Coordination Chemistry Reviews 412 (2020) 213263

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Novel applications of metal-organic frameworks (MOFs) as redox-active

materials for elaboration of carbon-based electrodes with
electroanalytical uses
J. Antonio Cruz-Navarro a,c,1,⇑, Fabiola Hernandez-Garcia b,1, Giaan A. Alvarez Romero a,1
a
Universidad Autónoma del Estado de Hidalgo, Área Académica de Química, Carretera Pachuca-Tulancingo, Km 4.5. C.P 42184, Mineral de la Reforma, Hidalgo, Mexico
b
Universidad Autónoma del Estado de Hidalgo, Área Académica de Ciencias de la Tierra y Materiales, Pachuca-Tulancingo, Km 4.5. C.P 42184, Mineral de la Reforma, Hidalgo, Mexico
c
Facultad de Ciencias Químicas, Universidad Veracruzana, C.P. 94340 Orizaba, Veracruz, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Metal-organic frameworks are novel materials with specific pore-size that presents unlimited applica-
Received 19 September 2019 tions in material sciences. The presence of metallic ions in the MOF structure offers a redox active mate-
Accepted 21 February 2020 rial with electrocatalytical properties towards diverse biomolecules, organic compounds and heavy
metals. This property can be combined with nanomaterials for create cheap carbon based electrodes with
enhanced electroanalytical features (like selectivity, good low detection limits and high stability on alkali
Keywords: or acid media). In this review, we have collected recent information about MOF applications in carbon
Metal-organic framework
electrodes and fundamental aspects on the electroactive MOFs design, fabrication of MOF-modified car-
MOF composites
MOF-modified carbon based electrodes
bon based electrodes, characterization of electrodes and examples of direct sensing with MOF-modified
Electrochemical sensors electrodes.
Ó 2020 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Metal-organic frameworks: an overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. MOF-modified carbon-based electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. MOF-Modified carbon paste electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. MOF-modified glassy carbon electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Characterization of MOF-modified carbon-based electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Applications of MOF-modified electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1. Biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1.1. Non-enzymatic MOF-modified carbon-based electrodes for glucose sensing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1.2. Non-enzymatic MOF-modified carbon-based electrodes for sensing other biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.2. Non-enzymatic MOF-modified carbon-based electrodes for peroxide sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.3. MOF modified carbon-based electrodes for organic contaminants sensing in water (nitroaromatics and pharmaceuticals) . . . . . . . . . . . 14
5.4. MOF modified carbon-based electrodes for heavy metals sensing in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

⇑ Corresponding author at: Universidad Autónoma del Estado de Hidalgo, Área Académica de Química, Carretera Pachuca-Tulancingo, Km 4.5. C.P 42184, Mineral de la
Reforma, Hidalgo, Mexico.
E-mail address: antonio_cn@live.jp (J.A. Cruz-Navarro).
1
ORCID: 0000-0003-0057-2132 (JACN); 0000-0001-6194-4855 (FHG); 0000-0002-9525-3937 (GAAR).

