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Article

Bismuth-Based Metal–Organic Framework as a Chemiresistive Sensor for Acetone Gas Detection

by
Ashraf Ali
1,
Yaser E. Greish
2,
Reem H. Alzard
2,
Lamia A. Siddig
2,
Ahmed Alzamly
2,
Naser Qamhieh
1 and
Saleh T. Mahmoud
1,*
1
Department of Physics, United Arab Emirates University, Al-Ain 15551, United Arab Emirates
2
Department of Chemistry, United Arab Emirates University, Al-Ain 15551, United Arab Emirates
*
Author to whom correspondence should be addressed.
Nanomaterials 2023, 13(23), 3041; https://doi.org/10.3390/nano13233041
Submission received: 11 November 2023 / Revised: 25 November 2023 / Accepted: 25 November 2023 / Published: 28 November 2023
(This article belongs to the Special Issue Metal Organic Framework (MOF)-Based Micro/Nanoscale Materials)
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Abstract

:
Analyzing acetone in the exhaled breath as a biomarker has proved to be a non-invasive method to detect diabetes in humans with good accuracy. In this work, a Bi-gallate MOF doped into a chitosan (CS) matrix containing an ionic liquid (IL) was fabricated to detect acetone gas with a low detection limit of 10 ppm at an operating temperature of 60 °C and 5 V operating bias. The sensor recorded the highest response to acetone in comparison to other test gases, proving its high selectivity along with long-term stability and repeatability. The sensor also exhibited ultra-fast response and recovery times of 15 ± 0.25 s and 3 ± 0.1 s, respectively. Moreover, the sensor membrane also exhibited flexibility and ease of fabrication, making it ideal to be employed as a real-time breath analyzer.

1. Introduction

As the world advances in technology and industries, this has also caused pollution of the environment to accelerate. The polluted environment harbors diseases that affect the pace of human existence. Focusing on one form of pollution, in line with the advancement in technology, there has been an exponential decline in the quality of the air we breathe. Low quality of the air has adverse effects on our health and lifestyle. In response to this scenario, the diagnosis of diseases triggered by this poor air quality at early stages greatly increases the chances of early treatment and the betterment of the individual’s health.
Amazingly, the human breath incorporates a lot of gases that can divulge information on the health state, but only if we have a way to decipher the data. Hence, sensors that can detect and distinguish these gases in real-time offer an inexpensive, non-invasive approach to gaining diagnostic information on the diseases people may have developed from inhaling polluted air. The gases that are exhaled by humans mostly contain a mixture of CO2, N2, H2O, O2, and trace levels of other volatile organic compounds (VOCs) such as ethane or acetone, to name a few. These gases assist as biomarkers in the detection of many diseases such as diabetes, lung cancer, etc. [1,2,3,4,5]. Acetone is a product of a biological process between the human and the invading micro-organisms. It then infuses into the bloodstream and is transported to the lungs. From here, it becomes a key component in the exhaled breath [6], enabling us to detect its concentration, based on which we can non-invasively distinguish numerous diseases. According to the World Health Organization (WHO), the level of acetone in a healthy human is supposed to be 0.2–1.8 ppm, in contrast to a diabetic patient, in whom it is between 1.25 and 2.5 ppm [7]. Determining the concentrations in terms of parts per billion (ppb) has proved to be quite a challenge, but there have been a few materials [8,9] that have been up for the task.
Researchers have not only been making groundbreaking advances in materials with the potential for acetone detection, but they have also been using acetone as a cleaning agent and solvent for their experimentations [10,11]. However, it has been demonstrated that prolonged exposure to acetone vapors exceeding 173 ppm can cause long-term health issues such as central nervous system anesthesia, skin and eye irritation, narcosis, nausea, headaches, and dizziness [12,13,14,15,16]. It is also flammable and explosive, with lower and upper explosive limits of 2.6% and 12.8%, respectively [17].
Metal–organic frameworks (MOFs) have been demonstrated to be a key component in developing devices that can detect hazardous gases evolving due to various processes. MOFs consist of metal cations lined by organic ligand molecules [18,19]. With properties like high porosity and tunable surface area diversity in structures, they have various applications such as gas separation and storage [20], catalysis [21], and energy applications and as sensing materials [22,23,24,25]. However, there is one obstacle for some of them, which is related to their high electrical resistance. As standalone materials, they would not serve the purpose of their designs, but when they are combined into an organic–inorganic matrix with ionic liquids (ILs), they can exhibit changes in their properties that can be recorded and evaluated.
Sensors based on these materials tend to operate under various principles such as impedance sensing [26], chemicapacitive sensing [27], chemiresistive sensing, Kelvin probe [28], capacitive sensing [29], field effect transistors [30,31], optical sensing, fluorescence sensing for the detection of various materials such as volatile gases, hazardous gases, and explosive compounds [32,33,34], ion sensing [35], biosensing [36,37], humidity sensing [38,39,40], pH sensing [41,42], and temperature sensing [43]. There are rapid photophysical, electrical, or mechanical changes in the properties of the material, with various circumstances that influence the behavior depending on the concentration of the analyte, active materials, ability to bond, electron accepting–donating ability, and hydrogen bonding, to name a few [44]. From the aforementioned principles, one of the simplest is chemiresistive sensing, which measures the change in resistance of the sensing material when exposed to the target gas. The mechanism of sensing in these materials is attributed to the transfer of electrons or holes, which results in an interaction between the surface of the sensing material and the target gas molecules via adsorption or surface reactions. Other advantages that these chemiresistive sensors have to offer are low cost of fabrication, easy integration with other electronic components for commercial devices, low operational costs, and ease of miniaturization [23,45,46]. In addition, the ability to detect trace-level analytes with efficiency and accuracy enables them to be successfully commercialized.
The change in resistance in these sensing materials is dependent on the type of material. With the diversity in the MOF and MOF-based materials, the sensing mechanism can also be altered. The interaction of the test gas on the surface can either donate an electron to the material or deprive it of one, thereby causing a change in resistance [47]. The linkers or the active functional organic groups that are used in the synthesis of these materials serve as effective adsorption sites that facilitate the transfer of charges within the system. Depending on the test gas, the reduction or oxidization reaction [48], due to its interaction with the material, can also be the cause for the change in the resistance of the material. Another parameter is the change in volume of the MOF on interaction with the gas modulating the number of electrons that are transferred during the interaction [49]. Depending on the concentration of the gas, the response of the sensor is recorded. As the synthesis methods of the materials advance, the MOFs show enhanced conductivities and porosities that increase the sensitivities multifold.
Bismuth-based materials have been traditionally used for cosmetics and drug delivery. Wang et al. [50] reported an elaborate study deciphering the structure of the Bi-MOF. Furthermore, Z. Wang et al. [51] reported a detailed review of the Bi-based MOFs and their derivatives, outlining that they have been traditionally used in catalysis applications [21,52,53], electrocatalysis, sensors [54], CO2 capture [51], electrochemical energy storage [20,55], biomedical imaging [56], drug delivery, fluorescence sensing [51], absorption, and separation [52,57]. Mirica et al. [58], meanwhile, reported the synthesis and characterization of Bi-based MOFs for the detection of VOC compounds such as acetone, MeOH, and EtOH. They demonstrated that the material can also detect NO and NH3 at room temperature. Some of the reported sensors from the literature have been consolidated in Table 1 for comparison with our work.
Our group has demonstrated that chitosan (CS) polymer incorporation with glycerol, as an IL [65], can detect H2S gas at 15 ppm operating at 80 °C [24]. Conventionally, it has also been used in combination with MOFs and ZIFs [25,59] to enhance the detection of H2S at room temperature. To the best of the authors’ knowledge, the Bi-gallate MOF has not been used as an acetone sensor in combination with an organic matrix. Hence, in this work, we present the possibility of employing the Bi-gallate MOF in combination with CS/IL matrix as an acetone sensor with a breath analyzer application for the detection of diabetic patients.

