Abstract
The sensing properties of the paddlewheel-type metal dimer (M-BTC: M = Fe, Ni, Cu, Zn, and Pd) toward SO2 gas were theoretically investigated using density functional theory (DFT) at the M06-L level of theory. Single-point calculations were carried at the M06 functional to correct the energetic properties and HOMO–LUMO energy gap. The O-bound adsorption complex of SO2 on the metal center of paddlewheels is found to be thermodynamically favorable than the S-bound ones. The trend of adsorption energy of SO2 on the metal center is in the order Pd-BTC < Cu-BTC < Ni-BTC < Zn-BTC < Fe-BTC. Among these five paddlewheels, the Ni-BTC and Zn-BTC paddlewheels are highly sensitive toward SO2 gas as compared to the other systems. The density of states reveals that the adsorption process significantly reduces the LUMO of the system to lower energies, enhancing the conductivity of the system. From DFT results, the energy gap of Ni-BTC and Zn-BTC is significantly reduced by 18.0 and 41.0% after the adsorption of SO2 on the metal center. These results suggest the great potential of Ni-, and Zn-BTC paddlewheels as SO2 sensors.
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Acknowledgements
This research was supported in part by grants from the Thailand Research Fund (Grant No. RSA5780069), the Commission on Higher Education, Ministry of Education (the National Research University Project of Thailand (NRU)), the Kasetsart University Research and Development Institute (KURDI). The author acknowledges the Laboratory for Computational and Applied Chemistry (LCAC), the KU Institute for Advanced Studies (KUIAS), and the National e-Science Infrastructure Consortium (http://www.e-science.in.th) for providing computing resources that have contributed to the research results reported within this paper.
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Sirijaraensre, J. Metal paddlewheels as sensors for detection of SO2 gas: a DFT study. Chem. Pap. 76, 2307–2315 (2022). https://doi.org/10.1007/s11696-021-02015-w
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DOI: https://doi.org/10.1007/s11696-021-02015-w