https://doi.org/10.1016/j.ccr.2020.213263
0010-8545/Ó 2020 Elsevier B.V. All rights reserved.
2 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263
1. Introduction
In recent years, the use of electroanalytical techniques such as
voltammetry and amperometry for quantifying important analytes
has grown exponentially due to the wide versatility, reproducibil-
ity, sensitivity, and the use of inexpensive instruments and
requirements in comparison with other analytical techniques such
as gas chromatography, HPLC or atomic absorption spectroscopy.
The basis of electroanalytical techniques is the use of modified
electrodes that are directly involved in the selective oxidation or
reduction of analytes. For this purpose, it is important to select
chemically inert and electrochemically stable materials for their
fabrication [1]. Modified metallic electrodes are the most used in
electroanalytical chemistry; however, the formation of metallic
oxides on the electrode affects the measure on the system, and
generates irreproducible data [2]. On the other hand, the use of
carbon-based electrodes has grown broadly owing to their low
cost, chemical inertness, wide potential window (from
1.4 to
+1.3 V), low background current and the ease of can be modified
using materials such as coordination complexes to enhance selec-
tivity toward different analytes and increase the electrochemical
signal.
Currently, the search for new materials with exceptional prop-
erties as modifiers of carbon-based electrodes has grown con-
stantly. MOFs offer a variety of advantages as electrode modifiers
due to its property of selective adsorption of molecules in their
pores, presence of metallic centers which induce electro-
oxidation of analytes, and the capability of increases the analytical
response [3]. The application of MOFs in the field of electrochem-
istry is new and implies a big challenge in design MOFs composites
with interesting architectures and redox properties for the detec-
tion of biomolecules and other compounds in aqueous media.
Currently, there are reported a variety of examples about
MOF-modified carbon-based electrodes for sensing applications;
however, the information about stability and electrochemical
behavior of MOFs in the electrode is limited.
Until now, there are several reviews about the use of MOFs in
electrochemical applications; nevertheless, the exclusive use of
MOFs as modifiers of carbon-based electrodes for sensing applica-
tion has not been reviewed. Herein, we provide an overview of the
synthesis of MOFs materials, their attractive properties as modi-
fiers, and the application in design modified carbon-based elec-
trodes for their use in voltammetric and amperometric sensing of
important biomolecules, nitrogenated compounds, pharmaceuti-
cals, and some heavy metals. Before this, we discuss the oxidation
and reduction mechanism of MOFs in/on the electrodes. The pur-
pose of this review is providing the necessary information to
inspire new research about the use of MOF as modifiers in elec-
trodes for electroanalytical application.
2. Metal-organic frameworks: an overview
Metal-organic frameworks (MOFs) are polymeric and crys-
talline materials formed by the coordination of metal cluster nodes
(also known as secondary building units (SBUs)) with organic
ligands to obtain infinite 2D or 3D networks with different topolo-
gies [4–6]. Most of the reported MOFs contain transition with
quare, tetrahedral or octahedral geometries, and MOFs based on
lanthanide ions demonstrates elevated degrees of coordination like
heptacoordinated and nonacoordinated compounds. Synthesis of
MOFs is not difficult and implies inexpensive reactants like inor-
ganic salts (generally nitrates and chlorides) and organic ligands
(generally commercial carboxylic acids) (Fig. 1). Different method-
ologies for synthesis are reported in several reviews [7–9] and
include microwave-assisted, electrochemical, mechanochemical
Fig. 1. Deconstruction of a MOF with a tetratopic ligand and a metal SBU.
and sonochemical synthesis; nevertheless, the solvothermal and
hydrothermal approach are the most used due to the high reaction
yields and the quality of the crystals obtained. During the synthesis
of MOFs, several molecules such as solvents or ligands may be
trapped in the pores of the structure affecting the surface area of
the material, due to this, it is important to activate the MOFs after
synthesis for acquire the permanent porosity and eliminate
trapped molecules. Diverse methods of activation have been briefly
described [7] and involve supercritical drying or vacuum drying
(with a previous solvent exchange treatment) method. This last
is the most used for activating MOFs.
MOFs have interesting features like high thermal stability,
water stability, insolubility on diverse solvents among others;
however, MOFs are extensively investigated due to their porosity
properties and huge internal surface area, overcoming 6000 m2/g
[10,11]. The porosity on MOFs allows the penetration of guest
molecules that can be removed without collapse the structure or
modify the topology [12], because of this, there are MOFs applica-
tions in storage of hydrogen [13–17], methane [18–20], carbon
dioxide[20–23] or oxygen [24] and the selective removal of sol-
vents [25–27], heavy metals[28–31] and dyes [32–36] from
wastewater. Other applications of MOFs are based on their surface
area for the heterogeneous catalysis on organic chemistry [37–41],
and the addition of metals from the f block leads to the MOFs to
obtain optical properties like luminescence [42–44] and IR emis-
sion [45] for biomedical applications.
MOFs are considered as materials with low electron conductiv-
ity properties due to their the poor overlap between frontier orbits
and the electronic states on ligands and metal ions [46,47], for that
reason, the direct application of pure MOFs is limited in its use on
electrodes or other electrochemical devices [48–50]. A smart strat-
egy for solving the conductivity problems of MOFs and enhancing
the electron conduction at macroscopic levels is to create MOFs
composites with high electron-conductive material such as metal-
lic NPs, metal nanocrystals, and conductive polymers
[46,48,49,51]. Recently, the use of carbon-based materials has
increased intensively in the design of devices with electrochemical
applications. There is a variety of diverse allotropes (Fig. 2) such as
graphite, single-wall carbon nanotubes (SWCNTs) or fullerenes
(C60) with extraordinary properties like wide mechanical strength,
thermal stability, high electron conductivity, low toxicity and low
cost (with some exceptions) that are used to obtain MOF compos-
ites with extraordinary characteristics, according to reported in lit-
erature [52]. MOF composites are extensively applied as the active
material for energy storage devices such as batteries and superca-
pacitors. In literature, diverse reviews about the elaboration and
working process of MOF composites for energy storage devices
are very detailed and well explained [47,50,51,53,54]; however,
the application of MOF composites in electroanalytical application
have not been reviewed completely.
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263
Fig. 2. Most of the common carbon allotropes used for elaborate MOF composites.
As mentioned before, modified electrodes are the basis of the
electroanalytical chemistry, and for this purpose, the selectivity
and sensitivity are important aspects to consider in the perfor-
mance of the modified electrodes used on voltammetric or amper-
ometric techniques [3], and MOF composites must provide this two
features. The architecture of MOFs plays an important role in the
composites used for modify electrodes due to the presence of pores
and metal ions. The pore size of MOFs enhances the electrochem-
ical response by adsorbing specific targets selectively. A vast
variety of topologies reported (Fig. 3) [6] and diverse pore sizes
(1–98 Å) can be obtained in MOFs by the use of flexible ligands
which can adopt different conformations according to the geome-
try of the metal ion [5,6,55]. In addition, the accurate selection of
ligands helps to increase the electron-transfer into the framework
and the conductivity in the composite. For this purpose, ligands
with conjugated systems such as aromatic acids, pyridines, imida-
zoles, or benzimidazoles are preferred for electrochemical applica-
tion. On the other hand, the selectivity, and electrocatalytic
properties of MOF composites is achieved by the presence of elec-
troactive species like metals ions [56]. The behavior in alkaline
media of some transition metals ion such as Ni2+, Cu2+, or Co2+
offers an excellent way to obtain a redox-active couple with cat-
alytic properties [57]. Transition metal MOF composites are used
as electrode modifiers for the selective electro-oxidation of alco-
hols and diverse biomolecules such as glucose, aminoacids or sec-
ondary metabolites, for this reason, the recent use of MOFs in the
elaboration of electrodes (specifically carbon paste or glassy elec-
trodes) is growing widely.
3. MOF-modified carbon-based electrodes
In the electrochemical analysis (specifically amperometric and
voltammetric techniques), the use of carbon-based electrodes is
3
quite common due to its easy construction and modification, its
wide suitability in the detection of various analytes, among other
properties discussed in the introduction. Generally, carbon allo-
tropes employed to fabricate electrodes are graphite (for carbon-
paste electrodes) and glassy carbon (for solid carbon electrodes).
The sp2 bonding and the presence of six-membered aromatic rings
in the structure of the allotropes allow performing conductivity [2].
In the modification of carbon-based electrodes, the preparation of
MOF-carbon composites is necessary for direct MOFs application.
For example, on glassy carbon electrodes (GCEs) the polished sur-
face is covered with the MOF-composite directly, and for the case
of carbon paste electrodes (CPEs), the composite used for elaborate
the electrode is synthesized in situ by mixing the graphite powder
and the MOF with an organic binder. Elaboration process and mod-
ification techniques for glassy carbon electrodes and carbon-paste
electrodes will is discussed briefly in this section.
3.1. MOF-Modified carbon paste electrodes
Carbon paste electrodes (introduced by Adams in 1958) were
designed with the purpose to obtain a surface renewable electrode
useful on positive potentials where mercury electrodes are not
functional [58,59]. Initially, CPEs were not suitable for electro-
chemical analysis for its high content of organic binder that pro-
duced an elevated electric resistance among other unwanted
effects; nevertheless, an accurate mixture of components created
an extraordinary conductive carbon-based electrode [60].
The CPEs are inexpensive electrodes elaborated from a graphite
powder composite, which is prepared by mixing different compo-
nents (graphite, a modifier, and an organic binder) in an accurate
proportion [2,61]. Graphite used for electrodes must to have chem-
ical purity, uniform particle size (about 5–20 lm), and low capac-
ity of adsorbing impurities and oxygen [59]. An inaccurate size of
4 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263

Fig. 3. Schematization of diverse MOFs topologies. Redrawn from reference [6].

the graphite particles could originate a rugous surface on the elec- the organic binder employed must be insoluble, electrochemically
trode and alter the electrochemical properties [60]; furthermore, stable and free of impurities. Mineral oils, paraffin, silicone oil, and
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 5

nujol are often employed as binder agents; however, other pasting

liquids like organic halides, ethers, esters, and highly concentrated
inorganic acids or alkalis (for electroactive CPEs) have been exten-
sively used [62].
Modification of CPEs started in the middle of the 70’s incorpo-
rating chelating agents for preconcentrate metals in the electrode
surface [58]; however, Ravichandran and Balwind [63] proposed
incorporating a modifier directly on the mixture. Their work was
the initiator of the wide expanse of modified CPEs [60]. Currently,
diverse modifiers for CPEs such as nanomaterials [64], conductive
polymers, amino acids, organic ligands, and inorganic compounds
have been broadly used on amperometric and voltammetric deter-
mination of analytes on foods, wastewater, drugs, and biological
systems. Fig. 4. Ex situ synthesis of graphite/MOF composite for CPE elaboration.

