CH4 Carbonylation to Acetic Acid Using H2O as an Oxidant on a Rh-Functionalized UiO-67 Combined with Oriented External Electric Fields: Selectivity and Mechanistic Insights from DFT Calculations.

Acetic acid (CH3COOH), as an industrially important petrochemical product, is predominantly produced via multistep energy-intensive processes. The development of a rhodium single-site heterogeneous catalyst has received considerable attention due to its potential to transform CH4 into CH3COOH in a single step. Herein, the reaction mechanism for the generation of CH3COOH from CH4, CO, and H2O catalyzed by Rh-functionalized metal-organic framework (MOF) UiO-67 and the selectivity of products CH3COOH, formic acid (HCOOH), methanol (CH3OH), and acetaldehyde (CH3CHO) under the oriented external electric fields (OEEFs) were systematically explored by density functional theory (DFT) calculations. The results reveal that the insertion of CO into Rh-CH3 is the rate-determining step with a free energy barrier of 21.0 kcal/mol in CH4 carbonylation to CH3COOH. Upon applying an OEEF of Fx = +0.0050 au along the C-C bond, the rate-determining step shifts toward H2O decomposition with the barrier of 19.6 kcal/mol, significantly improving the selectivity for CH3COOH production, compared to the major competitive HCOOH route. The Brønsted-Evans-Polanyi (BEP) relationships between key transition states, field strength, and NPA charge transfer were established. This study may guide the rational design of atomically dispersed MOF catalysts for the selective coconversion of CH4 and CO to CH3COOH using H2O as the oxidant under the OEEF.