Microporous and Mesoporous Materials 360 (2023) 112722

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Microporous and Mesoporous Materials

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

Proton conductive thin films of metal-organic framework for impedance

detection of formic acid
Fang-Ru Lin a, Zhi-Yuan Liu a, Han Zhang a, Meng Liu a, Hong-Bin Luo a, *, Yang Zou a,
Xiao-Ming Ren a, b, c, **
a
State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, PR
China
b
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 211816, PR China
c
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210023, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The development of a highly efficient sensor capable of detecting formic acid is crucial for monitoring air quality
Formic acid detection and determining the leakage because of the strong corrosivity and pungency. In this work, we present the su­
MOFs periority of a proton conductive metal-organic framework (MOF) thin film as a sensing material for highly
High chemical stability
efficient detection of formic acid at room temperature. Specifically, MOF-801, a zirconium-based MOF, exhibits
Inherent proton conduction
Thin films
exceptional chemical stability and inherent proton conduction, along with a significant surface area and high
porosity. Through the solvothermal synthetic method, highly uniform and densely packed thin films of MOF-801
are successfully fabricated on glass substrates. The resulting sensor, based on MOF-801 thin films, displays
exceptional sensitivity, selectivity, and durability for detecting formic acid at room temperature, outperforming
both other MOFs based sensors and the traditional metal-oxide-based sensors that operate at high temperatures.

1. Introduction selectivity and short analysis time [24]. Over the past decade,
metal-oxide semiconductors have been widely exploited as sensing
Formic acid has been extensively utilized as antiseptic, disinfectant materials in electrochemical sensors for detecting formic acid [25–30].
and organic chemical raw material in many industries, such as leather, For instance, Su et al. synthesized a series of WO3 with different mor­
medicine and pesticide [1–8]. However, formic acid is quite susceptible phologies via hydrothermal reaction, and revealed that the WO3 nano­
to transform into its gas counterparts with strong corrosivity and pun­ rod bundles exhibited superior sensing performance toward formic acid
gency because of the high volatility, causing the production equipment at 370 ◦ C [1]. Recently, it was demonstrated that the sensing properties
and pipelines to corrode [9]. Moreover, human exposure to formic acid of metal oxides can be improved by doping. Through the flame spray
may suffer from serious dermatosis, and excessive inhalation of the acid pyrolysis, Liewhiran et al. successfully synthesized Zn-doped SnO2
may lead to severe bronchitis, chemical pneumonitis, and even death nanoparticles, showing high remarkable sensitivity and selectivity in
[10–13]. Thus, from the perspective of industry and environment, pre­ detecting formic acid at 350 ◦ C [28]. Additionally, Meng et al. demon­
cise detection of formic acid is tremendous need to determine its leakage strated the adoption of SnO2 quantum dots to dope and sensitize LaFeO3,
and monitor air quality [2,9,14–16]. and the LaFeO3 doped with SnO2 quantum dots displayed a much
To date, the detection of formic acid can be realized by the means of improved sensing performance to formic acid at 210 ◦ C [29]. Never­
chemical ionization mass spectrometry [17], gas chromatography [18], theless, the electrochemical sensors based on metal-oxide sensing ma­
colorimetric [2,19] and electrochemical sensor [20–23], among which terials must operate at a high temperature of 200–400 ◦ C to promise the
electrochemical sensor has been identified as the most promising one, sensing activity, which hinder their real-life applications for preventing
owing to the appealing advantages of facile miniaturization, high corrosion and injury from formic acid [31].

* Corresponding author.
** Corresponding author. State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech
University, Nanjing, 211816, PR China.
E-mail addresses: [email protected] (H.-B. Luo), [email protected] (X.-M. Ren).

https://doi.org/10.1016/j.micromeso.2023.112722
Received 22 May 2023; Received in revised form 29 June 2023; Accepted 4 July 2023
Available online 5 July 2023
1387-1811/© 2023 Elsevier Inc. All rights reserved.
F.-R. Lin et al. Microporous and Mesoporous Materials 360 (2023) 112722

Fig. 1. (a) Schematic illustrating the construction of MOF-801. PXRD patterns of MOF-801 powders treated with (b) hot water (80 ◦ C) and formic acid (98 wt%)
vapor, (c) hydrochloric acid and (d) sodium hydroxide aqueous for 5 days.