Taking advantage of the conductive properties of graphite on

CPEs, the search for novel materials such as MOFs for the direct
modification of carbon-based electrodes is new and attractive.
MOF-modified CPEs combines the electrochemical features of CPE
and the selective capability of MOFs, which improve the electroan-
alytical signal of electrodes. The MOFs in CPE acts as a Lewis acid in
catalysis and decrease the charge transfer resistance and the over-
potential [46], as well as, the specific pore size offers preconcen-
trate the analyte and enhances the selective identification
between similar analytes.
The elaboration process of modified carbon paste electrodes
requires mixing the graphite powder and the modifier with the
organic binder in an agate mortar until to obtain a well-
dispersed composite, which is packed into an electrode body. After
that, an electric contact is established by introducing a copper wire
or a special plug-in in the electrode for its connection to the poten-
tiostat/galvanostat. Insulin syringes, Teflon tubes (with 0.5 cm of
diameter), or carbon paste holders are usually employed as elec-
trode bodies.
In most of the CPEs reported, the ratio of graphite powder and
the binder used to prepare the paste is according to the researcher
experience. For example, for dry carbon paste elaboration, Pin- Fig. 5. Glassy carbon fullerene related structure. Redrawn from reference [70].
garrón and Sanchez [60] recommend a ratio of 0.3–0.5 mL of the
binder per gram of graphite powder, while for humid paste the
ratio must be 0.5–0.9 mL per gram. 3.2. MOF-modified glassy carbon electrodes
To elaborate MOF/carbon-paste composites for electrodes fabri-
cation, diverse methods have been reviewed [52,65], and are Glassy carbon (GC) is a nongraphitizable and disordered kind of
divided on in-situ approach (The MOF is synthesized in the carbon carbon that combines glassy and ceramic properties. This material
composite) and ex-situ approach (The MOF is mixed with carbon is produced under controlled pyrolysis of phenol–formaldehyde
materials for creating the composite). A problem associated with resin, polyfurfuryl alcohol or cellulose in an inert atmosphere
in-situ synthesis is that the inappropriate amount of carbon-based [68]. Physical properties of GC include high anisotropy, high chem-
material could ruin the coordination reaction, the MOF structure, ical resistance (even on concentrated acids like H2SO4), elevated
and its properties [66], for these reasons, ex-situ approaches like thermal resistance, and low permeability for liquids and gases
direct mixing or mechanical methods are preferred to obtain due to the absence of open porosity in its structure [69,70]. These
desired composites for CPEs applications [52]. In this method features allows to GC being applied on several electrical applica-
(Fig. 4), the MOF and the graphite powder are mixed directly with tion, especially as an electrode material for electroanalytical appli-
a binder and the graphite in an accurate ratio to generate a MOF- cation. The structure of GC is unknown; some authors suggest a
composite. The composite is used to fabricate the modified carbon structure with sp2 curved graphene sheets [71]; however, other
paste electrode as mentioned in the procedure of modified carbon studies indicates that GC involves a fullerene-related structure
paste electrode elaboration. In this case, the graphite acts as an with broken fragments of fullerenes and the presence of curvatures
immobilizer for the MOF and improves it electron conductivity. [70] as illustrated in Fig. 5.
An example of MOF-modified CPE preparation is reported by Y. Li The first use of glassy carbon on voltammetry was reported by
and coworkers [61] where a mix of MOF (MIL-101) (7%), graphite Zittel and Miller on 1962 as from +1.2 to
0.8 V in an acid medium
powder (63%) and paraffin (30%) is used to elaborate an electrode in comparison with the saturated calomel electrode [72]. In their
for selective uric acid electrooxidation. Another example is reported paper, the electrode was elaborated by molding glassy carbon into
by H. Wang group [67] where a graphene oxide and MOF (MIL-101) a plastic rod and a Hg contact. Nowadays, glassy carbon electrodes
composite is grounded with graphite powder in a 14:1 ratio and (GCE) are very popular due to its broad potential windows, chem-
mixed with 30% of paraffin. In both cases, paraffin is the binder ical resistant, high mechanical properties, and reproducible perfor-
agent; however, other cases considerer mineral oil as an organic mance, due to these properties GCEs are the most used for
binder. Despite the advantages that MOF-modified CPEs could offer, elaborate chemically-modified electrodes and most of the MOF-
these electrodes are not preferred due to its difficult elaboration modified electrodes reported are GCE. On typical electroanalysis,
process and the low reproducibility. GCEs must be pretreated to increase their analytical performance.
6 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263

Fig. 6. Modification of a GCE with a Ni-MOF-Composite for glucose sensing. Redrawn from reference [57].

Fig. 7. Direct growth of HKUST-1 MOF onto GCE surface. Redrawn from reference [75].

Diverse techniques are explained briefly on a pretreated carbon
electrodes review [1] and includes solvent cleaning, vacuum heat
treatment, laser-based treatment, microwave plasma, and electro-
chemical polarization, however; the most used technique is the
mechanical polishing and requires the use of smaller alumina par-
ticles (0.05 lm) and a polishing cloth for obtain a mirror-like sur-
face on the electrode.
The modification process of a GCE with MOFs implies the syn-
thesis of composites due to the low conductivity of MOFs materi-
als. The composite prepared is dispersed in acetic acid, DMF, or
ethanol; then, the suspension is dip-coated onto the surface of
the electrode and dried at room temperature. A well-illustrated
example of this modification technique (Fig. 6) is reported by
Wang and coworkers [57]. In their work, a previously synthesized
3D flower-like Ni(TPA) is mixed in a SWCNTs-Cs dispersion in
acetic acid for creating a Ni(TPA)/SWCNT-Cs composite which is
used for modifying a GCE. In some cases [73,74], a Nafion solution
is cast onto the surface of the electrode after its modification.
A very detailed different methodology for modifying GCE
(Fig. 7) is reported by Shahrokhian and co-workers [75], which is
a direct growth of HKUST-1 on the surface of a GCE. Their method
implies the electrodeposition of metallic copper on the surface of
the GCE and the conversion of the electrodeposited copper to Cu
(OH)2 NTs for its use as a starting material on the synthesis of
HKUST-1. The Cu(OH)2 NTs@GCE is immersed in a 0.1 g linker
(H3BTC) solution for 4 min to obtain the MOF modified GCE. Other
methodologies imply the use of MOFs as a sacrificial material for
obtaining metal oxides used to elaborate non-enzymatic elec-
trodes; however, these methodologies will be discussed in other
sections of this text.
4. Characterization of MOF-modified carbon-based electrodes
During the elaboration of a MOF-modified carbon-based elec-
trode, it is necessary to characterize the MOF synthesized, the
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 7

Fig. 8. SEM images of crystal morphology of different MOFs: a) ZIF 67, b) HKUST-1, c) ZIF-9 and d) MIL-101. Redrawn and readapted from references: [76], [77], [78] and [79]
respectively.

Fig. 9. SEM images of the Ni-MOF (a) and the CNTs composite (b) obtained after pyrolysis. Redrawn and readapted from reference [80].

