sensors

Review
Metal–Organic Frameworks as Active Materials in
Electronic Sensor Devices
Michael G. Campbell 1, * and Mircea Dincă 2, *
1 Department of Chemistry, Barnard College, 3009 Broadway, New York, NY 10027, USA
2 Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge,
MA 02139, USA
* Correspondence: mcampbel@barnard.edu (M.G.C.); mdinca@mit.edu (M.D.);
Tel.: +1-212-854-2074 (M.G.C.); +1-617-253-4154 (M.D.)

Academic Editor: W. Rudolf Seitz

Received: 17 April 2017; Accepted: 8 May 2017; Published: 12 May 2017

Abstract: In the past decade, advances in electrically conductive metal–organic frameworks

(MOFs) and MOF-based electronic devices have created new opportunities for the development of
next-generation sensors. Here we review this rapidly-growing field, with a focus on the different
types of device configurations that have allowed for the use of MOFs as active components of
electronic sensor devices.

Keywords: metal–organic frameworks; porous materials; gas sensors; ion sensors; biosensors

1. Introduction
Owing to their high surface areas and robust chemical tunability based on a “bottom-up” synthetic
approach, metal–organic frameworks (MOFs) are enabling new applications in chemical sensing [1–3].
However, because most MOFs have intrinsically low electrical conductivity, their use in electronic
sensor devices is limited [4,5] and most reports in this area focus on optical responses (such as
luminescence quenching or enhancement) [6–11], or more complicated device architectures such as
MOF-coated microcantilevers [12] or quartz crystal microbalances [13–15]. Advances over the past
decade have led to new synthetic approaches towards MOFs that simultaneously display permanent
porosity and high electrical conductivity and/or charge mobility [16]. These advances are now enabling
a new generation of MOF-based electronic sensor devices, which display great promise as platform for
the development of improved sensing technologies.
In this Review, we survey the burgeoning field of MOF-based electronic devices for chemical
sensing, focusing on the different types of devices and measurement techniques that have been used
to date. We will examine here only sensor devices in which the MOF functions as an active electrical
component; therefore, we exclude devices in which the MOF plays a passive role such as an adsorbent
coating or a selective molecular sieve [17,18].

2. MOF-Based Gas Sensors

To date, the majority of the published studies on MOF-based sensor devices have looked at sensing
of gases and chemical vapors. A variety of device types and configurations have been investigated,
in large part as an effort to overcome the low conductivity of most MOF materials that have been
tested. Despite the limitations imposed by low conductivity, significant progress has been made in
recent years, and MOF-based electronic sensor devices are poised to make a meaningful impact on
gas sensing.

Sensors 2017, 17, 1108; doi:10.3390/s17051108 www.mdpi.com/journal/sensors

Sensors 2017, 17, 1108 2 of 11
Sensors 2017, 17, 1108 2 of 10

2.1.
2.1. Impedance
Impedance Sensors
Sensors
The
The first
first successful
successful examples
examples of of MOF-based
MOF-based electronic
electronic sensor
sensor devices
devices used
used impedance
impedance
spectroscopy
spectroscopy to to look
look at
atresponses
responsestotodifferent
differentgases
gases and
and vapors;
vapors; in this
in this measurement
measurement technique,
technique, a higha
high bulk electrical conductivity is not required for device performance. In 2009, Achmann
bulk electrical conductivity is not required for device performance. In 2009, Achmann et al. investigated et al.
investigated
five materials:five materials:
Al-BDC [Al(OH)(BDC)], Fe-BTC [FeIII (BTC)],
Al-BDC [Al(OH)(BDC)], Fe-BTCCu-BTC
[FeIII(BTC)], Cu-BTC
[Cu3 (BTC) [Cu3(BTC)
2 ], Li-doped 2], Li-
Fe-BTC,
doped Fe-BTC, and
and Fe(II)-doped Fe-BTCFe(II)-doped Fe-BTC (BDC = 1,4-benzenedicarboxylate;
(BDC = 1,4-benzenedicarboxylate; BTC = 1,3,5-
BTC = 1,3,5-benzenetricarboxylate) [19].
benzenetricarboxylate)
Two device configurations [19]. Two
were device
used, thick configurations
films coated onto were used, thickelectrodes
interdigitated films coated(IDEs)onto
and
interdigitated
pressed pellets.electrodes
Changes in (IDEs) and pressed
impedance pellets. Changes
were measured in impedance
with varying wereofmeasured
concentrations with
O2 , CO2 , C 3 H8 ,
varying
NO, H2 , concentrations of O2, COover
ethanol, and methanol, 2, C3H , NO, of
a 8range H2,temperature
ethanol, and(120–240
methanol, ◦ C)over
and ahumidity
range of levels.
temperature
Of the
(120–240
materials°C) and only
tested, humidity
Fe-BTC levels. Of theany
displayed materials tested,
observable only Fe-BTC
responses, displayed
to ethanol, any observable
methanol, and H2 O,
responses, to ethanol,
with the response methanol,
toward water and
being H2the
O, with the response
strongest (Figure toward
1). water being the strongest (Figure1).

