-2 diagnosis (blue and dark coupled with spectroscopy (MS), time of flight (TOF),
blue segments in Fig. 3C, respectively). and thermal desorption (TD), or by selected-ion flow-tube
On the other hand, it must be highlighted that most of mass spectrometry (SIFT-MS) and proton-transfer-reaction
the granted patents belong to the academic sector, and only mass spectrometry (PTR-MS). Most of these techniques
a few of them to the industry (Fig. 2B), which underlines show high selectivity and low detection limit but are often
that the shifting to real-world applications remains an open time-consuming and expensive. In addition, they frequently
challenge. Nevertheless, the trend of the last period indicates require complex pretreatment or need to be run by expert users.
that private companies are gradually paying more attention Lastly, they cannot perform real-time measurements. Thus,
to intellectual property rights, reflecting the growing interest the development of highly sensitive yet simple MOF-based
in the use of MOFs in industrial applications. This tendency sensors offers valuable alternatives to current techniques. The
is expected to rapidly grow whenever new technologies and most relevant types of analytes to be detected with the newest
processes for preparing MOF sensors will overpass current MOF-based sensors for food control, biomedical diagnosis,
limits for large-scale production, as further discussed in the and environmental monitoring are here summarized, pointing
final section. out the importance of each sector for the community.

Fig. 3 Segments of publications

in the three main research areas
(i.e., environmental analysis,
food control, and biomedi-
cal applications) from WOS
searches taken on the 14th of
October 2022

