Abstract
In this paper, a dual-ligand design strategy is demonstrated to modulate the performance of the electronically conductive metalorganic frameworks (EC-MOFs) thin film with a spray layer-by-layer assembly method. The thin film not only can be precisely prepared in nanometer scale (20–70 nm), but also shows the pin-hole-free smooth surface. The high quality nano-film of 2,3,6,7,10,11-hexaiminotriphenylene (HITP) doped Cu-HHTP enables the precise modulation of the chemiresistive sensitivity and selectivity. Selectivity improvement over 220% were realized for benzene vs. NH3, as well as enhanced response and recovery properties. In addition, the selectivity of the EC-MOF thin film sensors toward other gases (e.g. triethylamine, methane, ethylbenzene, hydrogen, butanone, and acetone) vs. NH3 at room temperature is also discussed.
Similar content being viewed by others
References
Kambe, T.; Sakamoto, R.; Hoshiko, K.; Takada, K.; Miyachi, M.; Ryu, J. H.; Sasaki, S.; Kim, J.; Nakazato, K.; Takata, M. et al. π-conjugated nickel bis(dithiolene) complex nanosheet. J. Am. Chem. Soc.2013, 135, 2462–2465.
Clough, A. J.; Skelton, J. M.; Downes, C. A.; De La Rosa, A. A.; Yoo, J. W.; Walsh, A.; Melot, B. C.; Marinescu, S. C. Metallic conductivity in a two-dimensional cobalt dithiolene metal-organic framework. J. Am. Chem. Soc.2017, 139, 10863–10867.
Koo, W. T.; Jang, J. S.; Kim, I. D. Metal-organic frameworks for chemiresistive sensors. Chem2019, 5, 1938–1963.
Dong, R. H.; Han, P.; Arora, H.; Ballabio, M.; Karakus, M.; Zhang, Z.; Shekhar, C.; Adler, P.; Petkov, P. S.; Erbe, A. et al. High-mobility band-like charge transport in a semiconducting two-dimensional metal-organic framework. Nat. Mater.2018, 17, 1027–1032.
Yao, M. S.; Zheng, J. J.; Wu, A. Q.; Xu, G; Nagarkar, S. S.; Zhang, G; Tsujimoto, M.; Sakaki, S.; Horike, S.; Otake, K. et al. A dual-ligand porous coordination polymer chemiresistor with modulated conductivity and porosity. Angew. Chem., Int. Ed.2020, 59, 172–176.
Hmadeh, M.; Lu, Z.; Liu, Z.; Gándara, F.; Furukawa, H.; Wan, S.; Augustyn, V.; Chang, R.; Liao, L.; Zhou, F. et al. New porous crystals of extended metal-catecholates. Chem. Mater.2012, 24, 3511–3513.
Huang, X.; Sheng, P.; Tu, Z. Y.; Zhang, F. J.; Wang, J. H.; Geng, H.; Zou, Y.; Di, C. A.; Yi, Y. P.; Sun, Y. M. et al. A two-dimensional π-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour. Nat. Commun.2015, 6, 7408.
Takaishi, S.; Hosoda, M.; Kajiwara, T.; Miyasaka, H.; Yamashita, M.; Nakanishi, Y.; Kitagawa, Y.; Yamaguchi, K.; Kobayashi, A.; Kitagawa, H. Electroconductive porous coordination polymer Cu[Cu(pdt)2] composed of donor and acceptor building units. Inorg. Chem.2009, 48, 9048–9050.
Erickson, K. J.; Léonard, F.; Stavila, V.; Foster, M. E.; Spataru, C. D.; Jones, R. E.; Foley, B. M.; Hopkins, P. E.; Allendorf, M. D.; Talin, A. A. Thin film thermoelectric metal-organic framework with high seebeck coefficient and low thermal conductivity. Adv. Mater.2015, 27, 3453–3459.