Figure
Figure1.1.Impe dance sesensing
Impedance nsing re sponse
response(|Z|), me asure
(|Z|), d at 1at
measured Hz,
1 of
Hz,a Fe
of-BTC thick film
a Fe-BTC se nsor
thick film de vice
sensor
to two se
device toque
twontial e xposure
sequential s to 1.5%to
exposures (v/v)
1.5%H2(v/v)
O/N2 .HImage
2 O/N re
2 . produce
Image d with pe
reproduced rmission
with from reference
permission from
[19], copyright
reference 2008 by the
[19], copyright authors.
2008 by the authors.

In a related study published in 2013, Zhang et al. fabricated devices on IDEs using NH2‐MIL‐
In a related study published in 2013, Zhang et al. fabricated devices on IDEs using NH2 -MIL-
125(Ti) ([Ti8O8(OH)4(abdc)6]; abdc = 2‐amino‐1,4‐benzenedicarboxylate) [20]. These devices were
125(Ti) ([Ti8 O8 (OH)4 (abdc)6 ]; abdc = 2-amino-1,4-benzenedicarboxylate) [20]. These devices were
sensitive to changes in relative humidity in the range 11 –95%, at an optimized frequency of 100 Hz,
sensitive to changes in relative humidity in the range 11–95%, at an optimized frequency of 100 Hz,
with response and recovery times of <1 min.
with response and recovery times of <1 min.

2.2.
2.2. Chemicapacitive
Chemicapacitive Sensors
Sensors
Changes
Changes in in capacitance
capacitance have
have also
also been
been investigated
investigated forfor MOF‐based
MOF-based sensor devices. In
sensor devices. In 2016,
2016,
Hosseini
Hosseini etetal.
al.reported
reportedthethefabrication
fabricationof ofaacapacitive
capacitivesenor
senorusing
usingCu‐BTC,
Cu-BTC,whichwhichwaswasgrown
growndirectly
directly
onto
onto aa copper substrateusing
copper substrate usingelectrochemical
electrochemical synthesis
synthesis [21].
[21]. In this
In this case,case, the copper
the copper substrate
substrate for MOFfor
MOF film growth served as the back electrode, and the top electrode was made using
film growth served as the back electrode, and the top electrode was made using connected spots of Ag connected spots
of Ag on
paste paste
topon topCu-BTC
of the of the Cu-BTC
film. Thefilm. The displayed
devices devices displayed
a reversible a reversible
“turn-on” “turn‐on”
response inresponse
capacitancein
capacitance in response to both ethanol and methanol vapor, with response/recovery
in response to both ethanol and methanol vapor, with response/recovery times on the order of several times on the
order of several
minutes. A muchminutes.
weaker A much weaker
“turn-off” response “turn‐off” response
was observed for was observed
non-polar for such
vapors non‐polar vapors
as n-hexane.
such Later
as n‐hexane.
in 2016, Yassine et al. reported a capacitive sensor fabricated by growing thin films of a
Later in
fumarate—based 2016,yttrium
YassineMOF,
et al. in
reported a capacitive sensor
which hexanuclear Y clustersfabricated by growing
are connected thin films
by fumarate of a
ligands
fumarate—based yttrium MOF,
in a UiO-66-type structure, onto in which
IDEs thathexanuclear Y clusters arewith
had been functionalized connected by fumarate
a self-assembled ligands
monolayer
in a UiO-66-type structure, onto IDEs that had been functionalized with a self-assembled
of 11-mercaptoundecanol [22]. These capacitive sensors displayed extraordinary sensitivity to H2 S monolayer
of 11-mercaptoundecanol
vapors (≤100 ppb) at room [22]. These capacitive
temperature, sensors
and high displayed
selectivity for Hextraordinary sensitivity to H2S
2 S over other gases such as NO2 ,
vapors (≤100 ppb) at room temperature, and high selectivity for H2S over other gases such as NO2,
CH4, H2, and toluene (Figure 2). The devices showed linear changes in capacitance over several orders
of magnitude H2S concentration (from 100 ppb to 100 ppm) and were stable up to 12 weeks.
Sensors 2017, 17, 1108 3 of 11

CH , H , and toluene (Figure 2). The devices showed linear changes in capacitance over several orders
4 2017,
2 17, 1108
Sensors 3 of 10
of magnitude H2 S concentration (from 100 ppb to 100 ppm) and were stable up to 12 weeks.

(a) (b)

Figure 2. Che micapacitive se nsing of H2 S using a fumarate -base d me tal–organic frame works (MOF)
Figure 2. Chemicapacitive sensing of H2 S using a fumarate-based metal–organic frameworks (MOF)
grown onto inte rdigitate d e le ctrode s (IDEs): (a) De te ction of H2 S at ppb le ve ls, showing a line ar
grown onto interdigitated electrodes (IDEs): (a) Detection of H2 S at ppb levels, showing a linear
de pe nde nce on conce ntration; (b) De monstration of se le ctivity compare d to othe r gase s. Image s
dependence on concentration; (b) Demonstration of selectivity compared to other gases. Images
re produce d with pe rmission from re fe re nce [22], copyright 2016 Wile y‐VCH Ve rlag GmbH & Co.
reproduced with permission from reference [22], copyright 2016 Wiley-VCH Verlag GmbH & Co.
KGaA, We inhe im.
KGaA, Weinheim.