13
Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2013

Food control Biomedical area

According to the World Health Organization (WHO), it A global increase in the quality of life requires excellent
is estimated that every year over 600 million people fall healthcare systems. Although the improvement of medi-
ill after eating contaminated food. Of those, more than cal care has been already pointed out in 2015 as the key
400,000 individuals suffer severe consequences leading to to address multiple targets of the UN’s SDGs “Ensure
death [62]. Besides, food contamination causes 110 US$ healthy lives and promote well-being for all at all ages,”
billion lost yearly [62] due to waste generation in produc- the COVID-19 pandemic has further highlighted this need
tion processes and due to medical expenses mainly in low- [64]. In this context, analytical chemistry plays a crucial
and middle-income countries. Food contamination can role in developing tools for the detection of diseases and in
be caused by many harmful bacteria, viruses, parasites, providing analytical data for the optimization of medical
chemicals, and heavy metals which are responsible for treatments. MOFs sensing materials have emerged for bio-
more than 200 diseases, ranging from fever to cancer. Food medical applications principally due to their low cytotox-
safety is achieved by high-quality standard operating pro- icity (which is critical for eventual in vivo applications),
cedures (SOPs), and by the analysis of food at each phase intrinsic biodegradability, biological affinity, and the pos-
of the food supply chain. Indeed, major food hazards can sibility of integrating biomolecules in the MOF structures
enter the food at any time during harvesting, processing, (i.e., to prepare biosensors). Recently developed MOF
transporting, and storing. Thus, the use of fast, on-site, sensing materials have been used for the detection of (i)
and cost-effective analytical devices is crucial. In recent pharmaceutical drugs [65]; (ii) biomarkers for non-com-
years, MOFs have been proposed as alternative materials municable diseases, such as cardiac troponin (myocardial
for the design of sensing elements for food safety analyses injuries) [66], microRNA (different disease states) [67],
especially thanks to enhanced photo/thermal stability and or VOCs (in the breath of patients and related to different
high selectivity. diseases) [68]; (iii) specific biomarkers for communicable
Among the different types of food contaminants, MOF- diseases (e.g., tuberculosis, malaria, hepatitis, HIV/AIDS),
based sensors have been recently used to detect [22]: (i) such as MPT64 and ESAT-6 proteins (biomarkers secreted
pesticides, such as organophosphorus pesticides and by Mycobacterium tuberculosis) [69, 70], or dipicolinic
organochlorine pesticides; (ii) antibiotics, including tetra- acid (biomarker for anthrax) [71]; (iv) pathogens (virus,
cyclines, cephalexin, and chloramphenicol; (iii) pathogens bacterium, or fungus), such as Pseudomonas Aeruginosa
such as Staphylococcus aureus and Escherichia Coli; (iv) [72], hepatitis-C [73], human immunodeficiency virus type
natural toxins which can be highly carcinogenic, terato- 1 (HIV-1) [74], and Ebola [75].
genic and mutagenic, including ochratoxin A and aflatoxin Within the biomedical area, a special focus should be
B1; (v) heavy metals; (vi) persistent organic pollutants given to the sensors for the detection of the SARS-CoV-2
(POPs) like polychlorinated benzenes; and (vii) biogenic virus. Indeed, the COVID-19 pandemic has generated unfor-
amines such as of putrescine (PUT) and cadaverine (CAD). tunately well-known socio-economic impacts (for example,