Metal-organic frameworks (MOFs), as an emerging family of crys­ predicted that MOF-801 thin film may display high-performance formic
talline porous materials, are composed of metal nodes and organic acid detection regarding MOF-802 thin film.
linkers, featuring exceptionally high porosity, large surface area and In this study, we present a study on the thin films of proton-
structural diversity. In recent years, MOFs are extensively exploited as conductive MOF-801 utilized as sensing materials for highly efficient
ideal sensing materials in electrochemical sensors for detecting a wide detection of formic acid at room temperature. Our findings highlight the
range of gas molecules (e.g., ammonia, nitrogen monoxide, hydrogen outstanding selectivity and exceptional durability exhibited by the MOF-
sulfide, and formaldehyde) [32–44], since their unique features of high 801 thin films, emphasizing their promising capabilities as advanced
porosity and large surface area are enable to facilitate the surface re­ sensing materials for formic acid detection.
action and adsorption of gas analytes. It is worth noting that MOFs have
been rarely developed as sensing materials toward formic acid detection 2. Experimental
[10,23,45], that is because most MOFs are tend to be decomposed when
exposed to formic acid. Li et al. demonstrated the capability of proton 2.1. Materials and chemicals
conductive MOFs with high chemical stability as sensing materials for
detecting formic acid, and realized formic acid detection at room tem­ All chemical reagents, including zirconium oxychloride octahydrate
perature, superior to metal-oxide sensing materials working at high (ZrOCl2⋅8H2O, ≥99.0%, Aladdin), fumaric acid (C4H4O4, ≥99.0%,
temperature [10,45]. Nonetheless, in their works, the electrochemical Macklin), formic acid (CH2O2, ≥99.0%, Macklin), N,N-dimethylforma­
sensors were fabricated from the MOF powders by the compressed mide (DMF, ≥99.5%, Macklin), acetic acid (C2H4O2, ≥99.0%, Macklin),
powder pellet or powder slurry casting [10,45]. It is important to note methanol (MeOH, ≥99.9%, Macklin), ethanol (EtOH, ≥99.5%, Mack­
that the compressed powder pellets are not acceptable for the integra­ lin), hydrochloric acid (HCl, 37%, Merckmillipore), sodium hydroxide
tion of sensor devices, and the sensor fabricated with powder slurry (NaOH, ≥98.0%, Aladdin) were purchased from available commercially
casting or compressed powder pellet may be subjected to poor stability sources and used without further purification.
and bad sensitivity as a consequence of the loose contacts between MOF
grain boundaries. 2.2. Preparation of MOF-801 powders
More recently, our study has shown that zirconium-based MOFs hold
great potential as sensing materials for detecting formic acid [23]. MOF-801 powders were synthesized by following the literature
Zr-MOFs are primarily composed of Zr6(μ3-O)4(μ3-OH)4 nodes and procedure [46,47]. ZrOCl2⋅8H2O (10 mmol, 3.22 g) and fumaric acid
multitopic carboxylate linkers by forming robust coordination bonds (10 mmol, 1.16 g) were first dissolved into the mixed solvent of
between Zr4+ ions and carboxylate oxygen atoms, and have exceptional DMF/formic acid (40 mL/14 mL) to give a mixture, which was then
chemical stability. In this regard, we successfully fabricated the thin transferred into a Teflon-lined autoclave (100 mL) and heated for 6 h at
films of zirconium-based MOF-802 on glass substrate, and the MOF-802 130 ◦ C. After the reaction finished, the participates of MOF-801 powders
thin film exhibited remarkable selectivity and good reproducibility in were collected through centrifugation, subsequently washed with DMF
detecting formic acid at room temperature but a mediocre response and ethanol, then dried for 24 h under vacuum at 80 ◦ C.
magnitude to formic acid [23]. Notably, MOF-801, another Zr-MOF, is
constructed from Zr6(μ3-O)4(μ3-OH)4 nodes and fumarate linkers. With 2.3. Fabrication of MOF-801 thin films
respect to MOF-802, MOF-801 shows a significantly large surface area
and higher porosity [46]. Since high porosity and large surface area are A piece of glass (size: 2.5 cm × 7.5 cm) was washed sequentially with
benefit for the surface reaction and adsorption of gas analytes, it is 0.1 M NaOH, deionized water, 0.1 M hydrochloric acid and deionized

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F.-R. Lin et al. Microporous and Mesoporous Materials 360 (2023) 112722