MOF-composite elaborated, and the MOF-modified electrode with
the purpose to know how the MOF affects the morphology and the
conductivity properties of the modified electrode.
In the characterization of MOF materials, the chemical structure
and the physical properties of the synthesized MOF are studied
prior its incorporation in an electrode. An indispensable character-
ization of MOF includes PXRD (powder X-ray diffraction) pattern to
clarify phase purity, bulk crystallinity [7] and is usually compared
with the obtained in sillico. Thermal stability is used to determinate
the breakdown temperature of the MOF and the presence of physi-
sorbed and chemisorbed water. The scanning electron microscopy
(SEM) is used in alliance with energy-dispersive X-ray spec-
troscopy (EDS) to evaluate the morphology of the crystals and
the chemical composition. The BET method aids to confirm the
type of porosity (meso, micro or nano) and calculate the surface
area according to the absorption/desorption isotherm. In Fig. 8,
are represented diverse examples of SEM images of the morphol-
ogy of diverse MOF such as ZIF-67 [76], HKUST-1 [77], ZIF-9 [78],
and MIL-101 [79].
For the characterization of the MOF-composite, the most impor-
tant techniques used are SEM and TEM, where the material is
deposited on a conductive diamond wafer before its analysis. These
8 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263
Fig. 10. SEM/XPS mapping of elemental composition of Cu and O, Cu/C. Redrawn from reference [81].
Fig. 11. SEM images of a CPE before (a) and after modification with a MOF (b). Redrawn from reference [82].
technique has been used to observe the morphology of the MOF
when is modified with carbon-based materials or metallic NPs.
For example, SEM images of a Ni-MOF derived composite [80]
(Fig. 9) indicated the presence of CNTs on the polyhedrons of the
MOF, originated by the direct pyrolysis Ni-MOF in presence of
nitrogen.
With SEM/XPS it is also possible to obtain an elemental map-
ping from the surface of the electrode. The provided graph is useful
to know the distribution of metal centers from the MOF in the
composite. An example of this technique is the elemental mapping
of a Cu-MOF@MWCNTs/GCE reported by Wu [81] (Fig. 10) where is
possible to observe the distribution of the Cu2+ centers in the
composite.
On electrode elaboration, several techniques are employed for
characterizing the morphology on the electrode surface and its
electrochemical behavior. SEM is very helpful for determinate the
morphology on the electrode surface before and after its modifica-
tion. For CPEs, it is possible to observe how the MOF-material mod-
ifies the flat surface of the carbon paste. The characterization by
SEM of the modified surface of a MOF-14/CPE is reported by Zhang
[82]. In the SEM images (Fig. 11) is observed the comparison of the
CPE electrode and the MOF-14/CPE. The incorporation of the MOF
in the electrode generates a rough surface in the electrode.
The important part of the modified electrode characterization is
its evaluation by cyclic voltammetry (CV) at a specific potential
window. In most of the MOF-modified electrodes reported, CV is
useful for evaluating the electrochemical behavior of the MOF in
the supporting electrolyte. Results obtained aids to understand
the redox properties of MOF by the analysis of cathodic and anodic
peaks in the cyclic voltammogram, which corresponds to the oxi-
dation states of the metallic center. Also, CV is useful to analyze
the electrochemical response. This experiment evaluates the elec-
trochemical behavior of the MOF-modified electrode in the
absence and presence of a specific analyte at positive or negative
potentials. If the MOF interacts with the analyte, an electrochemi-
cal signal is observed, and increase (oxidation process) or decrease
(reduction process) according to the analyte concentration. On the
other hand, CV helps to study the electrode interaction at different
pH and several scan rates to obtaining the best parameters for the
electrochemical assay. Fig. 12 represents an example of a complete
electrochemical characterization, where is carry out an evaluation
of a glucose sensor (CPO-27-Ni2+/GCE) [83] by CV. In this example,
the redox property of the CPO-27-Ni2+ in the modified electrode is
studied in the support electrolyte (NaOH 0.1 M), and compared
with the unmodified electrode. As observed in the cyclic voltam-
mogram from Fig. 12a, the GCE does not show any redox behavior
at the potential evaluated; however, CPO-27-Ni2+/GCE shows oxi-
dation and reduction peaks at 0.51 and 0.44 V, respectively. This
electrochemical behavior corresponds to the oxidation of Ni2+ to
Ni3+ (I0 ) and the reduction of Ni3+ to Ni2+ (I00 ), respectively.
Fig. 12b represent the behavior of the CPO-27-Ni2+/GCE in different
scan rates (25–500 mV/s). The increase of the redox peak current of
Ni2+ was directly proportional to the scan rate, indicating the redox
controlled process on the electrode surface. Additionally, the elec-
trochemical response was evaluated in presence of glucose, as
observed in Fig. 12c, the oxidation peak of Ni2+ to Ni3+ becomes
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 9

Fig. 12. Electrochemical characterization of a Ni-MOF/GCE. Redrawn and readapted from reference [83].

Fig. 14. Nyquist plot from the characterization of different GCEs modified with
CNTs and CNTs/Ni-MOF. Redrawn from reference [85].