To simply show a recent example in this area, two new the WHO has estimated that the total deaths directly or indi-
Co-based MOFs, BITSH-1 and BITSH-2 (Birla Institute rectly related to the pandemic during 2020 and 2021 were
of Technology and Science, Hyderabad), were reported for between 13.3. million and 16.6 million). Thus, researchers
the sensing of PUT and CAD, as key markers to monitor around the world have been intensively investigating dif-
food spoilage in protein-rich foods [63]. The UV adsorp- ferent strategies for the efficient, selective, and rapid detec-
tion spectra of these MOFs showed strong absorption tion of SARS-CoV-2, both considering the biomarkers, or
and emission bands at 278–280 nm and 332–333 nm, the pathogen. Currently, the most widely used technique in
respectively. The fluorescence intensity of the MOFs was clinical laboratories is the reverse transcriptase–polymerase
quenched by small addition of PUT and CAD and was chain reaction (RT-PCR). However, this technique has some
ascribed to photoinduced electron transfer between the important limitations, including false-negative rate of up to
biogenic amines and the MOFs. The LOD values achieved 37%, long analysis time (4 h on average), and the uncom-
were lower than those obtained with other MOFs thanks fortable sampling procedure (especially for infants). Some
to a higher HOMO level (∼ − 5.91 eV) of the BITSH-1 MOF-based sensors have been developed as valid alterna-
and BITSH-2, which facilitated the electron transfer from tives for the specific detection of COVID-19 [76], such as a
the HOMO of PUT and CAD to the HOMO of the MOF. highly sensitive, relatively low-cost, and fast-response (only
Importantly, the formation of a polymeric membrane mod- 5 min) sensor based on UiO-66 to determine the SARS-
ified with these MOFs resulted in a simple visual sensor, CoV-2 spike protein [77], or a fluorescent MOF-5/CoNi2S4
revealing changes of color upon exposure to real food sam- sensor decorated with porphyrin for efficient detection of
ples (Fig. 4A). recombinant SARS-CoV-2 spike antigen [78].

13
2014 Zuliani A. et al.

Fig. 4 A Visual detection of

biogenic amines from cheese
using a PVDF polymeric mem-
brane modified with Co-based
MOFs (BITSH-1 or BITSH-2)
as colorimetric sensors. Used
with permission of RSC, from
[63]; permission conveyed
through Copyright Clear-
ance Center, Inc. B Schematic
illustration of the fabrication
process of the MOF-based
aptasensor for the detection of
SARS-CoV-2 virus. Reprinted
(adapted) by permission form
Springer [79], copyright 2022.
C Scheme of the electronic
nose setup, composed of an
array of QCM sensors coated
with MOF films of six different
structures. Vapor concentration
is controlled by the flow rates
through the mass flow controller
and sensor array is located in
a gas flow chamber. Reprinted
(adapted) with permission from
[90]. Copyright 2022 American
Chemical Society

Here again to show just one example of MOF-based sen- of the sensor was evaluated by means of electrochemical
sor relevant to this area (Fig. 4B), a MOF-based aptasen- impedance spectroscopy (EIS) using [Fe(CN)6]3−/4− as redox
sor was developed using a screen-printed carbon electrode probe. The results showed an increase of the charge transfer
(SPCE) modified with a Ni-MOFs, specifically Ni3(BTC)2 resistance upon incubation with increasing concentrations
functionalized with the aptamer [SARS-CoV-2 virus], and of the virus, due to the formation of more SARS-CoV-2
it was used successfully for the detection of intact form of virus–aptamer complexes. The selectivity of the sensor was
the SARS-CoV-2 virus [79]. The analytical performance investigated by incubation with several potential types of