Park, S. S.; Hontz, E. R.; Sun, L.; Hendon, C. H.; Walsh, A.; Van Voorhis, T.; Dinca, M. Cation-dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene-based microporous metal-organic frameworks. J. Am. Chem. Soc.2015, 137, 1774–1777.
Darago, L. E.; Aubrey, M. L.; Yu, C. J.; Gonzalez, M. I.; Long, J. R. Electronic conductivity, ferrimagnetic ordering, and reductive insertion mediated by organic mixed-valence in a ferric semiquinoid metalorganic framework. J. Am. Chem. Soc.2015, 137, 15703–15711.
Dong, R. H.; Zhang, Z. T.; Tranca, D. C.; Zhou, S. Q.; Wang, M. C.; Adler, P.; Liao, Z. Q.; Liu, F.; Sun, Y.; Shi, W. J. et al. A coronenebased semiconducting two-dimensional metal-organic framework with ferromagnetic behavior. Nat. Commun.2018, 9, 2637.
Ko, M.; Mendecki, L.; Mirica, K. A. Conductive two-dimensional metal-organic frameworks as multifunctional materials. Chem. Commun.2018, 54, 7873–7891.
Dong, R. H.; Zhang, T.; Feng, X. L. Interface-assisted synthesis of 2D materials: Trend and challenges. Chem. Rev.2018, 118, 6189–6235.
Miner, E. M.; Fukushima, T.; Sheberla, D.; Sun, L.; Surendranath, Y.; Dincă, M. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2. Nat. Commun.2016, 7, 10942.
Sheberla, D.; Bachman, J. C.; Elias, J. S.; Sun, C. J.; Shao-Horn, Y.; Dincă, M. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater.2017, 16, 220–224.
Feng, D. W.; Lei, T.; Lukatskaya, M. R.; Park, J.; Huang, Z. H.; Lee, M.; Shaw, L.; Chen, S. C.; Yakovenko, A. A.; Kulkarni, A. et al. Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance. Nat. Energy2018, 3, 30–36.
Su, J.; He, W.; Li, X. M.; Sun, L.; Wang, H. Y.; Lan, Y. Q.; Ding, M. N.; Zuo, J. L. High electrical conductivity in a 2D MOF with intrinsic superprotonic conduction and interfacial pseudo-capacitance. Matter2020, 2, 711–722.
Wu, J.; Chen, J. H.; Wang, C.; Zhou, Y.; Ba, K.; Xu, H.; Bao, W. Z.; Xu, X. H.; Carlsson, A.; Lazar, S. et al. Metal-organic framework for transparent electronics. Adv. Sci.2020, 7, 1903003.
Yao, M. S.; Lv, X. J.; Fu, Z. H.; Li, W. H.; Deng, W. H.; Wu, G. D.; Xu, G. Layer-by-layer assembled conductive metal-organic framework nanofilms for room-temperature chemiresistive sensing. Angew. Chem, Int. Ed.2017, 56, 16510–16514.
Campbell, M. G.; Sheberla, D.; Liu, S. F.; Swager, T. M.; Dincă, M. Cu3(hexaiminotriphenylene)2: An electrically conductive 2D metalorganic framework for chemiresistive sensing. Angew. Chem., Int. Ed.2015, 127, 4423–4426.
Yao, M. S.; Xiu, J. W.; Huang, Q. Q.; Li, W. H.; Wu, W. W.; Wu, A. Q.; Cao, L. A.; Deng, W. H.; Wang, G. E.; Xu, G. Van der waals heterostructured MOF-on-MOF thin films: Cascading functionality to realize advanced chemiresistive sensing. Angew. Chem., Int. Ed.2019, 58, 14915–14919.
Meng, Z.; Aykanat, A.; Mirica, K. A. Welding metallophthalocyanines into bimetallic molecular meshes for ultrasensitive, low-power chemiresistive detection of gases. J. Am. Chem. Soc.2018, 141, 2046–2053.