Fig. 2. (a) Surface and (b) cross-sectional SEM images of MOF-801 thin film. (c) XRD patterns of MOF-801 for its powder and thin film.

water via sonication for 20 min. Afterward, the glass substrate was dried water stability. As shown in Fig. 1b, the powder X-ray diffraction (PXRD)
and immersed in a solution of 1 M NaOH in water/ethanol (50 mL/50 pattern of the water-treated sample is in good agreement with that of the
mL) under sonication for 30 min, which was repeated for 3 times to as-synthesized MOF-801, implying the structure was not damaged after
make the glass surface fully hydroxylated. The glass substrate was water treatment. Afterward, the alkaline stability of MOF-801 was
finally washed with deionized water and dried at room temperature. The examined by soaking powder samples in sodium hydroxide aqueous
MOF-801 thin films on glass substrate were fabricated by using in suit solutions. As illustrated by the PXRD patterns in Fig. 1d, MOF-801 dis­
solvothermal synthetic method. Typically, the pretreated glass substrate plays remarkable alkaline stability within the pH range of 7–12. This can
was placed into the solution of ZrOCl2⋅8H2O (10 mmol, 3.22 g) and be attributed to the strong coordination bonds between the Zr atoms and
fumaric acid (10 mmol, 1.16 g) in DMF/formic acid (40 mL/14 mL), carboxylate oxygen atoms, as well as the high connectivity of
followed by reacting in a Teflon-lined autoclave (100 mL) for 6 h at Zr6(μ3-O)4(μ3-OH)4 nodes. Furthermore, MOF-801 displays exceptional
130 ◦ C. This in suit solvothermal synthesis was repeated two times for acidic stability, after the treatment of placing powder samples into hy­
fabricating a continuous and dense thin film on the glass substrate. After drochloric acid aqueous solution (8 mol/L) or formic acid (98 wt %)
that, MOF-801 thin film was washed with ethanol and dried at room vapor for 5 days, the acid-treated samples show high similar PXRD
temperature. patterns to that of the pristine MOF-801 (Fig. 1b–c). Over all, MOF-801
has excellent chemical stability to water, together with conspicuous acid
and base resistance.
2.4. General methods
Computational and experimental studies reveal that the OH groups
on Zr6(μ3-O)4(μ3-OH)4 nodes of Zr-MOFs have a low pKa value, and can
X-ray diffraction (XRD) patterns were recorded on a Rigaku Mini­
generate protonic charge carriers [48]. As a result, Zr-MOFs possess
Flex600 X-ray diffractometer equipped with Cu Kα radiation (λ =
intrinsic proton conduction [49–52]. To assess the proton conduction of
1.5404 Å). Scanning electron microscopic (SEM) images were taken by
MOF-801, AC impedance analysis has been performed on the pellet of
using a Quanta FEG-250 field emission scanning electron microscope. N2
powder sample under high humid condition. As displayed in Fig. S3,
adsorption/desorption isotherms at 77 K were performed using a
MOF-801 exhibits considerable intrinsic proton conduction, with the
Micromeritics ASAP 2020 analyzer.
proton conductivity of 1.0 × 10− 3 S cm− 1 at room temperature, 1.57 ×
Altering current (ac) impedance analysis was performed by means of
10− 3 S cm− 1 at 323 K, and 2.45 × 10− 3 S cm− 1 at 348 K that are com­
a Gamry Reference 600+ electrochemical workstation. The proton
parable to the literature value [52].
conductivity (σ) was calculated according to the equation of σ = L/RS,
In view of the compelling inherent proton conduction coupled with
in which R represents the resistance, L and S refers to the thickness and
outstanding chemical stability, MOF-801 powder slurry was drop casted
cross-sectional area of the pellet sample, respectively.
on an interdigital electrode to build an electrochemical sensor for formic
The sensing tests for sensors were conducted in a glass chamber (340
acid sensing. Upon exposure to the formic acid vapor, the concentration
mL) that equipped with a vacuum pump. The formic acid vapor with
of protonic charge carriers in MOF-801 will increased owing to the
different concentration was achieved by injecting an accurate amount of
adsorption of formic acid molecules, and the H-bond networks will be
formic acid into the testing chamber. Other volatile chemical vapors,
formed to promote the proton transfer, leading to an improved proton
including acetic acid, methanol and ethanol were also acquired from the
conduction and decreased resistance. The impedance spectroscopy of
corresponding injected liquids. The impedance spectroscopy of sensor
sensor was recorded for the detection of formic acid vapor, and the
was recorded by using a Gemary 600+ electrochemical workstation,
sensor response is referred as RAir/RGas, where RAir is the resistance in air
with the frequency of 100 Hz and a signal amplitude of 100 mV.
and RGas is the steady resistance in chemical vapor. As illustrated in
Fig. S4, the sensor displays subtle response to formic acid with the
3. Results and discussion concentration range from 8.0 × 10− 5 mol/L to 4.0 × 10− 4 mol/L, and
exhibits much small response magnitude under the response time of ca.
MOF-801 is a zirconium-based MOF that built from Zr6(μ3-O)4(μ3- 300 s, with the value of 5 and 8 for the formic acid vapor with the
OH)4 nodes and fumarate linkers (Fig. 1a), in which each Zr6(μ3-O)4(μ3- concentration of 2.4 × 10− 4 mol/L and 3.2 × 10− 4 mol/L, respectively.
OH)4 node is coordinated with 12 fumarate linkers, and the 2-connected Moreover, the sensor shows inferior performance during the successive
fumarate linkers connect the adjacent Zr6(μ3-O)4(μ3-OH)4 nodes to give reproducibility cycling test, the response magnitude is much difference
a three-dimensional framework [46]. Within the MOF-801 framework, for each cycling test (Fig. S5). The unsatisfied durability and repro­
there are one type of octahedral cavities with a diameter of 7.4 Å, along ducibility of the sensor can be ascribed to poor-quality sensing layer
with two crystallographically independent tetrahedral cavities. The di­ with many defects, which was fabricated through the loose stacking
ameters of these tetrahedral cavities are 5.6 and 4.8 Å, respectively. In between the crystalline MOF-801 particles (Fig. S6), as well as the bad
contrast, MOF-802 only possesses one type of cavity with a diameter of contact between MOF-801 particles and electrode substrate.
5.6 Å [46], showing a significantly lower porosity compared to In order to improve the sensing performance to formic acid vapor, we
MOF-801. To investigate the chemical stability of MOF-801, MOF-801 have attempted to fabricated high-quality MOF-801 thin film on glass
powder was firstly immersed in 80 ◦ C water for 5 days to evaluate the