In addition to the use of neat MOFs as the active component in capacitive sensors, composites
In addition to the use of neat MOFs as the active component in capacitive sensors, composites
of MOFs with organic polymers have also been investigated as active materials. In 2016, Sachdeva et
of MOFs with organic polymers have also been investigated as active materials. In 2016, Sachdeva
al. reported the use of a NH2‐MIL‐53(Al)/polyimide composite to fabricate a capacitive sensor for
et al. reported the use of a NH2 -MIL-53(Al)/polyimide
methanol vapor [23]. Devices fabricated
composite to fabricate a capacitive sensor
with the composite material displayed a lower detection
for methanol vapor [23]. Devices fabricated with the composite material displayed a lower detection
limit as compared to the polymer alone or bare electrodes. The use of MOF‐based hybrid materials
limit as compared to the polymer alone or bare electrodes. The use of MOF-based hybrid materials
for sensing has not yet been extensively explored, and may provide exciting new opportunities for
for sensing has not yet been extensively explored, and may provide exciting new opportunities for
materials development.
materials development.
2.3. Chemiresistive Sensors
2.3. Chemiresistive Sensors
Chemiresistive sensors are perhaps the simplest and therefore most desirable sensor devices,
Chemiresistive sensors are perhaps the simplest and therefore most desirable sensor devices, and
and have been extensively studied for other porous nanomaterials such as carbon nanotubes (CNTs)
have been extensively studied for other porous nanomaterials such as carbon nanotubes (CNTs) [24,25].
[24,25]. Use of MOFs as the active material in chemiresistive sensors has only recently been
Use of MOFs as the active material in chemiresistive sensors has only recently been investigated, in
investigated, in large part due to the lack of MOFs with suitable electrical conductivity. The
large part due to the lack of MOFs with suitable electrical conductivity. The development of new
development of new synthetic approaches toward MOFs that display both porosity and electrical
synthetic approaches toward MOFs that display both porosity and electrical conductivity has enabled
conductivity has enabled the first applications of these materials in chemiresistive sensors.
the first applications of these materials in chemiresistive sensors.
In 2014, the Zhang group reported two examples of using zeolitic imidizolate frameworks (ZIFs)
In 2014, the Zhang group reported two examples of using zeolitic imidizolate frameworks (ZIFs) in
in resistive sensors, by coating ZIFs onto IDEs followed by annealing. It was first reported that
resistive sensors, by coating ZIFs onto IDEs followed by annealing. It was first reported that Co(mim)2
Co(mim)2 (ZIF‐67; mim = 2‐methylimidizolate) could be used to detect formaldehyde vapor, at
(ZIF-67; mim = 2-methylimidizolate) could be used to detect formaldehyde vapor, at concentrations
concentrations as low as 5 ppm [26]. However, the sensor required elevated temperatures (150 °C) to
as low as 5 ppm [26]. However, the sensor required elevated temperatures (150 ◦ C) to operate, and
operate, and the response/recovery times were on the order of several minutes over a concentration
the response/recovery times were on the order of several minutes over a concentration range of
range of 5–500 ppm formaldehyde. Subsequently, the related material Co(im)2 (im = imidazolate) was
5–500 ppm formaldehyde. Subsequently, the related material Co(im)2 (im = imidazolate) was used
used for the detection of trimethylamine vapor [27]. The devices displayed promising long-term
for the detection of trimethylamine vapor [27]. The devices displayed promising long-term stability,
stability, over the course of several weeks, but again elevated temperatures (75 °C) were required for
over the course of several weeks, but again elevated temperatures (75 ◦ C) were required for operation
operation and long response/recovery times were observed (Figure 3). The issues of temperature and
and long response/recovery times were observed (Figure 3). The issues of temperature and response
response times for the reported ZIF-based sensors are likely a result of the low intrinsic conductivity
times for the reported ZIF-based sensors are likely a result of the low intrinsic conductivity of Co
of Co ZIF materials.
ZIF materials.
Sensors 2017, 17, 1108 4 of 11
Sensors 2017, 17, 1108 4 of 10

(a) (b)

Figure 3. Che mical vapor se nsing with a Co(im) 2 se nsor: (a) Sche matic of the MOF se nsor de vice (Vh
Figure 3. Chemical vapor sensing with a Co(im)2 sensor: (a) Schematic of the MOF sensor device
= he ating voltage ; V c = circuit voltage ; V out = output voltage ; RL = load re sistance ); (b) Re sponse
(Vh = heating voltage; Vc = circuit voltage; Vout = output voltage; RL = load resistance); (b) Response
(de fine d as the ratio of de vice re sistance unde r the vapor atmosphe re ve rsus unde r air)ofthe sensor
(defined as the ratio of device resistance under the vapor atmosphere versus under air) of the sensor
to various
to various chemical
che micalvapors
vapors asas aa function
function of
of te mpe rature (100
temperature (100 ppm
ppm vapor
vaporconce ntrations, eexposure
concentrations, xposure
time s ~30 min). Image s re produce d with pe rmission from re fe re nce [27], copyright
times ~30 min). Images reproduced with permission from reference [27], copyright 2014 American 2014 Ame rican
Che mical Socie
Chemical Society. ty.