2. Materials and Methods

2.1. Materials

Bismuth (III) nitrate pentahydrate (Bi(NO3)3·5H2O), gallic acid (3,4,5-trihydroxybenzoic acid), and anhydrous dimethylformamide (DMF) were bought from Sigma-Aldrich, St. Louis, MO, USA. Chitosan (MW = 50,000–190,000 Da) (≥75%) and acetic acid were purchased from Polysciences, Warrington, PA, USA. Glycerol, as an ionic liquid (IL) (99.5%), was purchased from Quarek Corp company, Denver, CO, USA. All chemicals were used without further purification.

2.2. Synthesis of Bi-Gallate MOF

Bi-gallate MOF was synthesized following a slightly modified version of a previously published procedure [50]. In a scintillation vial, gallic acid (17 mg, 2 mmol) was dissolved in 3 mL of deionized water. Then, drops of 4 M NH4OH were added to the solution until the pH reached 8.5. In a separate scintillation vial, Bi(NO3)3·5H2O (24 mg, 1 mmol) was dissolved in 1 mL of DMF and then gradually added with continuous stirring to the gallic acid solution. The vial was sealed and placed in a preheated oven set at 85 °C for a duration of 24 h. After completion of the reaction, the resulting yellow powder was filtered and successively washed with distilled water and ethanol. Then, the Bi-gallate compound was subjected to activation in a vacuum oven at 90 °C for 24 h to remove any trapped solvent molecules.

2.3. Fabrication of the Bi-Gallate MOF/CS/IL Membrane

The Bi-gallate MOF/CS/IL membrane was fabricated by dissolving 2 wt% (0.4 g) of the Bi-gallate MOF with 0.4 g of CS and 5 vol% of IL into 20 mL of 3% acetic acid solution. The solution was then stirred for 24 h at room temperature and 1400 RPM on a magnetic stirrer. The prepared solution was then cast on a Petri dish and dried at 70 °C for 18 h in a drying oven. A flexible and uniform membrane formed, as shown in Figure 1. The thickness of the membrane was determined to be 0.20 mm using a screw gauge.

2.4. Characterization

Powder X-ray diffraction (PXRD) was conducted using a Rigaku MiniFlex X-ray diffractometer (Rigaku, Tokyo, Japan) with a CuKα radiation tube (wavelength = 1.542 Å) operated at 40 kV. PXRD measurements were taken within a 3° to 50° 2θ range at a rate of 2° min−1. Scanning electron microscopy (SEM) was performed using JSM-6010LA, JEOL, Tokyo, Japan, with an operating voltage of 5 keV. The secondary electron imaging configuration was used to procure the images with a working distance of 14 mm. The samples were made conductive with a gold sputtering system. The surface area and porosity were examined using nitrogen sorption analysis at 77 K. The N2 adsorption–desorption isotherm indicated gas adsorption (cm3 g−1) in relation to relative pressure (P/P0). Here, P represents N2 equilibrium pressure, and P0 represents saturated vapor pressure at 77 K. Prior to surface measurements, powder samples were placed in a glass tube and subjected to vacuum at 353 K for 3 h. Thermogravimetric analysis (TGA) was performed using a TGA-50 Shimadzu analyzer (Shimadzu, Kyoto, Japan) with an aluminum pan sample holder. FTIR analysis was carried out using a Shimadzu IRAffinity-1S with a scan range from 400 to 4000 cm−1.

2.5. Sensor Fabrication and Gas Testing

The sensor prototype was fabricated by sandwiching the active layer between a Cu plate with dimensions 1.5 cm × 1.5 cm as the bottom electrode and a stainless steel mesh with a grid size of 250 μm × 250 μm serving as the top electrode [59,66]. The layers were confined using temperature-resistive Kapton tape. The device was connected to the sensing system with electrical probes which were housed in a Teflon chamber connected to Bronkhorst mass flow controllers (MFCs). The setup was sealed to avoid leaking of the test gas and placed inside the fume hood for safety. The humidity of the chamber was maintained close to 0% throughout the testing sequences. The gas testing programs were sequenced to expose the sample to test gas in between cycles of synthetic air to exfoliate any residual test gas molecules.

