Sensing Behavior of Pristine and TM-decorated Zn12O12 Nanocage Towards Toxic Formaldehyde, Phosgene and Thiophosgene Gases

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The theoretical examination of the interaction among formaldehyde, phosgene, and thiophosgene molecules on both pristine Zn12O12 nanocage and TM-decorated (Cu, Ni, Ti, and Cr) Zn12O12 nanocage is conducted using density functional theory (DFT). The Zn12O12 nanocage by doping of Cu, Ni, Ti, and Cr atoms remarks in altering the electronic properties and actively reassuring the adsorption of these toxic gases. The finding revealed that Zn12O12 nanocages doped with metal atoms enhance reactivity. In this study, the adsorption energy, dipole moment, charges from natural bond orbitals (NBO), global reactivity parameters, and frontier molecular orbitals (FMOs) were analyzed. The results show that phosgene and thiophosgene are physisorbed on Zn12O12 nanocage with adsorption energies of -10.63, and -9.41 kcal/mol, respectively. The decoration of Zn12O12 nanocage with transition metals (Cu, Ni, Ti, and Cr), efficiently enhanced the adsorption of H2CO, COCl2, and CSCl2. The adsorption of these harmful gases on TM-decorated Zn12O12 nanocage resulted in strong chemisorption. Among the selected warfare agents, CSCl2@Cr-Zn12O12 and H2CO@Ti-Zn12O12 show the highest value of adsorption energy (− 77.86 and − 75.37 kcal/mol, respectively). These complexes also exhibit high chemical hardness value and low softness value suggesting their higher stability and lower reactivity as compared to other complexes. Moreover, the results of recovery time suggested that COCl2 can be desorbed from Ni-Zn12O12 with a recovery time of 0.014 s. Therefore, it is suggested that the Ni-Zn12O12 nanocage may be used as a potential reusable sensor for the detection of phosgene at room temperature due to its high sensitivity and short recovery time. Additionally, the results suggested that the adsorption energy and electrical conductivity of toxic gases on decorated Zn12O12 nanocage increase, potentially improving sensitivity towards these toxic gases.


This article was originally published in Journal of Inorganic and Organometallic Polymers and Materials in 2023.

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