MOFs with much higher electrical conductivity have appeared beginning in 2012, with the first
MOFs with much higher electrical conductivity have appeared beginning in 2012, with the
reports of layered two-dimensional (2D) π‐conjugated MOFs [28–30]. These advances enabled the
first reports of layered two-dimensional (2D) π-conjugated MOFs [28–30]. These advances enabled
first examples of MOF-based chemiresistors that could operate at room temperature and with
the first examples of MOF-based chemiresistors that could operate at room temperature and with
minimal power requirements. In 2015, Campbell et al. demonstrated that the conductive MOF
minimal power requirements. In 2015, Campbell et al. demonstrated that the conductive MOF
Cu3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) could be used to fabricate chemiresistive
Cu3 (HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) could be used to fabricate chemiresistive
sensors with sub-ppm sensitivity to ammonia vapor , at room temperature and with an applied
sensors with sub-ppm sensitivity to ammonia vapor, at room temperature and with an applied potential
potential of 100 mV [31]. Device performance was maintained under air with up to 60% relative
of 100 mV [31].
humidity. It was Device
also performance was maintained
found that devices fabricatedunderfromair thewith up to 60% relative
isostructural MOF Nihumidity. It was
3(HITP)2 did not
also found that devices fabricated from the isostructural MOF Ni 3 (HITP)
display sensitivity to NH3 vapor under identical conditions, indicating the potential for tuning the 2 did not display sensitivity
to NH3 vapor
sensor’s responseunder identical
based on theconditions,
MOF’s chemical indicating the potential for tuning the sensor’s response
structure.
basedSubsequently,
on the MOF’s Campbell
chemical structure.
et al. reported the use of structurally -related 2D MOFs to construct a
Subsequently, Campbell
cross-reactive sensor array that et al. reported
could the usediscriminate
successfully of structurally-related
between several 2D MOFs to construct
classes of volatilea
cross-reactive sensor array that could successfully discriminate between
organic compounds (VOCs) based on functional group [32]. The MOFs Ni3(HITP)2, Cu3(HITP)2, and several classes of volatile
organic
Cu3(HHTP) compounds (VOCs) based on functional group [32]. The MOFs Ni3 (HITP)
2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) were used,
, Cuchemiresis
and 2the 3 (HITP)2 , and
tive
Cu 3 (HHTP)
responses (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) were
of2 the devices were measured towards various VOC vapors at 200 ppm concentration used, and the chemiresistive
responses
levels (Figureof the4). devices
The were measured
individual MOF towards variousof
components VOC thevapors
sensorat array 200 ppm concentration
displayed levels
differential
(Figure 4). The individual MOF components of the sensor array displayed
responses to various groups of chemicals. Using statistical analysis , it was shown that the MOFs’ differential responses to
various groups of chemicals. Using statistical analysis, it was shown
chemiresistive responses could be used to distinguish between categories of VOCs with >90% that the MOFs’ chemiresistive
responses
accuracy.could be used to
Additionally, distinguish between categories
concentration-dependent studiesof VOCs
with amine with >90% indicated
vapors accuracy. that
Additionally,
multiple
concentration-dependent studies with amine vapors indicated that multiple
sensing mechanisms are operative, wit h high degrees of orthogonality. The mechanisms of VOC sensing mechanisms are
operative, with high degrees of orthogonality. The mechanisms of VOC
sensing with conductive 2D MOFs are still under investigation, but the preliminary results reported sensing with conductive 2D
MOFs
to dateare still under
suggest that investigation, but the preliminary
MOF‐based chemiresistors are a results
promisingreported
platform to date suggest
that that MOF-based
may offer advantages
chemiresistors are
over existing technologies.a promising platform that may offer advantages over existing technologies.
In
In 2016,
2016,Smith
Smithetetal.al.reported
reportedthe thedirect
directgrowth
growthofofMM 3 (HHTP)
3(HHTP) 22 films
films (M (M == Cu,
Cu, Ni)
Ni) onto
onto graphitic
graphitic
electrodes that had been patterned onto polymer films [33]. Consistent
electrodes that had been patterned onto polymer films [33]. Consistent with the previously-reportedwith the previously-reported
studies,
studies, devices
devices fabricated
fabricated in in this
thismanner
mannerfrom fromCu Cu3 (HHTP) displayed a chemiresistive response
3(HHTP)22 displayed a chemiresistive response
towards
towardsNH NH 3 vapor, while devices fabricated from Ni3 (HHTP)
3 vapor, while devices fabricated from 2 did not
Ni 3(HHTP) display an observable response.
2 did not display an observable
The authors further showed
response. The authors further showed that the M (HHTP)
3 that the devices could be used
2 M 3(HHTP)2 devices could to sense NO and
be used H2 S, and
to sense NO that
and
aHsensor array using the two types of devices could successfully differentiate
2S, and that a sensor array using the two types of devices could successfully differentiate between
between H 2 O, NH 3 , NO,
H2O, NH3, NO, and H2S vapors. These results reinforce the potential for creating simple MOF-based
chemiresistor devices and arrays that can offer high selectivity in ga s sensing applications.
Sensors 2017, 17, 1108 5 of 11