3. Results and Discussion

3.1. Structural and Morphological Characterization of Bi-Gallate MOF and Bi-MOF/CS/IL Membrane

The structural analysis of the Bi-gallate MOF and Bi-gallate MOF/CS/IL membranes was carried out using the XRD patterns obtained. The XRD pattern in Figure 2 confirmed the structure and phase purity of the synthesized Bi-gallate MOF. By comparing the resulting diffraction pattern with the simulated pattern derived from single-crystal data as previously reported [50], it was confirmed that the Bi-gallate we prepared was successfully and purely synthesized. The Bi-gallate material exhibited an orthorhombic lattice and unit cell dimensions of a = 8.80 Å, b = 4.66 Å, c = 24.09 Å. The XRD pattern of the Bi-gallate MOF/CS/IL with a broad hump confirmed the incorporation of the Bi-gallate MOF into the CS matrix, as can be seen in the top pattern in Figure 2. The characteristic peaks representing the (110), (310), (321), and (421) planes were observed.
The FTIR analysis of Bi-gallate MOF and Bi-gallate MOF/CS/IL membrane confirmed the interaction within the framework of Bi-gallate and confirmed its presence within the composite, as shown in Figure 3. The disappearance of the hydroxyl group (-OH) band confirmed the chelation of bismuth metal with the gallic acid linker. Furthermore, a band was observed around 1671 cm−1, which is attributed to the presence of (C=O) of a carboxylate (COO−) group. Analyzing the spectra of the Bi-gallate MOF/CS/IL membrane, a broad band at 3400 cm−1 was observed in the FTIR spectrum, and is attributed to the NH and OH stretching vibration, as well as the intermolecular hydrogen bonds of chitosan. Additionally, the bands at 2900 and 3000 cm−1 belong to the symmetric and asymmetric stretching of the C-H bond of chitosan, respectively. Meanwhile, the C-O bending and C-O stretching vibrations of chitosan were determined at 1100 and 980 cm−1, respectively. The presence of Bi-gallate MOF within the chitosan membrane was further confirmed through the sharp bands at 1700 and 1209 cm−1, which, respectively, belong to C=O and C-O stretching of the gallate linker. As can be observed in Figure 3, the band frequencies that are attributed to the carboxylate group (at 1671 cm−1) and the Bi-O group (at 439 cm−1) remained intact, which also confirms the stability of the MOF framework within the chitosan membrane.
The thermal analysis of the as-synthesized Bi-gallate MOF was performed using TGA under a nitrogen atmosphere (Figure 4). In the temperature range of room temperature to 150 °C, the sample experienced a weight reduction of approximately 10%, corresponding to the loss of water molecules. This finding aligned with previously reported results [50]. Decomposition of the Bi-gallate commenced in the range of 260–350 °C, and is attributed to the breakdown of the gallate linker of the MOF structure. From the TGA curves of the Bi-gallate MOF/CS/IL membrane, we can surmise that the first weight loss observed would be due to the loss of water molecules from the pores of the framework. The drastic loss in weight observed between 150 °C and 225 °C indicates the onset of the decomposition of the gallate linker from the matrix, followed by a gradual loss in weight due to the continued decomposition of the remaining linkers.
The SEM analysis of the Bi-gallate MOF powder, shown in Figure 5A, shows that the morphology of the as-synthesized powder is comparable to the reported morphologies of the same MOF [50]. The SEM micrographs of the Bi-gallate MOF/CS/IL membranes shown in Figure 5B displayed the incorporation of the MOFs into the matrix. The cross-section of the membrane showed numerous pores, as can be seen in Figure 5C. The EDX spectra we recorded of the as-synthesized MOF (Figure 5D) and the composite membrane (Figure 5E) showed the homogeneous distribution of the Bi-gallate MOF particles within the chitosan matrix.
The as-synthesized Bi-gallate MOF powder was also subjected to N2 adsorption measurements to evaluate the micro- and macroporosity in the MOF. The recorded loop shown in Figure 6 follows a type I isotherm with a calculated Brunauer–Emmett–Teller (BET) surface area of 31.58 m2/g, and shows a maximum pore volume of 0.0135 cm3/g.

3.2. Gas Sensing Performance

The sensor prototype was set up as detailed in our previous reports [59,66]. The CS/IL matrix was doped with different concentrations of Bi-gallate MOF. The membranes were subjected to different test gases at 100 ppm to evaluate their response. It was evaluated that 2 wt% doping of the Bi-gallate MOF into the CS/IL matrix was most sensitive toward acetone gas at an operating temperature of 60 °C and a bias voltage of 5 V. The response of the sensor was evaluated using Equation (1):
S   % = R g − R a R a × 100 = ∆ R R a × 100
where Ra is the resistance of the sensor in synthetic air and Rg is the resistance in the presence of the test gas.
The sensor was evaluated in terms of sensitivity, which showed a response to 10 ppm of acetone gas at 60 °C, as plotted in Figure 7. The inset graph shows the sensor’s response toward different concentrations of acetone gas. The sensor was further analyzed toward other test gases at 100 ppm and an operating temperature of 60 °C.
The other aspects of evaluation were repeatability and stability. The tests were performed with exposure to 100 ppm of acetone, with synthetic air flushing in between each cycle to exfoliate any residual molecules from the previous cycle. The stability response was calculated as 42.41 ± 1.8%, whereas the repeatability of the sensor was calculated as 39.95 ± 1.4% (Figure 8).
Another aspect of evaluating the sensor’s performance is the response and recovery times, which can be defined as the time taken from gas exposure for the sensor to reach 90% of its recorded response, and the time taken for the sensor to recover to 10% of its initial resistance from the shutdown of the gas, respectively. From the results shown in Figure 9A, the responses recorded were calculated as 15 ± 0.25 s and 3 ± 0.1 s, respectively. Yet another vital parameter is the selectivity among other test gases. It was recorded that the sensitivity toward acetone was the highest among other test gases such as H2, H2S, C2H4, CO, and CO2, as shown in Figure 9B.