13
Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2015

possible interferers such as MERS-CoV, influenza A H1N1, at 100 ppm the compositions of 16 ternary mixtures were
and influenza A H3N2, observing no significant response determined with an average classification accuracy of 96.5%.
was observed for off-target species. Importantly, the analysis
of real samples of sick and healthy individuals showed a
100% sensitivity with 100% specificity. The sensor was also Challenges and perspectives
usable after 14 days and stored at 4 °C, demonstrating good
long-term stability. Tremendous progress has been made from the pioneering
MOF-based sensors that first appeared in the early 2000s, such
as cyano-bridged Co(II) group–based colorimetric sensors for
Environmental monitoring vapor detection of diethyl ether [91], or a magnetic Cu-MOF
(MOROF-1) for the detection of some solvents (methanol and
The enormous industrial and social development of the ethanol) in a reversible manner [92], to more recent MOF-
last century and even more in recent decades has intensely based sensors capable of achieving ppb detection levels, as
increased environmental pollution, generating severe prob- is the case of a Zr-MOF (CJLU-1) with a fast response and
lems for the ecosystem and society [80–82]. Indeed, environ- very sensitive towards trinitrophenol (LOD = 83 ppb) [93].
mental pollution affects deforestation, acid rain, greenhouse Importantly, some MOF-based sensors have been patented,
effect, etc., and generates health problems such as cancer, which clearly demonstrates the industrial interest in the field
asthma, inflammation, and many other diseases. For exam- (such as US2020269225A1, EP2520929A1, CN113624752A,
ple, only in 2016, 7 million deaths resulted from indoor and US9983124B2, US9546887B1). However, there is still plenty
outdoor pollution (note that a person normally spends almost of room for improvement.
80% of his/her life in indoor environments) [83]. MOF-based Current challenges to be faced are related to optimizing
sensors show advantages for environmental analyses espe- the intrinsic sensing properties of MOFs (i.e., such as selec-
cially in terms of high selectivity, real-time analysis, and tivity, sensitivity, responsive properties, long-term stability,
fast response. MOF sensing materials have been developed reusability) by means of careful and rational MOF design
primarily with the goal of detecting environmental contami- approaches, as well as by developing innovative or improved
nants in: (i) Water, such as cations, including radioactive synthetic strategies to precisely control the ultimate struc-
cations, Hg2+, Pb2+, Cd2+, and Cu2+ [84], anions (PO4 −, ture-properties-functions of MOFs. Moreover, large-scale
NO2−, etc.) [85], or amines [86]; (ii) air, which analysis productions of MOF-based sensors are still infeasible with
requires MOF sensing materials with high selectivity since current technologies, and key requirements such as ease of
many gaseous chemicals have very similar molecular dimen- synthesis, reproducibility, and low production costs must
sions, for example, in the case of acetone [87], SO2 [88], or be met before possible scaling, translation to industry, and
NH3 (and derivates) [89]. device integration. In addition, environmental aspects must
One recent example in this field showing the potential also be seriously considered, which implies proper environ-
of MOFs for VOCs sensing consisted of a MOF film sen- mental impact assessment, use of sustainable sources, etc.,
sor array (electronic nose), which allowed the detection and as well as health concerns, since biocompatibility and non-
isomer discrimination of VOCs in mixtures [90] The sensor toxicity must be guaranteed in medical sensing applications.
was composed of six quartz crystal microbalances (QCMs)
coated with different MOFs, HKUST-1, Cu(BDC), and Optimization of MOF design and synthesis
Cu(BPDC), UiO-66, UiO-67, and UiO-68-NH2 (Fig. 4C).
The sensor array was firstly tested in the atmosphere of pure More precise optimization of the MOF-based material in
xylene isomers, and it was noted that each QCM showed terms of size, morphology, porosity, surface properties, and
different sensitivity to the different isomers, due to unique incorporation of additional functionalities should be made
adsorption properties. It was demonstrated, and supported by in order to finely control and potentially tune the thermody-
molecular simulations studies, that Cu(BDC) exhibited high namics and the kinetics aspects of the interactions between
affinity for p-xylene at low pressures and o-xylene at high MOFs and analytes, which will undoubtedly allow us to
pressures, while UiO-66 exhibited affinity for o-xylene. This improve the critical sensing features of the material, such as
was due to the rigid structure of the crystalline frameworks, selectivity, sensitivity, stability, response time, and reusabil-
which were strictly controlling the access to the adsorption ity. A critical issue is achieving highly selective recognition,
site by steric hindrance and allowed thus the clear distinction which remains unrealized for most analytes. Careful MOF
of the isomers (something truly unrealizable in poor/non- design can play a critical role, as demonstrated in some
crystalline materials). The performance of the sensor was examples by preparing a chiral framework that recognizes
analyzed with a machine learning algorithm, showing that only one enantiomer in a mixture. For example, a recent

