Authors: Xiaoyang Yue, Chen Guan, Hui Yang, Minshu Chen, Quanjun Xiang
Published: 2025-03-18
Source: Full article
AbstractFrontier orbital hybridization plays a vital role in the initial adsorption and activation process during catalysis. A formidable challenge is the precise determination of active orbitals/sites. Herein, 2D Bi3O4Br nanosheets are adopted as an operable platform for heteroatom doping of various transition metals (Fe, Ni, Zn/Cd). As the atom number of dopants increases, the capability of selective CO2 photoconversion is continuously amplified. The intrinsic nature is the variation of active functional orbital as indicated from band center distance (Δd/p‐p) indicators. The calculated charge transfer of various CO2‐bound geometries further demonstrates the p‐p orbital interaction overwhelms d‐p orbital interaction. X‐ray photoelectron spectroscopy and X‐ray absorption spectroscopy results verify the charged nature of Bi sites with 6p orbitals not fully filled by electrons. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis and Gibbs free energy change profile suggest the rapid emergence of the critical *COOH intermediate in a thermodynamically preferred pathway.