Other technique used for electrode characterization is electron

Fig. 13. Nyquist plot from the characterization of diverse modified GCEs where (a)
represents GCE, (b) GC/Zn-MOF, (c) GC/TA-Zn-MOF and (d) GC/AgNPs-Zn-MOF.
Redrawn from Reference [74].
in wide wave, demonstrating the high electrocatalytic activity
toward the analyte. The sensor demonstrates a linear response
when the glucose concentration increases, as shown in Fig. 12d.
impedance spectroscopy (EIS). This technique has been widely
used to characterize the energy storage on electrochemical capac-
itors or batteries, and for characterize modified electrodes used in
electroanalytical chemistry [84]. The obtained plots in EIS are rep-
resented as a semicircle and are known as Nyquist plot. Usually on
the characterization of a modified electrode, the Nyquist plot is
obtained for the electrode without modification (e.g., a GCE bare)
and after modification (e.g. a GCE modified with a material) with
the purpose to identify how the modifier (in this case the MOF
10 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263
material) affects the electron transference on the electrode surface.
For example, Arul [74] reported the characterization via EIS of a
GCE modified with a Zn-MOF/AgNPs composite. The results in
the Nyquist plot (Fig. 13) were fitted with a Randles circuit for
obtaining the resistance values for the GCE, GC/Zn-MOF, GC/TA-
Zn-MOF, and the GC/AgNPs-Zn-MOF electrodes are 30.16, 33.84,
22.33 and 18.10 kO, respectively. It is obvious that MOF material
acts as a capacitor increasing the GCE resistance from 30.16 to
33.84 kO; nevertheless, AgNPS decrease notably the resistance to
18.10 kO, indicating enhance of the electron transfer on the
electrode.
Some materials like CNTs or graphene may increase the elec-
trode resistance when are use as a single material for modifying
a carbon-based electrode; however, when are used to create MOFs
composites, the electron transfer is enhanced. An example of this is
reported by Zhang [85] where a GCE was modified with CNTs and
CNTs/Ni-MOF. The Nyquist plot obtained (Fig. 14) indicates GCE
modified with CNTs and GCE modified with Ni-MOF has low elec-
tron conductivity; however the CNTs/Ni-MOF composite has a
great electron conductivity and the resistance is decreased.
5. Applications of MOF-modified electrodes
The use of MOF-modified carbon-based electrodes has been
extendedly reported for amperometric and voltammetric tech-
niques in the determination and quantification of different ana-
lytes like biomolecules, pharmaceuticals, aromatic compounds,
and heavy metals. The limit of detections (LOD) of these sensors
surpasses the reported by other techniques or other modified elec-
trodes and shows the potential uses of MOF on electroanalytical
chemistry.
5.1. Biomolecules
The quantitative determination of biomolecules is very impor-
tant in clinical chemistry and food chemistry. Throughout history,
biomolecules have been determined by different methods that
include spectroscopy, immunodetection, and separation methods.
In recent years, extraordinary progress in the field of electrochem-
ical sensing of biomolecules is on expanding, with more than 2500
articles per year (Scopus search), and plays an important role in the
exact quantification of these molecules.
In most cases, quantification of biomolecules by electrochemi-
cal methods requires enzyme-modified electrodes with accurate
selectivity and the property of enhancing the analytical response.
Diverse enzymes are extendedly used for modifying carbon-
based electrodes to obtain specific selectivity on the quantification
of analytes with similar chemical properties; nevertheless,
enzymes are dependent on cofactors, cosubstrates [86], are not
stable at certain temperatures or pH values and their immobiliza-
tion on the electrode surface is quite difficult, for these reasons,
their applicability is limited [87]. Due to this, there is an increment
in the design of non-enzymatic or enzyme-free electrodes or sen-
sors. In these electrodes, enzymes are replaced with novelty mate-
rial such as metal oxides, nanomaterials and recently MOF-
composite materials with catalytic and redox properties. High sen-
sitivity, selectivity, and aqueous media stability are the advantages
of using MOF-composites as active materials for Non-enzymatic
sensors.
5.1.1. Non-enzymatic MOF-modified carbon-based electrodes for
glucose sensing
It has been demonstrated that materials based on transition
metals (specially Ni2+, Cu2+, Co3+, and Fe+2) have electrocatalytic
activity toward biomolecules such as hydrogen peroxide, urea,
ascorbic acid, and glucose [57]. This principle is used for designing
all kinds of modified electrodes with the capability of quantifying
biomolecules at micro and nanomolar concentrations.
Based on glucose is the most popular analyte in the scientific lit-
erature [88], a variety of non-enzymatic sensors modified with
transition metal MOFs are focused on selective oxidation of glucose
on the surface of the electrode to obtain gluconolactone. Some of
these sensors are MOF-modified carbon-based electrodes that have
been prepared using Ni-MOFs, Co-MOFs or Cu-MOFs as a sacrificial
material with a specific methodology (pyrolysis, electro-oxidation,
etc) to obtain a corresponding metal oxide or derivates with some
modifications. For example, Yin and coworkers [80] reported a GCE
modified with a Ni/NiO/CNTs composite obtained by the direct
pyrolysis of Ni-MOF at 900 °C. During the pyrolysis, CNTs are
formed in situ on the surface of the oxide synthesized due to the
organic moiety of the metal–organic framework. The modified
GCE was characterized by CV in the absence and presence of glu-
cose at different concentrations, displaying higher oxidation peaks
and the enhancement of this peaks accompanying with a decrease
of the reduction peak, and a linear response on chronoamperomet-
ric techniques according to the glucose concentration. Another
example reported by Asadian’s group [89] is the use of ZIF-67 as
a sacrificial template for the synthesis of NiCo LDH nanosheets
used for modifies a GCE with catalytic activity for glucose.
For all examples of non-enzymatic carbon-based sensors for
glucose where Ni or Cu is used as a MOF or it derivates, a redox
couple (Ni2+/3+ or Cu2+/3+) is generated on alkaline media which
allows to the formation of nickel oxyhydroxide (NiOOH)
[75,81,90,91] that catalyze the electro-oxidation of glucose. For
nickel and copper, the mechanism of glucose electro-oxidation is
the same and is described in the reactions (1–2) and Fig. 15 where
M represents nickel or copper.
 
M2 þ þ OH
! MOOH or M3þ þ e
ð1Þ
MOOH þ glucose þ e
! M2þ þ gluconolactone ð2Þ
In the first step, the M is oxidized in alkaline media to M3+
2+
which produces the catalytically active MOOH that generates an
oxidation peak current in voltammograms, then, MOOH oxidizes
glucose (C6H12O6) to gluconolactone (C6H12O7) increasing the oxi-
dation current and M2+ is regenerated again. This mechanism has
been extendedly used for selective electro-oxidation of methanol
on GCE modified with copper and nickel ions [92]. In Fig. 16, we
place two examples reported of the voltammetric and amperomet-
ric response toward glucose on GCE modified with CuO [91] and
Ni-Co [89] obtained from MOFs. The voltammograms show an oxi-
dation peak at about 0.4 V (Fig. 16a) and 0.6 V (Fig. 16b) which
Fig. 15. Schematic mechanism of glucose electrochemical oxidation on MOF-
modified carbon based electrode surface.
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 11

Fig. 16. Voltammometric (a, b) and amperometric (c, d) responses of MOF-modified electrode toward glucose. Redrawn and readapted from references [91] and [89].

Table 1
Examples of MOF-Modified carbon-based electrodes for amperometric sensing of glucose in alkaline media (0.1 M NaOH).

Electrode MOF Ligand MOF Composite Oxidation LOD Linear range Sensitivity Real Sample Reference
Potential
GCE Ni2+ Ni(TPA) H2BDC Ni-MOF@CNTs 0.6 V 0.82 lM 1.0 lM– 13.85 lA/mM Human serum [85]
1.6 mM cm2
GCE CPO-27-Ni H4DHTP – 0.55 V 1.46 lM N/R 40.95 lA/mM Human serum [83]
(II) cm2
GCE Ni-MOF 2- Ni/NiO@CNTs 0.57 V N/R 8.0–1500 lM 284.58 lA/mM N/R [80]
HmIm cm2
GCE Ni(TPA) H2BDC Ni-MOF@CNTs 0.4 V 4.6 lM 20 lM– N/R Human serum [57]
4.4 mM
GCE Ni(II)-CP N/R Ni2+-CP@C60 0.57 V 4.3 lM N/R 614 lA/mM Human plasma [109]
cm2
GCE Co2+ ZIF-67 2- ZIF-67@Ag 0.42 V 0.6 lM 2.0–1000 lM 334 lA/mM Human serum [110]
HmIm cm2
GCE Co-MOF H2BDC Co-MOF@Nickel 0.5 V 1.3 nM 0.001–3.0 mM 10,886 lA/mM Human serum and [111]
Foam cm2 peach juice
GCE Cu2+ Cu/Ni- H3BTC – 0.64 V 0.06 lM 0.1–2.2 lM N/R Honey [77]
MOF
GCE HKUST-1 H3BTC – 0.42 V 70 nM 0.0005– N/R Human serum [91]
5.0 lM
GCE HKUST-1 H3BTC – 0.5 V N/R N/R N/R N/R [75]
GCE HKUST-1 H3BTC HKUST- 0.3 V 0.4 lM 0.5 lM– 3878 lA/mM Human serum [81]
1@MWCNTs 11.84 mM cm2

N/R = not reported.