3.3. Gas Sensing Mechanism

The mechanism of the standalone CS–IL membrane was outlined by Hani et al. [24]. The functional groups along the chitosan polymeric matrix (-OH and -NH2) interact with the highly hydroxylated IL molecules through the formation of a network of H bonding. In the presence of hydroxy- and carboxy-functionalized Bi-gallate MOF particles in the matrix, an extended network of H bonding is produced, as shown in Figure 10. Compared with slightly polar or non-polar gas molecules, H2S and acetone showed adsorption to this H-bonded network by taking part in the network through H bonding, as well. This was observed when a low proportion of the Bi-gallate MOF (0.5 wt%) was added, as shown in Figure 9C. Upon increasing the proportion of Bi-gallate MOF to 2 wt%, a higher tendency of acetone to adsorb onto the extensively formed H-bonded network was observed, as shown in Figure 9B. Compared with H2S molecules with a dipole moment of 0.95 D, the preferential adsorption of acetone molecules is attributed to its higher polarity (with a dipole moment of up to 4.19 D). It should be mentioned that the highly polar acetone molecules interact with the H-bonded network of chitosan containing IL and Bi-gallate through the attraction of its highly polar C=O group to the H atoms along the other components of the sensor. Accordingly, an increase in the sensitivity of the composite sensor membrane was observed when increasing the Bi-gallate component of the sensor.

4. Conclusions

This study demonstrates the potential of fabricating a fast response and ultra-fast recovery sensor based on Bi-gallate MOF doped into a chitosan matrix containing IL. The fabricated membrane was investigated for its sensing performance. Previous studies conducted by our group demonstrated that CS/IL membranes showed potential for sensing toward H2S gas, and doping the matrix with 2 wt% Bi-gallate MOF showed sensitivity toward acetone vapor alone with a 5 V bias. The detection limit of the prototype is 10 ppm of acetone at 60 °C, with ultra-fast response and recovery times of 15 ± 0.25 s and 3 ± 0.1 s, respectively. The components of the membrane do not cause any harm to the environment, hence making the prototype highly eco-friendly. The proposed membrane can be used as an acetone sensor with ultra-fast response and recovery times, which can be used as a real-time breath analyzer.

Author Contributions

Conceptualization, Y.E.G. and S.T.M.; data curation, A.A. (Ashraf Ali), R.H.A. and N.Q.; formal analysis, A.A. (Ashraf Ali); funding acquisition, S.T.M.; investigation, A.A. (Ashraf Ali), R.H.A. and L.A.S.; methodology, A.A. (Ashraf Ali), R.H.A. and L.A.S.; project administration, S.T.M.; supervision, S.T.M.; validation, A.A. (Ashraf Ali), Y.E.G., A.A. (Ahmed Alzamly) and S.T.M.; writing—original draft, A.A. (Ashraf Ali), Y.E.G. and S.T.M.; writing—review and editing, A.A. (Ashraf Ali), Y.E.G., R.H.A., L.A.S. and S.T.M. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by United Arab Emirates University (grants code G00004169, 12R165-Research Center-ZCHS-2-2023, and grants code USRP-G00003232 with fund code 31R238-M4).

Data Availability Statement

The data that support the findings of this study are available from the corresponding authors upon request.