Wu, G. D.; Huang, J. H.; Zang, Y.; He, J.; Xu, G. Porous field-effect transistors based on a semiconductive metal-organic framework. J. Am. Chem. Soc.2016, 139, 1360–1363.
Mu, Q. Q.; Zhu, W.; Li, X.; Zhang, C. F.; Su, Y. H.; Lian, Y. B.; Qi, P. W.; Deng, Z.; Zhang, D.; Wang, S. et al. Electrostatic charge transfer for boosting the photocatalytic CO2 reduction on metal centers of 2D MOF/rGO heterostructure. Appl. Catal. B Environ.2020, 262, 118144.
Xu, C. Y.; Pan, Y. T.; Wan, G.; Liu, H.; Wang, L.; Zhou, H.; Yu, S. H.; Jiang, H. L. Turning on visible-light photocatalytic C–H oxidation over metal-organic frameworks by introducing metal-to-cluster charge transfer. J. Am. Chem. Soc.2019, 141, 19110–19117.
Jiang, H. Q.; Liu, X. C.; Wu, Y. S.; Shu, Y. F.; Gong, X.; Ke, F. S.; Deng, H. X. Metal-organic frameworks for high charge-discharge rates in lithium-sulfur batteries. Angew. Chem., Int. Ed.2018, 57, 3916–3921.
Meng, Z.; Stolz, R. M.; Mendecki, L.; Mirica, K. A. Electrically-transduced chemical sensors based on two-dimensional nanomaterials. Chem. Rev.2019, 779, 478–598.
Sun, L.; Campbell, M. G.; Dincă M. Electrically conductive porous metal-organic frameworks. Angew. Chem., Int. Ed.2016, 55, 3566–3579.
Choi, S. J.; Kim, I. D. Recent developments in 2D nanomaterials for chemiresistive-type gas sensors. Electron. Mater. Lett.2018, 14, 221–260.
Campbell, M. G.; Dincă, M. Metal-organic frameworks as active materials in electronic sensor devices. Sensors2017, 17, 1108.
Guo, L. L.; Chen, F.; Xie, N.; Kou, X. Y.; Wang, C.; Sun, Y. F.; Liu, F. M.; Liang, X. S.; Gao, Y.; Yan, X. et al. Ultra-sensitive sensing platform based on Pt-ZnO-In2O3 nanofibers for detection of acetone. Sens. Actuators B Chem.2018, 272, 185–194.
Liu, H.; Li, M.; Voznyy, O.; Hu, L.; Fu, Q. Y.; Zhou, D. X.; Xia, Z.; Sargent, E. H.; Tang, J. Physically flexible, rapid-response gas sensor based on colloidal quantum dot solids. Adv. Mater.2014, 26, 2718–2724.
Jian, Y. Y.; Hu, W. W.; Zhao, Z. H.; Cheng, P. F.; Haick, H.; Yao, M. S.; Wu, W. W. Gas sensors based on chemi-resistive hybrid functional nanomaterials. Nano-Micro Lett.2020, 12, 71.
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.
Zhang, J.; Liu, X. H.; Neri, G.; Pinna, N. Nanostructured materials for room-temperature gas sensors. Adv. Mater.2016, 28, 795–831.
Kim, H. J.; Lee, J. H. Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview. Sens. Actuators B Chem.2014, 192, 607–627.
Li, T. M.; Zeng, W.; Wang, Z. C. Quasi-one-dimensional metaloxide-based heterostructural gas-sensing materials: A review. Sens. Actuators B Chem.2015, 221, 1570–1585.
Shi, Z. L.; Tao, Y.; Wu, J. S.; Zhang, C. Z.; He, H. L.; Long, L. L.; Lee, Y.; Li, T.; Zhang, Y. B. Robust metal-triazolate frameworks for CO2 capture from flue gas. J. Am. Chem. Soc.2020, 142, 2750–2754.