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F.-R. Lin et al. Microporous and Mesoporous Materials 360 (2023) 112722

Fig. 3. (a) Response of MOF-801 thin film sensor to formic acid with different concentration. (b, c) Reproducibility cycles and (d) response− recovery time curve of
MOF-801 thin film sensor to formic acid with a concentration of 3.2 × 10− 4 mol/L.

substrate by solvothermal synthetic method (See experimental section). glass-supported MOF-801 thin film, and the formic acid sensing per­
As indicated by the surface-view SEM image shown in Fig. 2a and formance was further investigated. As displayed in Fig. S8 and Fig. 3a,
Fig. S7, the irregular polyhedral particles of MOF-801 are densely the senor presented a noticeable response to formic acid with the con­
stacked on the glass substrate, forming a uniform and continuous thin centration range from 8.0 × 10− 5 mol/L to 4.0 × 10− 4 mol/L, and the
film without obvious cracks or defects. The cross-sectional SEM image response magnitude is increased with the increasing formic acid con­
reveals that the MOF-801 thin film has a uniform thickness of ca. 1.2 μm, centration. Noteworthy, compared to the sensor fabricated via the drop-
moreover, the MOF-801 thin film is tightly adhered to the glass substrate casting of MOF-801 powder slurry (Fig. S4), the MOF-801 thin film
(Fig. 2b). The high crystallinity and phase purity of MOF-801 thin film sensor shows a much high response magnitude, with the response
was verified by XRD analysis. The XRD pattern of MOF-801 thin film is magnitude of 117 and 871 for the concentration of 2.4 × 10− 4 mol/L and
well consistent with that of MOF-801 powders, as well as the simulated 3.2 × 10− 4 mol/L, respectively. It is noteworthy that the response
one (Fig. 2c). The above results demonstrate the successful fabrication of magnitude of the MOF-801 thin film sensor is approximately six times
high-quality MOF-801 thin film, and it may be utilized as an efficient higher compared to that of the MOF-802 thin film sensor [23]. This
sensing layer for detecting formic acid. significant difference demonstrates that the MOF-801 thin film sensor
Next, an interdigitated electrode sensor was fabricated based on the exhibits a substantially higher sensitivity. The increased sensitivity can

4
Fig. 4. Time-dependent (a) impedances and (b) responses of the MOF-801 thin film sensor to a variety of volatile chemicals at a concentration of 3.2 × 10− mol/L.