demonstrate the electroactive behavior of the MOF material and
the presence of the electron transfer process described in the reac-
tion 1–2. The oxidation peak current increases with the glucose
concentration and this behavior is demonstrated by amperometric
tests. In the amperometric experiments, the oxidation potential
applied is usually the potential of the oxidation peak present in
the voltammogram. For the amperograms shown in Fig. 16, the
applied potential is 0.4 V (Fig. 16c), and 0.6 V (Fig. 16d). At these
potentials, in the absence of glucose, the faradaic current in the
system is 0; however, when glucose is added at various lapses,
the faradaic current increases markedly, indicating the potential
use of the sensor for detecting glucose at low concentrations.
As part of this work, we summarized several examples of glu-
cose sensing with electrodes modified with MOF-derived materi-
als. The potential of work, limits of detection and other analytic
parameters are mentioned in the Table 1.
12 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263
Fig. 17. Simultaneous determination of different biomolecules on a single MOF-
modified electrode using differential pulse voltammetry. Redrawn from reference
[93].
5.1.2. Non-enzymatic MOF-modified carbon-based electrodes for
sensing other biomolecules
As mentioned above, most of the MOF-modified carbon-based
electrodes are focused on glucose-sensing; however, based on
hosting properties of MOFs or redox properties, a vast diversity
of MOF-modified carbon-based electrodes have been developed
for quantify interesting biomolecules like dopamine, steroids, plant
metabolites, aminoacids among others. For example, Zhang and
coworkers [93] modified a GCE with a MOF composite (Pt NPS/
MIL-101) for the simultaneous detection of dopamine, uric acid
and xanthine derivates (Fig. 17). In this case, the design of the sen-
sor is based on a core–shell structure with two important aspects.
In the first one, the selected MOF (MIL-101) plays an important
role as a hoster framework for nanoparticles and acts like a
Fig. 18. Fabrication process of a GCE modified with MIL-101/CNTs combined with molecular impressed polymer for recognition of estradiol. Redrawn and readapted from
reference [113].
recognition agent that mimic molecular sieves; in the second
aspect, the Pt-NPs enhances conductivity and increase efficiency
for electrocatalytic oxidation of the biomolecules. The electro-
chemical response of the PtNPS/MIL-101@GCE to xanthine was
evaluated by DPV with different interferences such as ascorbic acid
(AA), dopamine (DA), uric acid (UA) and hypoxanthine (HXA). Four
anodic peaks were observed and are originated by the oxidation of
DA (0.13 V), UA (0.28 V), XA (0.68 V) and HXA (1.05 V), respectively
and there was no response to AA. Obtained results show that the
Pt/MIL-101@GCE is suitable for the selective determination of XA
in the presence of diverse interferences.
Another interesting example is a GCE reported by Jiang and
coworkers [78]. The GCE was modified with Co3O4@C obtained
by direct pyrolysis of ZIF-9. The electrode was used to understand
the mechanism of different antioxidant fruit extracts against the
oxidative stress on the cells (glioma cells) through the direct sens-
ing of superoxide (O

2 ).
On the other hand, MOF-composites can be combined with
molecular impressed polymers to create a highly selective sensor
for biomolecules. Duan [113] reported a MIL-101/CNTs composite
which is combined with polypyrrole to recognize estradiol in lake
water samples (Fig. 18). In this example, the printed polymer takes
the form of estradiol allowing preconcentrate it, and the MIL-101
generates a redox-active couple (Fe2+/Fe3+) that induces the elec-
trooxidation of estradiol, showing an electrochemical signal at
0.2 V that increases at different concentrations. To show the appli-
cation of MOF in sensor for biomolecules sensing, we summarized
diverse examples of MOF-modified electrodes in Table 2.
5.2. Non-enzymatic MOF-modified carbon-based electrodes for
peroxide sensing
Hydrogen peroxide (H2O2) is a short molecule industrially used
due to its oxidative properties and plays an important function in
defense of the organism; however, elevated concentrations of
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 13

Table 2
Examples of MOF-Modified carbon-based electrodes for amperometric or voltammetric sensing of diverse biomolecules.

Electrode Analyte MOF Ligand MOF Composite Work pH LOD Linear range Sensitivity Real Reference
Potential Sample
NPCP Luteoline ZIF-67 2- CuCo@NPCP 0.1 V 7.0 0.08 nM 0.2 nM– 134.57 lA/mM Human [76]
HmIm 2.5 mM cm2 serum
GCE Dopamine ZIF-8 2- ZIF-8@G 0.3 V 7.0 1.0 lM 3.0 lM– 0.34 lA/mM Cow serum [112]
HmIm 1.0 mM cm2
GCE L-Cysteine HKUST-1 H3BTC Au-SH-SiO2@Cu- 0.4 V 5.0 0.008 lM 0.02–300 lM N/R N/R [113]
MOF
GCE Ascorbic HKUST-1 H3BTC HKUST-1@GO
0.02 V 7.0 20 nM 0.5– 57.73 lA/mM N/R [49]
acid 6965.5 lM cm2
CPE Chatecol MIL-101 H2BDC MIL-101 (Cr) N/R 7.0 4.0 lM 10–1400 lM N/R Lake water [79]
(Cr) @rGO
GCE Xanthine MIL-101 H2BDC Pt-NPs@MIL-101 0.28 V 7.0 0.42 lM 0.5–162 lM N/R Human [114]
(Cr) serum
GCE 17b- MIL-53 H2BDC MIP-Pb/MIL- 0.21 V 3.0 0.00615 pM 0.01– N/R Tap water [115]
estradiol 53@CNT 1000 pM

Fig. 19. HKUST-1@GC electrode for amperometric determination of H2O2 in biological samples. The response is enhanced according the MOF morphology. Redrawn from
reference [96].

H2O2 in the body, may induce damage to the cell proliferation and
cause Alzheimer’s, Parkinson, or cancer disease [94]. Because of
this, diverse methods to quantify H2O2 like titrimetry or spec-
troscopy has been widely reported. Electrochemical sensing of per-
oxide is not new and the electrodes applied in voltammetric or
amperometric detection implies the use of enzymes or bacteria.
Recently, the quantification of H2O2 by electrochemical methods
using enzyme-free sensors have been intensely researched [95]
and transition metals have played an important role being extend-
edly used as active materials in these electrodes; however, transi-
tion metals do not present selectivity toward H2O2 and allow to
oxidize uric acid and ascorbic acid that are present with the
H2O2 in biological media [96]. MOF materials based on transition
metals such as Cu2+, Ni2+, and Co2+ allow selective electrocatalysis
of H2O2 in alkaline or neutral media. Owing to this behavior, there
are reported diverse electrodes based on transition metals MOFs
composites with metallic NPs or carbon-based materials like
MWCNTs or graphene.
As the same way of non-enzymatic glucose sensors, the basis of
H2O2 electrocatalysis is the presence of a redox couple in the
framework; nonetheless, for this case, the redox couple (M1+/M2+
or M°/M1+) induces an electro-reduction process, where H2O2 is
reduced to H2O and the M° or M1+ is oxidized by the H2O2 to M1+
or M2+ respectively. This process carries out at physiological or
alkaline pH. An example of this is a GO-HKUST-1@GCE reported
by Wang and co-workers [96], which is used for direct sensing of
H2O2 in cells at pH 7.0 (Fig. 19). In the example, the electrode is
based on the redox properties of the couple Cu°/Cu1+ that can
reduce significantly H2O2 into H2O according to the next
mechanism:
Cu1þ
HKUST
1 þ e
! Cuo
HKUST
1 ð3Þ
Cuo
HKUST
1 þ 1=2H2 O2 ! OH
þ Cu1þ
HKUST
1 ð4Þ
In the first step, the Cu2+ present on the framework is reduced
to Cu1+ showing a cathodic peak in voltammetry and then, with
another cathodic sweep, Cu1+ is immediately reduced to Cu° which
is oxidized by H2O2 producing hydroxyl ions and regenerating
Cu1+. Other examples of this are the sensors reported by Naseri
[95] and Meing [97]. In both works, a Cu2+ based MOF is used as
a modifier of a GCE, and the redox couple is Cu2+/Cu1+ (obtained
in pH 6.7 and alkaline media correspondingly) that induce the
reduction of H2O2 at
0.2 V and
0–45 V respectively, following
the same mechanism of Cu1+:
14 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263