and H2 S vapors. These results reinforce the potential for creating simple MOF-based chemiresistor
devices and arrays that can offer high selectivity in gas sensing applications.
Sensors 2017, 17, 1108 5 of 10

Figure 4.
Figure 4. Re sponse s of
Responses of aache mire sistive se
chemiresistive nsor array,
sensor array, constructed
constructe dfrom
from conductive
conductive 2D 2D MOFs,
MOFs, toto
diffe re nt categories
different cate gorie sof
of volatile
volatile organic
organic compounds
compounds (VOCs),
(VOCs), whe
where ∆G/G
re ∆G/G 0 is the
0 isrelative
the response
relative (change
response
in conductance
(change ) upon a upon
in conductance) 30 s e xposure to 200 ppm
a 30 s exposure ofppm
to 200 the VOC
of thevapor
VOCatvapor
room temperature; eachresponse
at room temperature; is
each
ave rage d from 12 me asure me nts (4 e xposure s to 3 se parate de vices for each MOF);
response is averaged from 12 measurements (4 exposures to 3 separate devices for each MOF); error error bars show one
standard
bars show de
oneviation. Image
standard adapteImage
deviation. d withadapted
pe rmission
withfrom re fe re nce
permission from[32], copyright
reference [32],2015 Ame rican
copyright 2015
Che mical Chemical
American Socie ty. Society.

It is noteworthy that, in the work reported to date on MOF‐based chemiresistors, a wide range
It is noteworthy that, in the work reported to date on MOF-based chemiresistors, a wide range
of device fabrication methods have been used: coating the MOFs onto electrodes using a solvated
of device fabrication methods have been used: coating the MOFs onto electrodes using a solvated
“paste” [26]; drop‐casting [31,32]; solvent‐free mechanical abrasion [32]; and in situ film growth [33].
“paste” [26]; drop-casting [31,32]; solvent-free mechanical abrasion [32]; and in situ film growth [33].
These studies demonstrate that multiple fabrication techniques are viable; however, very little work
These studies demonstrate that multiple fabrication techniques are viable; however, very little work
has been done so far on understanding the effect of different deposition methods or film
has been done so far on understanding the effect of different deposition methods or film morphologies
morphologies on sensing performance. In moving towards practical applications, these additional
on sensing performance. In moving towards practical applications, these additional technical issues
technical issues will need to be systematically investigated.
will need to be systematically investigated.
2.4. Kelvin
2.4. Probe and
Kelvin Probe and Field
Field Effect
Effect Transistor
Transistor Sensors
Sensors

As with
As withchemiresistors,
chemiresistors, field
field effect
effect transistors
transistors (FETs) (FETs)
are a are a useful
useful device device configuration
configuration for sensing for
sensing because
because they have theythehave the potential
potential to be sensitive,
to be sensitive, robust, androbust, and compatible
compatible with inexpensive
with inexpensive and scalableand
scalable fabrication techniques [34,35]. Examples of MOF-based FETs are
fabrication techniques [34,35]. Examples of MOF-based FETs are rare thus far [36,37], and to our rare thus far [36,37], and to
our knowledge have not been used for chemical vapor sensing. A common
knowledge have not been used for chemical vapor sensing. A common mechanism for FET-based mechanism for FET‐based
sensor devices
sensor devices is is aa change
change in in work
work function
function ofofthe
theactive
activematerial
material upon
upon exposure
exposureto tothe
theanalyte
analytevapor.
vapor.
Changes in work function can also be measured using the Kelvi n probe
Changes in work function can also be measured using the Kelvin probe technique, which is compatible technique, which is
compatible
with MOFs with that do MOFsnot that do not
exhibit exhibitelectrical
sufficient sufficientconductivity
electrical conductivity for use
for use in FETs in FETs5).
(Figure (Figure
Several 5).
Several groups have investigated vapor sensing with MOFs via changes
groups have investigated vapor sensing with MOFs via changes in work function, using the Kelvin in work function, using the
Kelvinmethod.
probe probe method.
Although Although
such a devicesuch configuration
a device configuration is not
is not practical forpractical for use
use in sensing in sensing
technologies,
technologies,
these preliminarythesestudies
preliminary
providestudies
evidenceprovide evidence
that work thatgas
function work function
sensors such gas sensors such
as MOF-based FETs as
MOF‐based FETs should display good performance
should display good performance if they can be experimentally realized.if they can be experimentally realized.
The first
The example of
first example of this
this approach
approach was was reported
reported by by Pohle
Pohle etet al.
al. In
In 2011,
2011, using
using Cu -BTC [38].
Cu-BTC [38].
Exposures to a variety of gases (hexanal, pentanal, toluene, dimethyl ether,
Exposures to a variety of gases (hexanal, pentanal, toluene, dimethyl ether, ammonia, H2 S, ethanol, ammonia, H 2S, ethanol,