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F.-R. Lin et al. Microporous and Mesoporous Materials 360 (2023) 112722

be attributed to the large surface area and high porosity of MOF-801, materials for formic acid detection at room temperature. The high
which enhances surface reactions and the adsorption of molecules dur­ chemical stability, inherent proton conduction, large surface area and
ing formic acid detection. Besides, the enhanced sensitivity of the high porosity of MOF-801, coupled with the high-quality thin films that
MOF-801 thin film sensor towards formic acid can also be attributed to exhibited high compactness and uniformity, enabled the sensor to
its comparatively lower proton conduction when compared to MOF-802. exhibit high sensitivity, good selectivity, and remarkable durability to­
MOF-801 exhibits a proton conductivity of 10− 3 S cm− 1, which is wards formic acid detection at room temperature. The performance of
approximately one order of magnitude lower than that of MOF-802, the sensor based on MOF thin films was found to be greatly superior to
with a proton conductivity of 10− 2 S cm− 1 [49]. Furthermore, the the sensor with its powder slurry casting, and more competitive than
sensing test with successive cycles have been performed for MOF-801 conventional metal-oxide-based sensors operating at high temperatures.
thin film sensor to evaluate the durability and reproducibility
(Fig. 3b). Fig. 3c depicts the response curves of the thin film sensor CRediT authorship contribution statement
during the successive cycling test to formic acid with the concentration
of 3.2 × 10− 4 mol/L. The response-recovery curves of each test cycle Fang-Ru Lin: Writing – original draft, Methodology, Formal anal­
possess high similarity, and the response magnitude is maintained ysis, Data curation. Zhi-Yuan Liu: Methodology, Formal analysis. Han
without significant debasement during the successive cycling test, Zhang: Software, Formal analysis. Meng Liu: Software, Methodology.
demonstrating that the thin film sensor possesses good durability and Hong-Bin Luo: Writing – review & editing, Writing – original draft,
reproducibility for the detection of formic acid. In addition, with the Supervision. Yang Zou: Writing – review & editing, Software. Xiao-
injection of formic acid, the thin film sensor exhibits a shorter response Ming Ren: Writing – review & editing, Supervision.
time of ca. 100 s (Fig. 3d) and the response is vanished quickly with the
remove of formic acid vapor, indicating the thin film sensor acquires a Declaration of competing interest
rapid response to formic acid. Apparently, MOF-801 thin film sensor
displays a high performance for formic acid sensing, being greatly su­ The authors declare that they have no known competing financial
perior to that of the sensor with drop-casted MOF-801 powder slurry. interests or personal relationships that could have appeared to influence
That is because the fabricated MOF-801 thin film features high the work reported in this paper.
compactness and good uniformity, together with the strong adhesion
between MOF-801 thin film and glass substrate, endowing the sensing Data availability
layer of MOF-801 thin film with exceptional stability and durability
during the sensing process. Data will be made available on request.
Finally, the selectivity of MOF-801 thin film sensor has been assessed
by exposing it to different volatile chemicals, i.e., acetic acid, methanol, Acknowledgements
ethanol, hydrochloric acid and methylene dichloride. As depicted in
Fig. 4a and b, in comparison with the response to formic acid, MOF-801 This work is financially supported by the Priority Academic Program
thin film sensor shows a weak response to acetic acid, methanol and Development of Jiangsu Higher Education Institutions, the National
ethanol, together with negligible response to hydrochloric acid and Natural Science Foundation of China (Grant Nos. 22073047 and
methylene dichloride, suggesting that MOF-801 thin film sensor pos­ 22101131), and Natural Science Foundation of Jiangsu Province (Grant
sesses high selectivity to formic acid. In terms of methanol and ethanol, No. BK20210543).
it is understandable that the alcohols with much high pKa values (>15)
[53], and a slight increase in the proton conduction of MOF-801 thin Appendix A. Supplementary data
film is mainly ascribed to the H-bond networks built between the
adsorbed alcohol molecules and MOF-801 frameworks. Notably, Supplementary data to this article can be found online at https://doi.
although both formic acid and acetic acid are simple carboxylic acids org/10.1016/j.micromeso.2023.112722.
that capable of providing protonic charge carriers, MOF-801 thin film
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