Designing high-performance catalytic systems for carbon conversion: insights into co oxidation and CO2 reduction reactions

Emissions of toxic gases from fuel combustion in vehicles and industrial processes significantly undermine both environmental and human health, primarily due to the hazards posed by carbon monoxide (CO) and carbon dioxide (CO2). Accordingly, mitigating these emissions or converting them efficiently into high-value chemicals is imperative. This study employs Density Functional Theory (DFT) calculations to design a high-performance catalytic system for carbon conversion, derived from an in-depth computational investigation of CO oxidation (COOR) and CO2 reduction reactions (CO2RR). For CO oxidation, twelve dual-metal atom catalysts including Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au were evaluated on boron nitride surfaces with three distinct vacancy configurations: BNVBB, BNVNN, and BNVBN. The reaction pathways were investigated through two fundamental mechanisms: the Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms. Catalyst screening based on binding energy, formation energy, gas adsorption energy, and activation barriers identified Pd2@BNVBB and Ag2@BNVBB as the most promising candidates. Both catalysts followed the LH mechanism, exhibiting exceptionally low activation barriers of 0.44 eV and 0.31 eV, respectively. This study introduces a novel class of boron nitride-based catalysts and provides critical mechanistic insights into CO oxidation, laying a robust theoretical foundation for future experimental advancements.
For CO2 reduction to C1 products, eighteen single-atom catalysts (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Ir, Pt, and Au) were designed and supported on porous boron nitride surfaces with two distinct vacancy types: p-BNVB and p-BNVN. The results revealed that V@p-BNVB, Fe@p-BNVB, Ni@p-BNVB, Cu@p-BNVB, and Pd@p-BNVB exhibited outstanding catalytic performance, demonstrating exceptional activity and selectivity toward C1 products while effectively suppressing the competing hydrogen evolution reaction. Notably, V@p-BNVB and Fe@p-BNVB achieved impressive efficiency in HCOOH and CH3OH formation, with ultralow limiting potentials of-0.16 V and -0.12 V for V@p-BNVB and -0.05 V and -0.20 V for Fe@p-BNVB, respectively. Furthermore, this study introduces an innovative descriptor (o) that quantitatively elucidates the structure-activity relationships governing C1 product formation. Derived from fundamental properties such as d-electron count, metal electronegativity, and the generalized electronegativity of catalyst atoms and key intermediates, this descriptor provides a simple yet effective framework for predicting catalytic performance based on intrinsic chemical properties.