13
2016 Zuliani A. et al.

patent reported the controlled synthesis of enantiopure MOF involved in reported MOF-based sensors, and consequently
structures for the detection of chiral odorants such as R- and reoptimizing the MOF structure to reach the desired sens-
S-limonene (EP3964830A1). ing performance. In this context, exhaustive and reliable
Currently, the most employed techniques for the synthe- characterization tools are fundamental. These techniques
sis of MOFs are the diffusion method and the solvother- are aimed at studying the morphology, the chemical/struc-
mal method [94]. On the one hand, the diffusion method, tural composition, the particle number concentration, and
based on the gradual convey of reactants in solvent (or gel), the functionalization with molecules/inorganic particles,
requires the absence of interfering species (that can affect and the stability of the MOFs. Currently, most used tech-
the growth of the crystals), and the strict control of the dif- niques include electron microscopy, both scanning (SEM)
fusion parameters (temperature, humidity, etc.). On the other and transmission (TEM), for determining the morphology
hand, the solvothermal method can produce crystals with (size and shape) and usually coupled to energy dispersive
high porosity, purity, and surface area. This is the case of a X-ray (EDX) detector for elemental mapping analysis;
patent describing a nitrogen-rich Co-MOF used to prepare dynamic light scattering (DLS), Z-potential measurements,
a highly sensitive fluorescent sensor (CN114213671A). and nanoparticle particle tracking analysis (NTA) to study
However, solvothermal methods generally require high- the motional behavior of MOFs in solution, including hydro-
temperature, high-boiling polar solvents (e.g., dimethylfor- dynamic size, surface charge, colloidal stability over time,
mamide), and are limited by the use of soluble precursors, and absolute concentrations (number of particles/mL); spec-
which reduces the possible structures of MOFs. Alternative troscopy techniques such as ultraviolet–visible (UV–vis) and
non-conventional methods for the synthesis of MOFs allow photoluminescence for determining optical properties; X-ray
overcoming some of the drawbacks of conventional routes. diffraction (XRD) to assess the crystallinity and structure;
For example, the electrochemical method can produce X-ray photoelectron (XPS) to determine the elemental com-
MOFs under mild reaction conditions. Ultrasonic-assisted position and oxidation states of elements; thermogravimetric
and microwave-assisted methods [95–97] can produce uni- analysis (TGA) to evaluate the thermal behavior; N2/CO2/
formly seeded MOFs with better size control [98, 99]. This CH4 adsorption isotherms to study the porosity; inductively
is the case of a recent study for the preparation of Co-MOFs coupled plasma mass spectrometry (ICP-MS) for elemental
(TMU-51) by an ultrasound-assisted technique, in which, analysis; nuclear magnetic resonance (NMR) for characteri-
by tuning the power of ultrasound, smaller particles with zation of the linkers and surface functionalization; and chro-
controlled morphology were achieved, which finally resulted matographic techniques (e.g., HPLC–DAD) for determining
in an improved sensing performance for nitrophenol detec- functionalization efficiency. Other more sophisticated but
tion [100]. Therefore, advances in unconventional synthetic less accessible techniques include, for example, high-res-
methods are expected to lead to significant advances in MOF olution TEM (HRTEM), cryogenic TEM (cryo-TEM), or
synthesis in the coming years. annular dark-field imaging in scanning transmission electron
Furthermore, the limited long-term stability of many microscopy (HAADF-STEM) for atomic-scale resolution.
MOFs under working conditions, especially under humid, Recent trends in characterization techniques target, among
acidic, or alkaline conditions, at high temperature or pres- others, the in situ analysis of MOF crystal growth [101], and
sure, is an important drawback, which undoubtedly will the fine study of the spatial proximity between linkers, metal
affect the sensing performance of MOF-based sensors and clusters, and the eventual guest molecules/particles [102].
eventually shorten their lifetime. To overcome this problem,
besides the selection of MOFs with highly robust coordina- Computational studies
tion bonds connected by high valent metal centers and multi-
dentate hydrophobic ligands, new surface functionalization A powerful strategy still poorly explored for the synthe-
strategies to improve their stability, for example, through sis of MOF-based material for sensing applications is the
polymeric surface coatings, should be explored. It is worth use of computational techniques. In reality, it is difficult to
noting that the stability needs to be evaluated under real combine all the MOF design aspects required for an “ideal
working conditions, that is, using real samples such as dirty sensor” if experimental research is not aided by computa-
environmental samples or complex human body fluids, to tion and theoretical chemists. In the process of designing
truly determine the feasibility and reliability of the prepared a MOF for sensing, the ideal approach is to first define the
MOF-based sensor in real scenarios. sensing application (specific analyte, working conditions
Nevertheless, further systematic investigations on cor- since this will imposes stability requirements for the MOF,
relating experimental synthetic conditions, structural MOF etc.) to subsequently (and by taking into consideration avail-
features, adsorption enthalpies, kinetics, and sensing perfor- able linkers and suitable metals) to perform computational
mance must be considered. This will greatly contribute to calculations ought to give trial MOFs structure, as digital
fully understanding the interactions and sensing mechanisms ideal prototypes [103]. Once selected and prepared the MOF,