acetone) were
acetone) studied over
were studied over aa temperature
temperature range range ofof 25–200
25–200 ◦°C. Temperature had
C. Temperature had aa significant
significant effect
effect
on performance,
on performance, with with higher
higher temperatures
temperaturesleadingleadingto toaa stronger
strongerresponse.
response.Although
Although almost
almost all allofof the
the
polar analytes produced an observable response, size‐exclusion effects were
polar analytes produced an observable response, size-exclusion effects were also observed: pentanal also observed: pentanal
produced aa response
produced response whereas
whereas hexanal
hexanal diddid not;
not; additionally,
additionally,NH NH3 and
and H H2SS produced
produced aa response
response
3 2
whereas dimethyl
whereas dimethyl ether ether did
did not.
not. Finally,
Finally, the
themetal
metalused
usedfor forthe
theback
backelectrode
electrodeofof thethe
device
device (Au(Au or
or Pt) had a pronounced effect on response, suggesting that the observed responses result from aa
Pt) had a pronounced effect on response, suggesting that the observed responses resu lt from
combined effect of the MOF and the metal substrate on which it was deposited. A follow‐up study in
2013 by Davydovskaya et al. further showed the effect of analyte size on performance for aldehyde
sensing with Cu-BTC [39]. As in the initial report, studies comparing pentanal and hexanal showed
that only pentanal produced a response, consistent with a size‐exclusion effect; however, additional
measurements with ethanal and propanal showed that these smaller aldehydes also produced a
Sensors 2017, 17, 1108 6 of 11

combined effect of the MOF and the metal substrate on which it was deposited. A follow-up study in
2013 by Davydovskaya et al. further showed the effect of analyte size on performance for aldehyde
sensing with Cu-BTC [39]. As in the initial report, studies comparing pentanal and hexanal showed
Sensors
that 2017,
only 17, 1108 produced a response, consistent with a size-exclusion effect; however, additional
pentanal 6 of 10
measurements with ethanal and propanal showed that these smaller aldehydes also produced a much
much weaker
weaker response response as compared
as compared to pentanal.
to pentanal. Furthermore,
Furthermore, the response
the response to pentanal
to pentanal couldcould
only only
be
be observed at relative humidity levels ≥30%, indicating that water vapor also
observed at relative humidity levels ≥30%, indicating that water vapor also plays a role in aldehyde plays a role in aldehyde
sensing. Overall,
sensing. Overall, these
these studies
studies point
point toto the
the complexity
complexity of of MOF‐analyte
MOF-analyte interactions
interactions thatthat can
can occur
occur in in
sensing: the ability to tune pore size and chemical functionality within the MOF
sensing: the ability to tune pore size and chemical functionality within the MOF is a benefit for sensoris a benefit for sensor
development, but
development, but these
these complexities
complexities can can also
also make
make elucidation
elucidation of of sensing
sensingmechanisms
mechanismschallenging.
challenging.
Further work
Further work by by Davydovskaya
Davydovskayaet et al.
al. in
in 2014
2014 examined
examined the the sensing
sensing performance
performance for for aa series
series ofof
M-BTC frameworks (M = Co, Ni, Cd, Al) upon exposure to various linear alkanes
M-BTC frameworks (M = Co, Ni, Cd, Al) upon exposure to various linear alkanes and linear aliphatic and linear aliphatic
alcohols [40].
alcohols [40]. AsAs expected,
expected, non-polar
non-polar alkanes
alkanes had had aa negligible
negligible effect
effect on
on work
work function
function for
for all
all of
of the
the
MOFs studied, whereas the polar alcohols produced changes in work function.
MOFs studied, whereas the polar alcohols produced changes in work function. Alcohols with longer Alcohols with longer
carbon chains
carbon chains were
wereshown
shownto toproduce
produce aa stronger
stronger response,
response, andand humidity
humidity level
level was
was again
again shown
shown to to
have an
have an impact
impacton onresponse.
response.Surprisingly,
Surprisingly,the thesensing
sensing performance
performance was
was notnot significantly
significantly impacted
impacted by
by the identity of the MOF’s metal center, with all of the MOFs showing
the identity of the MOF’s metal center, with all of the MOFs showing comparable changes in comparable changes in work
work
function. A
function. Arelated
relatedstudy
studybybyPentyala
Pentyalaetetal.al.inin2016
2016 also showed
also showed similar alcohol
similar alcoholsensing behavior
sensing behavior for
Zn‐BTC
for Zn-BTC [41]. As As
[41]. with thethe
with initial studies
initial studies reported
reportedinin2011,
2011,these
theseresults
resultsmay
maysuggest
suggestthat
that in these
in these
devices the MOF/substrate interaction is more important for sensing than the
devices the MOF/substrate interaction is more important for sensing than the electronic structure of electronic structure of
the MOF
the MOF itself.
itself.