Acknowledgments

The authors are thankful for the financial support and Facilities provided by United Arab Emirates University.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Güntner, A.T.; Pineau, N.J.; Chie, D.; Krumeich, F.; Pratsinis, S.E. Selective sensing of isoprene by Ti-doped ZnO for breath diagnostics. J. Mater. Chem. B 2016, 4, 5358–5366. [Google Scholar] [CrossRef] [PubMed]
  2. Chen, H.; Bo, R.; Shrestha, A.; Xin, B.; Nasiri, N.; Zhou, J.; Di Bernardo, I.; Dodd, A.; Saunders, M.; Lipton-Duffin, J. NiO–ZnO nanoheterojunction networks for room-temperature volatile organic compounds sensing. Adv. Opt. Mater. 2018, 6, 1800677. [Google Scholar] [CrossRef]
  3. de Lacy Costello, B.; Amann, A.; Al-Kateb, H.; Flynn, C.; Filipiak, W.; Khalid, T.; Osborne, D.; Ratcliffe, N.M. A review of the volatiles from the healthy human body. J. Breath Res. 2014, 8, 014001. [Google Scholar] [CrossRef] [PubMed]
  4. Rudnicka, J.; Kowalkowski, T.; Buszewski, B. Searching for selected VOCs in human breath samples as potential markers of lung cancer. Lung Cancer 2019, 135, 123–129. [Google Scholar] [CrossRef] [PubMed]
  5. Guntner, A.T.; Abegg, S.; Konigstein, K.; Gerber, P.A.; Schmidt-Trucksass, A.; Pratsinis, S.E. Breath sensors for health monitoring. ACS Sens. 2019, 4, 268–280. [Google Scholar] [CrossRef] [PubMed]
  6. Schnabel, R.; Fijten, R.; Smolinska, A.; Dallinga, J.; Boumans, M.-L.; Stobberingh, E.; Boots, A.; Roekaerts, P.; Bergmans, D.; van Schooten, F.J. Analysis of volatile organic compounds in exhaled breath to diagnose ventilator-associated pneumonia. Sci. Rep. 2015, 5, 17179. [Google Scholar] [CrossRef] [PubMed]
  7. Masikini, M.; Chowdhury, M.; Nemraoui, O. Metal oxides: Application in exhaled breath acetone chemiresistive sensors. J. Electrochem. Soc. 2020, 167, 037537. [Google Scholar] [CrossRef]
  8. Majhi, S.M.; Ali, A.; Greish, Y.E.; El-Maghraby, H.F.; Qamhieh, N.N.; Hajamohideen, A.R.; Mahmoud, S.T. Accordion-like-Ti3C2 MXene-based gas sensors with sub-ppm level detection of acetone at room temperature. ACS Appl. Electron. Mater. 2022, 4, 4094–4103. [Google Scholar] [CrossRef]
  9. Majhi, S.M.; Ali, A.; Greish, Y.E.; El-Maghraby, H.F.; Mahmoud, S.T. V2CTX MXene-based hybrid sensor with high selectivity and ppb-level detection for acetone at room temperature. Sci. Rep. 2023, 13, 3114. [Google Scholar] [CrossRef]
  10. Xu, X.; Chen, Y.; Ma, S.; Li, W.; Mao, Y. Excellent acetone sensor of La-doped ZnO nanofibers with unique bead-like structures. Sens. Actuators B 2015, 213, 222–233. [Google Scholar] [CrossRef]
  11. Xiao, T.; Wang, X.-Y.; Zhao, Z.-H.; Li, L.; Zhang, L.; Yao, H.-C.; Wang, J.-S.; Li, Z.-J. Highly sensitive and selective acetone sensor based on C-doped WO3 for potential diagnosis of diabetes mellitus. Sens. Actuators B 2014, 199, 210–219. [Google Scholar] [CrossRef]
  12. Toda, K.; Furue, R.; Hayami, S. Recent progress in applications of graphene oxide for gas sensing: A review. Anal. Chim. Acta 2015, 878, 43–53. [Google Scholar] [CrossRef] [PubMed]
  13. Du, Y.; Xue, Q.; Zhang, Z.; Xia, F. Great enhancement in H2 response using graphene-based Schottky junction. Mater. Lett. 2014, 135, 151–153. [Google Scholar] [CrossRef]
  14. Xu, K.; Fu, C.; Gao, Z.; Wei, F.; Ying, Y.; Xu, C.; Fu, G. Nanomaterial-based gas sensors: A review. Instrum. Sci. Technol. 2018, 46, 115–145. [Google Scholar] [CrossRef]
  15. Perreault, F.; De Faria, A.F.; Elimelech, M. Environmental applications of graphene-based nanomaterials. Chem. Soc. Rev. 2015, 44, 5861–5896. [Google Scholar] [CrossRef]
  16. Amiri, V.; Roshan, H.; Mirzaei, A.; Neri, G.; Ayesh, A.I. Nanostructured metal oxide-based acetone gas sensors: A review. Sensors 2020, 20, 3096. [Google Scholar] [CrossRef]
  17. Drmosh, Q.A.; Olanrewaju Alade, I.; Qamar, M.; Akbar, S. Zinc Oxide-Based Acetone Gas Sensors for Breath Analysis: A Review. Chem. Asian J. 2021, 16, 1519–1538. [Google Scholar] [CrossRef]
  18. Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O.M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 1999, 402, 276–279. [Google Scholar] [CrossRef]
  19. Tranchemontagne, D.J.; Hunt, J.R.; Yaghi, O.M. Room temperature synthesis of metal-organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199, and IRMOF-0. Tetrahedron 2008, 64, 8553–8557. [Google Scholar] [CrossRef]
  20. Murray, L.J.; Dincă, M.; Long, J.R. Hydrogen storage in metal–organic frameworks. Chem. Soc. Rev. 2009, 38, 1294–1314. [Google Scholar] [CrossRef]
  21. Dhakshinamoorthy, A.; Li, Z.; Garcia, H. Catalysis and photocatalysis by metal organic frameworks. Chem. Soc. Rev. 2018, 47, 8134–8172. [Google Scholar] [CrossRef] [PubMed]
  22. Campbell, M.G.; Dincă, M. Metal–organic frameworks as active materials in electronic sensor devices. Sensors 2017, 17, 1108. [Google Scholar] [CrossRef] [PubMed]
  23. Yi, F.Y.; Chen, D.; Wu, M.K.; Han, L.; Jiang, H.L. Chemical sensors based on metal–organic frameworks. ChemPlusChem 2016, 81, 675–690. [Google Scholar] [CrossRef] [PubMed]