Heinke, L.; Wöll, C. Surface-mounted metal-organic frameworks: Crystalline and porous molecular assemblies for fundamental insights and advanced applications. Adv. Mater.2019, 31, 1806324.
Gu, Y. F.; Wu, Y. N.; Li, L. C.; Chen, W.; Li, F. T.; Kitagawa, S. Controllable modular growth of hierarchical MOF-on-MOF architectures. Angew. Chem., Int. Ed.2017, 56, 15658–15662.
Shekhah, O.; Hirai, K.; Wang, H.; Uehara, H.; Kondo, M.; Diring, S.; Zacher, D.; Fischer, R. A.; Sakata, O.; Kitagawa, S. et al. MOF-on-MOF heteroepitaxy: Perfectly oriented [Zn2(ndc)2(dabco)]n grown on [Cu2(ndc)2(dabco)]n thin films. Dalton Trans.2011, 40, 4954–4958.
Richardson, J. J.; Björnmalm, M.; Caruso, F. Technology-driven layer-by-layer assembly of nanofilms. Science2015, 348, aaa2491.
Li, W. H.; Ding, K.; Tian, H. R.; Yao, M. S.; Nath, B.; Deng, W. H.; Wang, Y. B.; Xu, G. Conductive metal-organic framework nanowire array electrodes for high-performance solid-state supercapacitors. Adv. Funct. Mater.2017, 27, 1702067.
Hu, N. T.; Yang, Z.; Wang, Y. Y.; Zhang, L. L.; Wang, Y.; Huang, X. L.; Wei, H.; Wei, L. M.; Zhang, Y. F. Ultrafast and sensitive room temperature NH3 gas sensors based on chemically reduced graphene oxide. Nanotechnology2013, 25, 025502.
Chen, E. X.; Yang, H.; Zhang, J. Zeolitic imidazolate framework as formaldehyde gas sensor. Inorg. Chem.2014, 53, 5411–5413.
Yao, M. S.; Li, Q. H.; Hou, G. L.; Lu, C.; Cheng, B. L.; Wu, K. C.; Xu, G.; Yuan, F. L.; Ding, F.; Chen, Y. F. Dopant-controlled morphology evolution of WO3 polyhedra synthesized by RF thermal plasma and their sensing properties. ACS Appl. Mater. Interfaces2015, 7, 2856–2866.
Yao, M. S.; Cao, L. A.; Tang, Y. X.; Wang, G. E.; Liu, R. H.; Kumar, P. N.; Wu, G. D.; Deng, W. H.; Hong, W. J.; Xu, G. Gas transport regulation in a MO/MOF interface for enhanced selective gas detection. J. Mater. Chem. A2019, 7, 18397–18403.
Acknowledgements
This research was supported by the National Natural Science Foundation of China (Nos. 21801243, 21822109, 21975254, 21773245, 21850410462, and 21805276), the Key Research Program of Frontier Science, CAS (No. QYZDB-SSW-SLH023), China Postdoctoral Science Foundation (Nos. 2018M642576 and 2018M642578), International Partnership Program of CAS (No. 121835KYSB201800), the Natural Science Foundation of Fujian Province (No. 2019J01129), and the Youth Innovation Promotion Association CAS.
Author information
Authors and Affiliations
Corresponding authors
Electronic Supplementary Material
12274_2020_2823_MOESM1_ESM.pdf
Layer-by-layer assembled dual-ligand conductive MOF nano-films with modulated chemiresistive sensitivity and selectivity
Rights and permissions
About this article
Cite this article
Wu, AQ., Wang, WQ., Zhan, HB. et al. Layer-by-layer assembled dual-ligand conductive MOF nano-films with modulated chemiresistive sensitivity and selectivity. Nano Res. 14, 438–443 (2021). https://doi.org/10.1007/s12274-020-2823-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-020-2823-8