Cu2þ
MOF þ e
! Cu1þ
MOF

organic compounds dissolved in wastewater or effluents.
Cu 1þ

MOF þ 1=2H2 O2 ! OH þ Cu 2þ

MOF
An interesting Co-based MOF used to modify a GCE for H2O2
sensing on alkaline media was reported by Yang [73], the redox
couple described in this case is Co3+/Co2+ obtained at
0.4 V which
induce the electrochemical reduction of H2O2. Due to the presence
of terephthalic acid in the framework, is evaluated the perodixase-
like activity. The catalysis of H2O2 with Co-MOF, produce OH
that
easily reacts with the terephthalic acid to form highly fluorescent
2-hydroxy terephthalic acid.
To the interest of the reader, we have resumed several examples
of H2O2 sensing by MOF-modified in Table 3.
5.3. MOF modified carbon-based electrodes for organic contaminants
sensing in water (nitroaromatics and pharmaceuticals)
The pore size of MOF materials allows absorbing molecules of
interest. This property is used to remove contaminants such as
dyes, metal ions, or solvents. Based on this feature, MOFs and MOFs
ð5Þ composites can be easily used for electrochemical sensing of
ð6Þ Recently, different MOF-modified carbon-based electrodes
have been used for specific detection and sensing of many water
contaminants. For example, Yadav’s group [98] reported the syn-
thesis of MOF-5 composite and its use in modifying a GCE for
electrocatalytic transformation of nitrite and nitrobenzene
(Fig. 20). In their work, the MOF-5/AuNPS composite induce an
effective oxidation of nitrite at 1.01 V and a reduction of
nitrobenzene at
0.77 V. The MOF-5/AuNPS@GCE electrode was
evaluated as a sensor for the direct sensing of nitrates and
nitrobenzene in the presence of diverse interferences such as
ascorbic acid and metal ions.
Another example of the determination of nitrogenated com-
pounds is the work reported by Zhang [99], where a Co-MOF
([Co2(4-ptz)2(bpp)(N3)2]n) is used to modify a GCE. The produced
electrode induced the electrocatalytic conversion of hydrazine
and nitrobenzene at 0.2 and
0.7 V respectively. The electrode
shows a linear response of the current which increase at different
concentrations of the analytes.

Table 3
Examples of MOF-Modified carbon-based electrodes for amperometric quantification of H2O2 in different media.

Electrode MOF Ligand MOF Reduction pH LOD Linear range Sensitivity Real Sample Reference
Composite Potential
CPE Ni-MOF Adipic –
0.25 V 13.0 0.0009 mM 0.004– N/R Cleaning [116]
acid 60 mM solution
GCE Y1-4-NDC-MOF H2NDC AgNPs@MOF/
0.5 V 7.0 0.43 lM 4.0–
80.23 lA/mM A549 cells [117]
ERGO 11000 lM cm2
GCE Ce1-xTbx-MOF H3BTC – 0.75 V 7.0 7.7 lM 0.1 mm– 12.99 lA/mM N/R [118]
4.2 mM cm2
GCE [Cu(adp)(BIB)(H2O)] H2ADP/ – N/R 13.0 0.068 lM 0.1–2.75 lM N/R N/R [119]
n BIB
GCE Cu(btec)0.5DMF H4BTEC –
0.2 V 6.5 0.865 lM 5–8000 lM N/R N/R [95]
GCE {[Cu2(bep)(ada)2] BEB/ADA Cu-MOF@AB
0.45 V 13.0 0.014 lM 0.05–3 lM 5.56 lA/mM N/R [97]
H2O}n cm2
CPE Cu-MOF H3BTB –
0.2 V 7.2 1.0 lM 1 lM– N/R N/R [82]
0.99 mM
GCE HKUST-1 H3BTC Cu-MOF@S-
0.4 V 7.0 0.49 lM 1.0–5.6 lM 135.4 lA/mM Raw 264.7 [96]
GO cm2 cells
GCE (Co(pbda)(4,4-bpy) H2PBDA –
0.4 V 13.0 3.76 lM 5.0 lM– 83.10 lA/mM Disinfectant [73]
2H2O]n 9.0 mM cm2
CPE Co-MOF H4DOBDC –
0.3 V 7.2 0.5 lM 1.0–823 lM N/R N/R [120]
GCE Zn-MOF H2BDC Zn-
0.80 V 7.2 67 nM 1 lM–5 mM N/R Milk [74]
MOF@AgNPs
GCE MIL-53-Cr(III) TPA –
0.37 V 13.0 3.52 lM 25–500 lM N/R Human [121]
Serum

Fig. 20. Cyclic voltammograms of nitrite (1) and nitrobenzene transformation (2) at a0 ) GCE, b0 )MOF-5@GCE, c0 )MOF-5/AuNPs@GCE. Absence of analyte in the electrodes is
represented by a, b and c. Redrawn from reference [98].
 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263 15

Table 4
Examples of MOF-Modified carbon-based electrodes for determination of aromatics, nitro aromatics, nitrites and pharmaceuticals in aqueous media.

Electrode Analyte MOF Ligand MOF Composite Potential of pH LOD Linear Real Sample Reference
detection range
CONTAMINANTS
GCE Nitrobencene MOF-5 H2BDC AuNPS@MOF-5
0.79 V 7.0 15.3 lM 20–500 lM N/R [98]
GCE Nitrite MOF-525 TCPP- N/R 0.9 V 8.0 2.1 lM 20–800 lM N/R [122]
H2
CPE Nitrite Cu-MOF H3BTB Cu-MOF@CPE 0.9 V 7.2 30 nM 50 nM– Lake water [123]
712 lM
GCE Hydrazine [Co2(4-ptz)2(bpp) 4- Co-MOF@MPC 0.2 V N/R N/R 5–630 lM N/R [99]
(N3)2]n ptzbpp
GCE Dihydroxybenzene HKUST-1 H3BTC HKUST-1@GN N/R 7.0 0.59 lM 1–1000 lM Tap water [124]
GCE Hydroxylamine MMPF-6 H2TCPP AuNPS@ MMPF- 0.35 V 7.0 0.004 lM 1–20 lM Tap water [125]
6
GCE BPA Ce-MOF H3BTC Ce-MOF/CTAB 0.52 V 7.0 2.0 nM 0.005– Milk [126]
5.0 lM
PHARMACEUTICALS
GCE Paracetamol HKUST-1 H3BTC AuNPS@HKUST-
0.06 V 6.0 0.0011 nM 0.01– Commercial [100]
1 100 lM tablets
GCE Metfotmin HKUST-1 H3BTC HKUST- 0.6 V 13.0 0.12 lM 5.0–25 lM Commercial [101]
1@MWCNTs tablets
GCE Chloramphenicol IRMOF-8 H2NDC IRMOF-8@EPC
0.1 V 7.5 0.0029 lM 0.01–1 lM Honey [102]

About pharmaceuticals, at the time of writing, only three exam-

ples have been reported and include paracetamol [100], metformin
[101] and chloramphenicol [102]. In the first example, the MOF
HKUST-1 is loaded with AuNPS to enhance the conductivity and
the electrocatalytic activity in the electrode; however, the
electro-oxidation is carried out by the AuNPS specifically and the
MOF is only a sieve for immobilizing the NPS. In the second and
third example, the redox process is carried out directly by the
MOF and the process is pH-dependent.
A huge list of diverse application of MOF to modify carbon-
based electrodes and it use on contaminants sensing is summa-
rized on Table 4.