  24. Abu-Hani, A.F.; Greish, Y.E.; Mahmoud, S.T.; Awwad, F.; Ayesh, A.I. Low-temperature and fast response H2S gas sensor using semiconducting chitosan film. Sens. Actuators B 2017, 253, 677–684. [Google Scholar] [CrossRef]
  25. Ali, A.; Alzamly, A.; Greish, Y.E.; Alzard, R.H.; El-Maghraby, H.F.; Qamhieh, N.; Mahmoud, S.T. Enhancing Hydrogen Sulfide Detection at Room Temperature Using ZIF-67-Chitosan Membrane. Membranes 2023, 13, 333. [Google Scholar] [CrossRef] [PubMed]
  26. Achmann, S.; Hagen, G.; Kita, J.; Malkowsky, I.M.; Kiener, C.; Moos, R. Metal-organic frameworks for sensing applications in the gas phase. Sensors 2009, 9, 1574–1589. [Google Scholar] [CrossRef] [PubMed]
  27. Hosseini, M.; Zeinali, S.; Sheikhi, M. Fabrication of capacitive sensor based on Cu-BTC (MOF-199) nanoporous film for detection of ethanol and methanol vapors. Sens. Actuators B 2016, 230, 9–16. [Google Scholar] [CrossRef]
  28. Stassen, I.; Bueken, B.; Reinsch, H.; Oudenhoven, J.; Wouters, D.; Hajek, J.; Van Speybroeck, V.; Stock, N.; Vereecken, P.; Van Schaijk, R. Towards metal–organic framework based field effect chemical sensors: UiO-66-NH2 for nerve agent detection. Chem. Sci. 2016, 7, 5827–5832. [Google Scholar] [CrossRef]
  29. Yassine, O.; Shekhah, O.; Assen, A.H.; Belmabkhout, Y.; Salama, K.N.; Eddaoudi, M. H2S sensors: Fumarate-based fcu-MOF thin film grown on a capacitive interdigitated electrode. Angew. Chem. 2016, 128, 16111–16115. [Google Scholar] [CrossRef]
  30. Panda, T.; Banerjee, R. High Charge Carrier Mobility in two dimensional indium(III) isophthalic acid based frameworks. Proc. Natl. Acad. Sci. India Sect. A Phys. Sci. 2014, 84, 331–336. [Google Scholar] [CrossRef]
  31. Wu, G.; Huang, J.; Zang, Y.; He, J.; Xu, G. Porous field-effect transistors based on a semiconductive metal–organic framework. J. Am. Chem. Soc. 2017, 139, 1360–1363. [Google Scholar] [CrossRef] [PubMed]
  32. Hu, Z.; Deibert, B.J.; Li, J. Luminescent metal–organic frameworks for chemical sensing and explosive detection. Chem. Soc. Rev. 2014, 43, 5815–5840. [Google Scholar] [CrossRef] [PubMed]
  33. Hu, Z.; Pramanik, S.; Tan, K.; Zheng, C.; Liu, W.; Zhang, X.; Chabal, Y.J.; Li, J. Selective, sensitive, and reversible detection of vapor-phase high explosives via two-dimensional mapping: A new strategy for MOF-based sensors. Cryst. Growth Des. 2013, 13, 4204–4207. [Google Scholar] [CrossRef]
  34. Pramanik, S.; Hu, Z.; Zhang, X.; Zheng, C.; Kelly, S.; Li, J. A Systematic Study of Fluorescence-Based Detection of Nitroexplosives and Other Aromatics in the Vapor Phase by Microporous Metal–Organic Frameworks. Chem. Eur. J. 2013, 19, 15964–15971. [Google Scholar] [CrossRef] [PubMed]
  35. Wang, Y.; Wu, Y.; Xie, J.; Ge, H.; Hu, X. Multi-walled carbon nanotubes and metal–organic framework nanocomposites as novel hybrid electrode materials for the determination of nano-molar levels of lead in a lab-on-valve format. Analyst 2013, 138, 5113–5120. [Google Scholar] [CrossRef] [PubMed]
  36. Ma, W.; Jiang, Q.; Yu, P.; Yang, L.; Mao, L. Zeolitic imidazolate framework-based electrochemical biosensor for in vivo electrochemical measurements. Anal. Chem. 2013, 85, 7550–7557. [Google Scholar] [CrossRef] [PubMed]
  37. Shen, W.-J.; Zhuo, Y.; Chai, Y.-Q.; Yuan, R. Ce-based metal-organic frameworks and DNAzyme-assisted recycling as dual signal amplifiers for sensitive electrochemical detection of lipopolysaccharide. Biosens. Bioelectron. 2016, 83, 287–292. [Google Scholar] [CrossRef]
  38. Zhang, Y.; Chen, Y.; Zhang, Y.; Cong, H.; Fu, B.; Wen, S.; Ruan, S. A novel humidity sensor based on NH 2-MIL-125(Ti) metal organic framework with high responsiveness. J. Nanopart. Res. 2013, 15, 2014. [Google Scholar] [CrossRef]
  39. Yu, Y.; Zhang, X.-M.; Ma, J.-P.; Liu, Q.-K.; Wang, P.; Dong, Y.-B. Cu(I)-MOF: Naked-eye colorimetric sensor for humidity and formaldehyde in single-crystal-to-single-crystal fashion. Chem. Commun. 2014, 50, 1444–1446. [Google Scholar] [CrossRef]
  40. Yu, Y.; Ma, J.-P.; Dong, Y.-B. Luminescent humidity sensors based on porous Ln3+-MOFs. CrystEngComm 2012, 14, 7157–7160. [Google Scholar] [CrossRef]
  41. Harbuzaru, B.V.; Corma, A.; Rey, F.; Jordá, J.L.; Ananias, D.; Carlos, L.D.; Rocha, J. A miniaturized linear pH sensor based on a highly photoluminescent self-assembled europium(III) metal–organic framework. Angew. Chem. Int. Ed. 2009, 48, 6476–6479. [Google Scholar] [CrossRef] [PubMed]
  42. Li, H.-Y.; Wei, Y.-L.; Dong, X.-Y.; Zang, S.-Q.; Mak, T.C. Novel Tb-MOF embedded with viologen species for multi-photofunctionality: Photochromism, photomodulated fluorescence, and luminescent pH sensing. Chem. Mater. 2015, 27, 1327–1331. [Google Scholar] [CrossRef]
  43. Cui, Y.; Zhu, F.; Chen, B.; Qian, G. Metal–organic frameworks for luminescence thermometry. Chem. Commun. 2015, 51, 7420–7431. [Google Scholar] [CrossRef] [PubMed]
  44. Kreno, L.E.; Leong, K.; Farha, O.K.; Allendorf, M.; Van Duyne, R.P.; Hupp, J.T. Metal–organic framework materials as chemical sensors. Chem. Rev. 2012, 112, 1105–1125. [Google Scholar] [CrossRef] [PubMed]