13
Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2017

computational tools are also highly useful to understand the remarkable breakthrough when the hydrothermal synthesis
mechanism of interactions in order to optimize the syn- (at the tonne level) of Basolite A520 was fully optimized.
thetic parameters [104, 105]. For example, it was possible BASF currently has a portfolio of various MOFs sold under
to evaluate the best sensing performances among nine dif- the trade name Basolite™.
ferent MOFs for the detection of gases by a Kullback-Liebler The MOF type and selection of the raw materials greatly
divergence study [106]. In other works, computational impact the large-scale implementation because the price
screening investigations of a comparatively limited library must be as low as possible. In this sense, oxides and sulfates
of MOFs were able to identify MOFs capable of discriminat- are preferentially chosen as metals centers, and carboxylic
ing between relatively similar molecules (e.g., xylenes and acids (e.g., terephthalic, isophthalic, and formic acids) are
TNT) [107], or to identify one MOF with a strong preference selected as the basis of the organic linkers instead of those
for sorption of xenon versus krypton, in both cases by means more complex and not readily available or highly expen-
of grand canonical Monte Carlo (GCMC) simulations [108]. sive [110]. Moreover, the multi-Kg production of MOFs is
Computational studies were also carried out by means of determined by the synthetic method in terms of easiness,
density functional theory calculation to evaluate the poten- temperature, and pressure conditions, use of acids and bases,
tial of several MOFs to detect biomarkers of SARS-CoV-2 batch-to-batch reproducibility, processability, and produc-
[109]. Despite progress in this direction, the implementation tion costs. Regarding the simplicity and reproducibility of
of high throughput screening of MOFs for highly specific the synthesis, the diffusion and solvothermal methods are
analyte adsorption/recognition will only be possible when generally slow and difficult to apply on a large scale, espe-
computational techniques become routinely available, and cially because of the use of strong bases and acids, high
more reliable computational methods for a wider scope of temperature, and the difficulty of kinetically controlling
molecule/MOF interactions are also required. the growth of MOF crystals in large reactors. On the other
hand, electrochemical methods are sensitively influenced
Signal transduction by small variations in current density, which significantly
affects purity and yields. Mechanochemical synthesis can
Most of the MOF-based sensors reported to date rely on cause MOF crystals to amorphize, while microwaves and
optical or electrochemical transduction mechanism. On ultrasonics consume too much energy, and irradiation can
the one hand, a better understanding of the function of the destroy the MOF structure. The cost and potential scalability
MOFs in each sensing scheme, not only in the recognition- of the purification steps required after MOF synthesis must
sorption process but especially in how this analyte-frame- also be considered, as the filtration, washing, and drying pro-
work interaction is transduced into a detectable signal, is cedures are often time-consuming and expensive, given the
crucial to fully exploit the potential of MOFs and to design amount of solvent required and the length of time required
more advanced transduction architectures. Very few works (including waste disposal).
make a clear explanation of the working transduction mecha- Despite the mentioned drawbacks, non-conventional
nism and compare it with other reported mechanism. On the technologies are showing promising results in the large-
other hand, taking advantage of the multifunctional poten- scale production of MOFs, as is the case of the multi-Kg
tial of MOFs, MOF composites integrating either NPs (e.g., (ca. 771.6 kg/m3/day) microwave-assisted continuous-flow
plasmonic, magnetic, fluorescent), enzymes, or responsive synthesis of MIL-100(Fe) [111] or the multi-grams sono-
polymers, should be more explored to endow the MOF with chemical synthesis of amine-functionalized metal–organic
additional responsiveness, and providing thus more oppor- framework/graphene oxide nanocomposite [112]. Some
tunities in the sensor design. patents have also explored new synthetic paths for the pro-
duction of MOFs, such as in the case of a novel synergistic
Scale‑up production microwave-ultrasound-assisted technique (CN112452357A),
or the synthesis of MOFs by flow-chemistry methods
Nowadays, only a small number of companies sell MOFs, (US2016346757A1). Thus, engineering approaches may
with a few crystalline structures commercially available provide solutions to achieve a simple and highly reproduc-
out of the thousands reported. Chemical companies such as ible synthesis of MOFs to prepare sensors in large scale.
BASF and MOF Technologies have been improving manu- The processability of MOFs depends instead on the physical
facturing MOF techniques, achieving the full development nature of the MOFs and the possibility of integrating them
of industrial scale-up processes for some remarkable MOF into the measurement system or device during the produc-
compounds. Indeed, BASF company claims to be the pio- tion process or in a later step. Most MOFs are currently
neer in the large-scale production of MOFs by developing produced as a powder product, which has significant han-
an electrochemical method for the industrial preparation dling, toxicity, and processability issues. Therefore, there are
of HKUST-1 (US8163949B2 patent). BASF achieved a many research efforts focused on the production of MOFs

13
2018 Zuliani A. et al.