5.4. MOF modified carbon-based electrodes for heavy metals sensing in

water

Electrochemical methods such as polarography, anodic strip-
ping voltammetry (ASV) and cathodic stripping voltammetry
(CSV) for determinate trace analysis is not new and have been
widely used on direct quantification of heavy metals [60]. In these
methods, diverse carbon-based modified electrodes with porous
materials such as mesoporous or nanoporous materials [103], car-
bon nanotubes/eggshell [104], modified multiwalled carbon nan-
otubes [105], modified chitosan [106], polypyrrole film and
imprinted polymers [107] have received considerable attention
for ASV because they exhibit significant improvements due to it
selectivity, low detection limit, renewability, and low cost.
Advanced materials like MOFs, offers multiple advantages over
ordinary modifier materials. These characteristics include selective
absorption and electrocatalytic activity toward diverse metallic
ions.
All reported works use MOF-modified carbon paste electrodes
due to the adsorptive properties of the carbon paste, which is
enhanced with the presence of MOF materials. The functioning of
a MOF-modified carbon paste electrode is focused on the precon-
centration of metallic ions followed by a stripping voltammetry
method for direct quantification. A perfect example to describe
how MOF improves a carbon paste electrode is reported by Wang
and co-workers [108]. Their electrode for lead sensing was modi-
fied with a Zn-MOF (MOF-5). According to the authors, the electro-
analytical procedure reported comprises two steps: adsorption of
Fig. 21. Differential pulse anodic stripping voltammograms of different concentra-
tions of Pb2+ at MOF-5 modified CPE. Redrawn from reference [108].
lead ions at the modified electrode surface with a preconcentration
potential of
0.9 V and electrochemical detection of the precon-
centrated species by anodic stripping voltammetry (Fig. 21) at

0.4 V approximately in pH 5.0. The same author reported an
amino-MOF (NH2-CU3(BTC)2) as a modifier material for a GCE.
The amino groups in the MOF interact with metal ions and allow
absorbing them on the surface of the electrode. The quantification
of Pb2+ was carried out by anodic stripping voltammetry at
0.6 V
in pH 4.5.
A similar procedure using amino-MOF is reported by Roushani
[126], in this work, the amino-MOF ([Zn2(NH2-BDC)2(4-bpdh)]3
DMF) is used as a modifier for CPE. The electrode reported is used
for sensing Cd2+ by differential pulse anodic stripping voltammetry
at pH 13.0 (Fig. 20). The electrode reported is used for sensing Cd2+
by differential pulse anodic stripping voltammetry at pH 13.0
(Fig. 22).
Determination of heavy metals by MOF-modified carbon-based
electrodes is new, and at present, few works been reported despite
all advantages that MOF materials offer; however, we summarized
several works based on carbon electrodes modified with MOFs on
Table 5.
16 J.A. Cruz-Navarro et al. / Coordination Chemistry Reviews 412 (2020) 213263

Fig. 22. Differential pulse anodic stripping voltammograms of different concentrations of Cd2+ at Zn-aminoMOF@CPE. Redrawn from reference [126].

Table 5
Examples of MOF-Modified carbon-based electrodes for stripping voltammetry quantification of heavy metals in water.

Electrode Analyte MOF MOF Composite Method Precocentration Time Potential of pH LOD Linear Real Reference
potential detection range Sample
CPE Cd2+ [Zn2(NH2-BDC)2 MOF@Graphene ASV
1.0 V 300 s
0.77 V 3.0 0.2 lg/L 0.7– Tap [127]
(4-bpdh)]3DMF 120 lg/L water
CPE Pb2+ MOF-5 – ASV
0.9 V 300 s
0.50 V 5.0 4.9 nM 10– Tap [108]
1000 nM water
2+
GCE Pb NH2-CU3(BTC)2 – ASV
1.0 V 300 s
0.60 V 4.5 5.0 nM 10– Powder [128]
500 nM milk
GCE Pb2+ ZIF-8 NaF/BiF/ZIF-8 ASV
1.2 V 120 s
0.64 V 4.7 4.16 ppb 12– N/R [129]
100 ppb
CPE Pb2+ MOF-235 – ASV N/R N/R N/R N/ 50 mg/L N/R Tap [130]
R water

6. Conclusions comparison with CPE. Most of MOF-modified carbon-based elec-

MOFs materials have been widely studied in recent years and its
applications for electrochemistry and electronics are unlimited;
however, the use of MOF composites in carbon-based electrodes
for direct sensing of biomolecules or inorganic compounds is new.
The aqueous media stability, pore size, and selectivity toward
similar analytes are the advantages of using of MOFs composites
as modifiers in carbon-based electrodes, likewise, to incorporate
MOF composites in carbon-based electrodes creates an inexpen-
sive powerful tool for electroanalytical chemistry.
Diverse mechanism of oxidation or reduction for several ana-
lytes has been proposed according to the metallic center of the
MOF. This capability is highly dependent on valence state from
the metal center and the pH of the media; nevertheless, there are
many questions left unanswered about the real behavior of the
MOF into/onto the carbon-based electrode and is necessary more
research about it. Several MOFs reported in this review are electro-
catalytically active and were fabricated with H3BTC (benzene-
1,3,5-tricarboxylic acid), H2BDC (terephthalic acid) and Cu2+ or
Ni2+ ions.
Different MOFs composites have demonstrating excellent selec-
tivity toward the specific analyte and in some case, the MOF mod-
ified electrode shows capability of multiple analyte sensing
according to the potential imposed. The majority of the
MOF-modified carbon-based electrodes are elaborated with GCE
due to its high reproducibility and easy modification process in
trodes reported in literature are focused on amperometric sensing
of glucose or peroxide. This is because there is an importance in
design real time glucose monitoring for the body, and the results
obtained by MOF-modified electrodes are promising due to its
capability of identify glucose in micromolar concentrations. MOF-
modified electrodes could be used to create smart devices for sens-
ing biomolecules and other compounds with a high level of relia-
bility. It is hoped that in the future, MOF materials are going to
be the cornerstone of electronic devices and will be able to design
chips to detect multiple biomolecules in a single analysis.
Declaration of competing interest
Authors of this work declare having any conflicts of interest
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ccr.2020.213263.
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