  45. Li, H.-Y.; Zhao, S.-N.; Zang, S.-Q.; Li, J. Functional metal–organic frameworks as effective sensors of gases and volatile compounds. Chem. Soc. Rev. 2020, 49, 6364–6401. [Google Scholar] [CrossRef]
  46. Koo, W.-T.; Jang, J.-S.; Kim, I.-D. Metal-organic frameworks for chemiresistive sensors. Chem 2019, 5, 1938–1963. [Google Scholar] [CrossRef]
  47. Campbell, M.G.; Sheberla, D.; Liu, S.F.; Swager, T.M.; Dincă, M. Cu3(hexaiminotriphenylene)2: An electrically conductive 2D metal–organic framework for chemiresistive sensing. Angew. Chem. Int. Ed. 2015, 54, 4349–4352. [Google Scholar] [CrossRef]
  48. Aubrey, M.L.; Wiers, B.M.; Andrews, S.C.; Sakurai, T.; Reyes-Lillo, S.E.; Hamed, S.M.; Yu, C.-J.; Darago, L.E.; Mason, J.A.; Baeg, J.-O. Electron delocalization and charge mobility as a function of reduction in a metal–organic framework. Nat. Mater. 2018, 17, 625–632. [Google Scholar] [CrossRef]
  49. Rubio-Giménez, V.; Almora-Barrios, N.; Escorcia-Ariza, G.; Galbiati, M.; Sessolo, M.; Tatay, S.; Martí-Gastaldo, C. Origin of the chemiresistive response of ultrathin films of conductive metal–organic frameworks. Angew. Chem. 2018, 130, 15306–15310. [Google Scholar] [CrossRef]
  50. Wang, Y.; Takki, S.; Cheung, O.; Xu, H.; Wan, W.; Öhrström, L.; Inge, A.K. Elucidation of the elusive structure and formula of the active pharmaceutical ingredient bismuth subgallate by continuous rotation electron diffraction. Chem. Commun. 2017, 53, 7018–7021. [Google Scholar] [CrossRef]
  51. Wang, Z.; Zeng, Z.; Wang, H.; Zeng, G.; Xu, P.; Xiao, R.; Huang, D.; Chen, S.; He, Y.; Zhou, C. Bismuth-based metal–organic frameworks and their derivatives: Opportunities and challenges. Coord. Chem. Rev. 2021, 439, 213902. [Google Scholar] [CrossRef]
  52. Kalmutzki, M.J.; Diercks, C.S.; Yaghi, O.M. Metal–organic frameworks for water harvesting from air. Adv. Mater. 2018, 30, 1704304. [Google Scholar] [CrossRef] [PubMed]
  53. Ye, S.; Yan, M.; Tan, X.; Liang, J.; Zeng, G.; Wu, H.; Song, B.; Zhou, C.; Yang, Y.; Wang, H. Facile assembled biochar-based nanocomposite with improved graphitization for efficient photocatalytic activity driven by visible light. Appl. Catal. B Environ. 2019, 250, 78–88. [Google Scholar] [CrossRef]
  54. Wang, H.; Zeng, Z.; Xu, P.; Li, L.; Zeng, G.; Xiao, R.; Tang, Z.; Huang, D.; Tang, L.; Lai, C. Recent progress in covalent organic framework thin films: Fabrications, applications and perspectives. Chem. Soc. Rev. 2019, 48, 488–516. [Google Scholar] [CrossRef] [PubMed]
  55. Yi, H.; Yan, M.; Huang, D.; Zeng, G.; Lai, C.; Li, M.; Huo, X.; Qin, L.; Liu, S.; Liu, X. Synergistic effect of artificial enzyme and 2D nano-structured Bi2WO6 for eco-friendly and efficient biomimetic photocatalysis. Appl. Catal. B Environ. 2019, 250, 52–62. [Google Scholar] [CrossRef]
  56. Lu, K.; Aung, T.; Guo, N.; Weichselbaum, R.; Lin, W. Nanoscale metal–organic frameworks for therapeutic, imaging, and sensing applications. Adv. Mater. 2018, 30, 1707634. [Google Scholar] [CrossRef]
  57. Liu, S.; Lu, X.F.; Xiao, J.; Wang, X.; Lou, X.W. Bi2O3 nanosheets grown on multi-channel carbon matrix to catalyze efficient CO2 electroreduction to HCOOH. Angew. Chem. 2019, 131, 13966–13971. [Google Scholar] [CrossRef]
  58. Aykanat, A.; Jones, C.G.; Cline, E.; Stolz, R.M.; Meng, Z.; Nelson, H.M.; Mirica, K.A. Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing. ACS Appl. Mater. Interfaces 2021, 13, 60306–60318. [Google Scholar] [CrossRef]
  59. Ali, A.; Alzamly, A.; Greish, Y.E.; Bakiro, M.; Nguyen, H.L.; Mahmoud, S.T. A Highly Sensitive and Flexible Metal–Organic Framework Polymer-Based H2S Gas Sensor. ACS Omega 2021, 6, 17690–17697. [Google Scholar] [CrossRef]
  60. Ding, D.; Xue, Q.; Lu, W.; Xiong, Y.; Zhang, J.; Pan, X.; Tao, B. Chemically functionalized 3D reticular graphene oxide frameworks decorated with MOF-derived Co3O4: Towards highly sensitive and selective detection to acetone. Sens. Actuators B 2018, 259, 289–298. [Google Scholar] [CrossRef]
  61. Cui, W.; Kang, X.; Zhang, X.; Zheng, Z.; Cui, X. Facile synthesis of porous cubic microstructure of Co3O4 from ZIF-67 pyrolysis and its Au doped structure for enhanced acetone gas-sensing. Phys. E Low-Dimens. Syst. Nanostruct. 2019, 113, 165–171. [Google Scholar] [CrossRef]
  62. Xiao, J.; Diao, K.; Zheng, Z.; Cui, X. MOF-derived porous ZnO/Co3O4 nanocomposites for high performance acetone gas sensing. J. Mater. Sci. Mater. Electron. 2018, 29, 8535–8546. [Google Scholar] [CrossRef]
  63. Yao, M.S.; Tang, W.X.; Wang, G.E.; Nath, B.; Xu, G. MOF thin film-coated metal oxide nanowire array: Significantly improved chemiresistor sensor performance. Adv. Mater. 2016, 28, 5229–5234. [Google Scholar] [CrossRef] [PubMed]
  64. Jang, J.-S.; Koo, W.-T.; Kim, D.-H.; Kim, I.-D. In situ coupling of multidimensional MOFs for heterogeneous metal-oxide architectures: Toward sensitive chemiresistors. ACS Cent. Sci. 2018, 4, 929–937. [Google Scholar] [CrossRef]