Figure 5.
Figure 5. Sche matic drawing
Schematic drawing ofof the
the Ke lvin probe
Kelvin se tup for
probe setup for measuring
me asuringchanges
change sininwork
workfunction:
function: the
the
MOF film is
MOF is grown
grown oror de posite d on top
deposited top of
ofaastationary
stationary eelectrode,
le ctrode ,which
which is
is connected
conne cte dto
toan
anoscillating
oscillating
re fe re nceelectrode,
reference e le ctrode with
, withboth
both electrodes
e le ctrode sexposed
e xpose dtotothe
the analyte
analytevapor.
vapor. Image re produce d with
Image reproduced with
pe rmission from reference [42], copyright 2016 The Royal Socie ty
permission from reference [42], copyright 2016 The Royal Society of Chemistry. of Che mistry.

As the most recent example in this class, in 2016 Stassen et al. applied the Kelvin probe approach
As the most recent example in this class, in 2016 Stassen et al. applied the Kelvin probe approach
to the detection of alkyl phosphonate nerve agents using UiO‐66‐NH2, wherein [Zr 6O4(OH)412+ ] 12+
to the detection of alkyl phosphonate nerve agents using UiO-66-NH2 , wherein [Zr6 O4 (OH)4 ]
clusters are connected by 2‐amino‐1,4‐benzenedicarboxylate ligands [42]. The test molecule dimethyl
clusters are connected by 2-amino-1,4-benzenedicarboxylate ligands [42]. The test molecule dimethyl
methylphosphonate (DMMP), used as a mimic for nerve agents such as Sarin gas, could be reversibly
methylphosphonate (DMMP), used as a mimic for nerve agents such as Sarin gas, could be reversibly
detected by changes in work function at concentrat ions as low as 3 ppb (Figure 6). Even under high‐
detected by changes in work function at concentrations as low as 3 ppb (Figure 6). Even under
humidity conditions (50% relative humidity), ppb -level concentrations of DMMP could be detected,
high-humidity conditions (50% relative humidity), ppb-level concentrations of DMMP could be
and a lower‐limit of detection was calculated to be 2 ppb. A combination of experimental and
detected, and a lower-limit of detection was calculated to be 2 ppb. A combination of experimental
theoretical studies suggests that the high sensitivity towards DMMP results from the presence of
and theoretical studies suggests that the high sensitivity towards DMMP results from the presence of
missing‐linker defect sites that create unique binding pockets within the material.
missing-linker defect sites that create unique binding pockets within the material.

Figure 6. Se nsing re sponse of UiO-66-NH2 to dime thyl me thylphosphonate (DMMP) at ppb

 methylphosphonate (DMMP), used as a mimic for nerve agents such as Sarin gas, could be reversibly
detected by changes in work function at concentrat ions as low as 3 ppb (Figure 6). Even under high‐
humidity conditions (50% relative humidity), ppb -level concentrations of DMMP could be detected,
and a lower‐limit of detection was calculated to be 2 ppb. A combination of experimental and
theoretical studies suggests that the high sensitivity towards DMMP results from the presence of
Sensors 2017, 17, 1108 7 of 11
missing‐linker defect sites that create unique binding pockets within the material.