in dispersed forms, including gels, membranes, or films such as the case of wearable biosensors placed directly on
[113], as in the case of a patented Zn, Fe, Cu, or Cd-MOF the human skin or other part of the body for in situ and/or
films used to improve the performance of a chloroform gas real-time measurements of analytes in body fluids or tissues;
QCM sensor (CN109799159A), or a patented fluorescent however, it does not apply to sensing methods performed in
ink based on MOFs (CN114350207A). the laboratory on biological samples (blood, plasma, urine,
etc.). Due to this safety requirement, the use of mercury
Environmental aspects as the electrode in many electrochemical sensors has been
replaced by more biocompatible bismuth and gold electrodes
The need for sustainable development is crucial in all aspects to develop wearable biosensors [117].
of life, including industrial production as well. However, the
actual shift from a petroleum-based, energy-inefficient, and
environmentally unfriendly industry to a sustainable indus- Conclusions
try is still far from taking significant steps forward. What
seems most likely is a “green washing” of old methods (i.e., The strength of MOFs over other materials strongly relies on
the appearance of sustainable production with no metrics or their well-defined structures, having linking units which are
tests to prove the fact), also involving R&D in MOF produc- amenable to chemical modification by following a rational
tion and all the manufacture of MOF sensors. In fact, most “design-for-purpose” approach. This allows establishing
research articles related to MOFs do not explore the topic structure–property-function relationships, which in turn will
of sustainable development (beyond some mere theoretical allow access to the desired sensing properties in terms of
considerations), nor do they calculate some simple green selectivity, sensitivity, responsiveness, stability, etc.
metrics, such as the E-Factor (the amount of waste produced Due to continuous research efforts directed at the syn-
in a process per kg of product [114, 115]). Some good works thesis and optimization of new materials, MOF-based sen-
have started to investigate environmental aspects, such as sors are on the way to improving their performance, and
the use of sustainable resources (water instead of more toxic some are expected to reach commercialization in the next
organic solvents, earth-abundant transition metals instead few years. In fact, the increasing number of patents for new
of expensive precious metals, use of organic linkers derived MOFs with sensing properties and sensing devices integrat-
from biomass, etc.), carrying out reactions under mild con- ing MOFs clearly supports the bright future of MOF sen-
ditions, thus limiting energy consumption, reducing the sors in diverse industrial applications. The open issues and
amount of waste produced, using safer chemical products, challenges discussed above point to future directions in the
etc. These works have certainly highlighted the issue of sus- progress of MOF-based sensors. By solving these problems,
tainable development in the field as well but, considering the the researchers will take important steps to pave the way
mature level of MOFs, a substantial step forward should be towards the ultimate goal of having MOF-based sensors on
taken. In principle, for a correct analysis, life cycle analy- the market.
sis (LCA) and life cycle cost (LCC) should be considered Finally, it should be noted that the development of MOF-
as fundamental as any of the typical characterization tech- based sensors from the structural design to the fabrication
niques performed. However, considering the complexity of of the analytical sensing device is a multidisciplinary task,
these analyses, at least the reported sustainable characteris- and therefore the involvement of synthetic chemists, mate-
tics of a MOF or a MOF-based sensor should be corrobo- rial science scientists, theoretical chemists, engineers, and
rated with objective quantitative data, such as green metrics. clinicians (in case of biomedical sensors) is necessary to
ultimately succeed in translating academic research into
Health aspects industry and/or real-world applications.

Biosafety is a major concern when developing materials

for biomedical applications. Therefore, more systematic Funding Open Access funding provided thanks to the CRUE-CSIC
agreement with Springer Nature. A. Zuliani received the financial
in vitro and in vivo studies for investigating the toxicity of support by the Consejería de Transformación Económica, Industria,
MOF-based sensors are mandatory in these cases before Conocimiento y Universidades de la Junta de Andalucía in the frame-
their translation to clinical evaluation. Very few studies on work of the Plan Andaluz de Investigación, Desarrollo e Innovación
the in vivo toxicity of MOFs have been conducted to date (PAIDI 2020, programme 54A “Investigación científica e innovación,”
“POSTDOC_21_00594”). C.C.-C. received the financial support by the
[116] clearly limiting the progress of MOF-based biosen- Spanish Ministry of Science, Innovation and Universities (MICINN)
sors to some extent. This issue applies only to the case of and the Spanish Research Agency (AEI) through “Ramón y Cajal”
sensors incorporated in the body for in situ measurements, programme (RYC-2019–027527-I).

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Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards… 2019

Declarations 11. Tan KX, Barhoum A, Pan S, Danquah MK. Risks and toxicity
of nanoparticles and nanostructured materials. In: Barhoum A,
Conflict of interest The authors declare no competing interests. Salam A, Makhlouf H, editors. Emerging applications of nano-
particles and architecture nanostructures. Elsevier; 2018, pp
Open Access This article is licensed under a Creative Commons Attri- 121–39. https://doi.org/10.1016/B978-0-323-51254-1.00005-1.
bution 4.0 International License, which permits use, sharing, adapta- 12. Grande CA, Blom R, Spjelkavik A, Moreau V, Payet J. Life-cycle
tion, distribution and reproduction in any medium or format, as long assessment as a tool for eco-design of metal-organic frameworks
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