  65. Chiappe, C.; Signori, F.; Valentini, G.; Marchetti, L.; Pomelli, C.S.; Bellina, F. Novel (glycerol) borate-based ionic liquids: An experimental and theoretical study. J. Phys. Chem. B 2010, 114, 5082–5088. [Google Scholar] [CrossRef]
  66. Ali, A.; AlTakroori, H.H.; Greish, Y.E.; Alzamly, A.; Siddig, L.A.; Qamhieh, N.; Mahmoud, S.T. Flexible Cu3(HHTP)2 MOF Membranes for Gas Sensing Application at Room Temperature. Nanomaterials 2022, 12, 913. [Google Scholar] [CrossRef]
Nanomaterials 13 03041 g001
Figure 1. (A) A 1 cm × 1 cm portion of the membrane. (B) Demonstration of high flexibility.
Figure 1. (A) A 1 cm × 1 cm portion of the membrane. (B) Demonstration of high flexibility.
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Figure 2. PXRD pattern of the Bi-gallate MOF and the composite membrane.
Figure 2. PXRD pattern of the Bi-gallate MOF and the composite membrane.
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Figure 3. FTIR curves of the as-synthesized Bi-gallate MOF powder and the composite membrane.
Figure 3. FTIR curves of the as-synthesized Bi-gallate MOF powder and the composite membrane.
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Figure 4. TGA curves of the Bi-gallate MOF powder and the composite membrane.
Figure 4. TGA curves of the Bi-gallate MOF powder and the composite membrane.
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Figure 5. (A,D) SEM image and EDX spectra of the as-synthesized Bi-gallate MOF. (B,E) SEM image and EDX spectra of the Bi-gallate MOF/CS/IL membrane. (C) Cross-section of the membrane.
Figure 5. (A,D) SEM image and EDX spectra of the as-synthesized Bi-gallate MOF. (B,E) SEM image and EDX spectra of the Bi-gallate MOF/CS/IL membrane. (C) Cross-section of the membrane.
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Figure 6. N2-sorption isotherms of as-synthesized Bi-gallate MOF.
Figure 6. N2-sorption isotherms of as-synthesized Bi-gallate MOF.
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Figure 7. Sensitivity of the Bi-gallate MOF/CS/IL membrane as a function of time and acetone concentration measured at 60 °C. Inset: Sensitivity for corresponding gas concentration.
Figure 7. Sensitivity of the Bi-gallate MOF/CS/IL membrane as a function of time and acetone concentration measured at 60 °C. Inset: Sensitivity for corresponding gas concentration.
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Figure 8. (A) Repeatability of the sensor. (B) Long-term stability of the Bi-gallate MOF/CS/IL membrane to 100 ppm of acetone gas at 60 °C.
Figure 8. (A) Repeatability of the sensor. (B) Long-term stability of the Bi-gallate MOF/CS/IL membrane to 100 ppm of acetone gas at 60 °C.
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Figure 9. (A) The calculated response and recovery time of the sensor. (B) Selectivity of the sensor containing 2 wt% Bi-gallate MOF in comparison to other test gases. (C) Selectivity of the sensor containing 0.5 wt% Bi-gallate MOF to H2S and acetone gases.
Figure 9. (A) The calculated response and recovery time of the sensor. (B) Selectivity of the sensor containing 2 wt% Bi-gallate MOF in comparison to other test gases. (C) Selectivity of the sensor containing 0.5 wt% Bi-gallate MOF to H2S and acetone gases.
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Figure 10. Sensing mechanism of the Bi-gallate-doped CS-IL membrane.
Figure 10. Sensing mechanism of the Bi-gallate-doped CS-IL membrane.
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Table 1. Sensor performance comparison with literature-reported values.
Table 1. Sensor performance comparison with literature-reported values.
Sensor/MaterialTarget GasOptimum Operating Temperature (°C)Detection Limit (ppm)Ref.
Bi-gallate MOF/CS/IL membrane Acetone6010This Work
MOF-5/CS/IL membraneH2SRT 1[59]
ZIF-67Acetone220100[60]
25050[61]
ZIF-67/ZIF-8Acetone2751[62]
ZnO/ZIF-CoZnAcetone25010[63]
Hierarchical MOF derived ZnO-Co3O4Acetone4505[64]
Bi(HHTP)NH3RT 0.29[58]
NORT 0.15
AcetoneRT 41.2
MeOHRT 278
EtOHRT 185
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MDPI and ACS Style

Ali, A.; Greish, Y.E.; Alzard, R.H.; Siddig, L.A.; Alzamly, A.; Qamhieh, N.; Mahmoud, S.T. Bismuth-Based Metal–Organic Framework as a Chemiresistive Sensor for Acetone Gas Detection. Nanomaterials 2023, 13, 3041. https://doi.org/10.3390/nano13233041

AMA Style

Ali A, Greish YE, Alzard RH, Siddig LA, Alzamly A, Qamhieh N, Mahmoud ST. Bismuth-Based Metal–Organic Framework as a Chemiresistive Sensor for Acetone Gas Detection. Nanomaterials. 2023; 13(23):3041. https://doi.org/10.3390/nano13233041

Chicago/Turabian Style

Ali, Ashraf, Yaser E. Greish, Reem H. Alzard, Lamia A. Siddig, Ahmed Alzamly, Naser Qamhieh, and Saleh T. Mahmoud. 2023. "Bismuth-Based Metal–Organic Framework as a Chemiresistive Sensor for Acetone Gas Detection" Nanomaterials 13, no. 23: 3041. https://doi.org/10.3390/nano13233041

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