Sensors 2017, 17, 1108 7 of 10

3. MOF-Based Ion Sensors and Biosensors

There have been limited examples so far of using MOFs for solution-phase sensing of ions or
biologically relevant molecules. The lack of work in this area may be due, in part, to the fact that
many MOFs are not stable in water; however, water ‐stable MOFs have been extensively developed
Figure 6. Se nsing re sponse of UiO-66-NH2 to dime thyl me thylphosphonate (DMMP) at ppb
in recent
Figure 6.years, including
Sensing responsesomeofofUiO-66-NH
the conductive 2D MOFs described
to dimethyl above. This(DMMP)
methylphosphonate area of research
at ppb
conce ntration le ve ls, me asure d using a Ke lvin 2 probe se tup (CPD = contact potentialdifference).Image
therefore seems
concentration ripe for exploration in the near future.
re producelevels, measured
d with pe rmissionusing
from re a ference
Kelvin[42],
probe setup (CPD
copyright = contact
2016 The potential
Royal Socie difference). Image
ty of Chemistry.
An example
reproduced of ion sensing
with permission was reported
from reference in 2013 by
[42], copyright 2016Wang et al.,
The Royal in which
Society Cu -BTC/CNT
of Chemistry.
composites were used for the detection of nanomolar quantities of lead [43]. The experiment was
conducted by modifying a glassy carbon electrode (GCE) surface with the MOF/CNT composite, itself
3. MOF-Based Ion Sensors and Biosensors
produced solvothermally. Lead, from solution, was allowed to accumulate on the modified electrode
surface, and was
There have beenthen quantified
limited usingso
examples differential pulse
far of using anodic
MOFs forstripping voltammetry
solution-phase (Figure
sensing 7). or
of ions
The modified electrodes were more sensitive towards lead as compared to a bare
biologically relevant molecules. The lack of work in this area may be due, in part, to the fact that many GCE surface, and
MOFs theare
measurement
not stable inmethod w as validated
water; however, by measuring
water-stable MOFs several
have beenstandard lead-containing
extensively developedwater
in recent
samples and comparing to the certified values for the standards.
years, including some of the conductive 2D MOFs described above. This area of research therefore
Co(mim)2 (ZIF‐67) has also been used to prepare modified GCEs, as reported by Zhao et al. in
seems ripe for exploration in the near future.
2015 [44]. These ZIF-modified electrodes efficiently detected glutathione, a tripeptide that plays a key
An example of ion sensing was reported in 2013 by Wang et al., in which Cu-BTC/CNT composites
role in cellular processes, in solution. In addition to the chemical structure, it was found that the
were used for the detection of nanomolar quantities of lead [43]. The experiment was conducted by
faceting of the ZIF‐67 crystals had an impact on the sensing performance, with the {110} facets proving
modifying
optimal.a glassy carbon electrode (GCE) surface with the MOF/CNT composite, itself produced
solvothermally.
A handful Lead, from examples
of other solution, was allowed to
of biosensing accumulate
using MOFs have on the
beenmodified
reported,electrode
targetingsurface,
glucoseand
was and
thenlipopolysaccharide
quantified using differential pulse anodic
[45,46]. However, in thesestripping
cases the voltammetry (Figure 7).
MOFs serve primarily The modified
as carriers or
electrodes were more
encapsulating sensitive
agents, rathertowards
than as lead as compared
the active to a bare Moving
electrocatalysts. GCE surface,
forward,andwetheexpect
measurement
that
method was
recent validated by
developments in measuring several conductive
using water‐stable, standard lead-containing water samples
MOFs as electocatalysts will leadand comparing
to expanded
applications
to the in aqueous
certified values for thesensing of ions and biomolecules [47,48].
standards.

Figure 7. Se nsing of le ad in solution using an e le ctrode modifie d with a Cu-BTC/CNT composite ; the
Figure 7. Sensing of lead in solution using an electrode modified with a Cu-BTC/CNT composite; the
plot shows diffe re ntial pulse voltammograms re corde d at varying le ad conce ntrations, andthe inset
plot shows differential pulse voltammograms recorded at varying lead concentrations, and the inset
shows the line ar re lationship be twe e n pe ak curre nt and le ad conce ntration. Image re pro ducedwith
shows the linearfrom
pe rmission relationship between
reference [43], peak2013
copyright current and lead
The Royal Socieconcentration. Image reproduced with
ty of Che mistry.
permission from reference [43], copyright 2013 The Royal Society of Chemistry.
4. Outlook
The field of MOF-based sensors is rapidly expanding to include electronic sensor devices that
feature MOFs as an active component. Although early work in t his area was limited by a lack of
efficient signal transduction due to the insulating behavior of most MOFs, the work described here
clearly shows that the field is beginning to move beyond these limitations. Most significant in this
Sensors 2017, 17, 1108 8 of 11

Co(mim)2 (ZIF-67) has also been used to prepare modified GCEs, as reported by Zhao et al. in
2015 [44]. These ZIF-modified electrodes efficiently detected glutathione, a tripeptide that plays a
key role in cellular processes, in solution. In addition to the chemical structure, it was found that
the faceting of the ZIF-67 crystals had an impact on the sensing performance, with the {110} facets
proving optimal.
A handful of other examples of biosensing using MOFs have been reported, targeting glucose
and lipopolysaccharide [45,46]. However, in these cases the MOFs serve primarily as carriers or
encapsulating agents, rather than as the active electrocatalysts. Moving forward, we expect that
recent developments in using water-stable, conductive MOFs as electocatalysts will lead to expanded
applications in aqueous sensing of ions and biomolecules [47,48].

4. Outlook
The field of MOF-based sensors is rapidly expanding to include electronic sensor devices that
feature MOFs as an active component. Although early work in this area was limited by a lack of
efficient signal transduction due to the insulating behavior of most MOFs, the work described here
clearly shows that the field is beginning to move beyond these limitations. Most significant in this
sense is the continued development of chemical strategies for the synthesis of electrically conductive
MOFs, which will provide a source of promising new materials candidates. Computational studies that
identify potential candidates for devices from among the thousands of known MOFs will also prove
important: such studies have already pointed towards possible materials for MOF-based sensors and
sensor arrays [49–51]. Furthermore, successful demonstrations of MOF-based functional devices have
begun to appear in recent years [52,53], including the sensor devices described here. We believe that
a focus should be placed on targeting practical devices with the potential for “real-world” use, such
as chemiresistors and FETs. Because of their ease of fabrication, low power requirements, and ready
integration into more complex circuitry, these categories of devices represent an exciting opportunity
for MOFs to make a significant impact in the field of sensing.

Conflicts of Interest: The authors declare no conflict of interest.

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