Breaking Structural Instability and Orbital Symmetry Mismatch in p-Block Metal Monochalcogenides for CO2 Electroreduction via Noninvasive van der Waals Doping

• DOI: 10.1021/jacs.5c03556
• Publication Date: 2025-04-25T03:14:16Z
• Authors: Pengfei Li; Xu Han; Fangqi Yang; Ning Li; Meng-Xuan Li; Jing Li; Xiaoxu Zhao; Meng Zhao; Zejun Li; Wenping Hu; Jiong Lu

P-block metal monochalcogenides (MX) adopting black phosphorus (BP)-like structures are promising electrocatalysts due to their abundant exposed sites and tunable electronic structures. However, practical application is limited by structural instability arising from lone-pair electron-induced distortions, along with an inherent orbital symmetry mismatch the frontier orbitals of small molecules (e.g., CO2), reducing activation efficiency. Here, we report a noninvasive doping strategy overcome both in p-block for efficient CO2 electroreduction, through engineering periodic van der Waals (vdW) superlattice, known as misfit superlattice. These vdW superlattices sublayer ratios contain catalytically active p-electron-rich MX sublayers conductive transition dichalcogenide current collectors. Taking [BiS]1[TaS2]1 proof-of-concept, presence ionic interactions between crucial modulating stabilizing BiS transforming Bi into higher valence state Bi(2+δ). Concurrently, interlayer induces uneven electron redistribution Bi's p-orbitals, breaking its LUMO CO2, thereby barrier. In situ characterization theoretical calculations reveal that optimized exhibit moderate adsorption *OCHO, endowing superlattice exceptional selectivity (>90%) formate electroreduction. This work advances versatile platform synergistically layered materials tailoring alignment leveraging doping, achieving optimal catalytic performance electrochemical conversion molecules.