Modulating the catalytic activity of metal-organic frameworks for CO oxidation with N2O through an oriented external electric field

• Published in: Molecular catalysis Vol. 516; p. 111970
• Main Authors: Sittiwong, Jarinya, Jaturajamrenchai, Thanaporn, Wongkampuan, Pitchaya, Somwatcharajit, Nutchanon, Impeng, Sarawoot, Maihom, Thana, Probst, Michael, Limtrakul, Jumras
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.11.2021
• Subjects: CO oxidation; DFT; Metal-organic frameworks; N2O decomposition; Oriented external electric field; Oriented external electric field; DFT; CO oxidation; N2O decomposition; Metal-organic frameworks
• ISSN: 2468-8231; 2468-8231
• DOI: 10.1016/j.mcat.2021.111970

•The OEEF effect on the CO oxidation with N2O over the Fe3(btc)2 is studied by using DFT calculations.•The charge transfer process has an important role in activating N–O bond of N2O.•The applied OEEF can facilitate charge transfer from Fe3(btc)2 to N2O.•The catalytic activity of Fe3(btc)2 for CO oxidation with N2O can be controlled by the applied OEEF. One of the most promising ways to solve various environmental issues caused by toxic gasses is to effectively reduce them to less hazardous gasses. Here, we investigate the effect of an oriented external electric field (OEEF) on the oxidation of CO with N2O over the metal-organic framework Fe3(btc)2 (btc=1,3,5-benzentricarboxylate) by deriving the relevant reaction profiles with density functional theory calculations. We apply the OEEF to Fe3(btc)2 in the range of -0.010 to +0.010 a.u. The reaction is assumed to proceed in two steps: the breaking of the NO bond of N2O and CO bond formation. The applied OEEF is found to mainly affect the transition states and intermediates along the reaction path. A strong correlation between the activation barriers for NO bond breaking, the rate-determining step of the reaction, and the magnitude of the OEEF is observed. The activation energies are reduced from 16.0 to 10.5 and 4.0 kcal/mol by applying positive OEEFs of +0.005 and +0.010 a.u., respectively. In contrast, by applying negative OEEFs of -0.005 and -0.010 a.u., the barriers increase to 20.1 and 23.1 kcal/mol, respectively. Based on charge transfer analysis, the applied positive OEEF enhances the charge transfer from the catalytic site to antibonding molecular orbitals of N2O, thus facilitating NO bond breaking. The results show that an OEEF can customize the catalytic performance of CO oxidation with N2O over MOF catalysts. [Display omitted]