Interfacial Differentiated Recoordination Trigger Asymmetric Bi (δ⁺)-Bi (δ^-) Regions for Robust CO₂ Photosynthesis to CH₃COOH.

Abstract

Direct solar-driven conversion of CO₂ and H₂O into high-value-added C₂ products, such as acetic acid, represents a critical frontier challenge in artificial photosynthesis. However, its efficiency is primarily constrained by sluggish photogenerated charge migration and the dynamics limitations for C-C coupling. This paper reports a "disorder-induced reconstruction" strategy that utilizes the inherent local disorder of covalent organic frameworks (COFs) to induce the construction of asymmetric active centers on the surface of Bi₂₄O₃₁Br₁₀ (BOB), inducing atomic-scale reconstruction and spontaneously forming extended regions with asymmetric Bi(δ+)-Bi(δ-) bimetallic sites. Without the use of sacrificial agents or noble metal co-catalysts, the resulting catalyst exhibits excellent performance in the conversion of CO₂ to acetate, with a yield as high as 1.03 mmol g^-1 h^-1 and a selectivity of 97.63%. The apparent quantum efficiencies of catalyst can reach 13.75% and 8.33% at 380 and 400 nm, respectively. This work reveals a previously unknown mechanism for reconstructing inorganic surfaces into asymmetric active structural units using local disorder in organic modifiers, providing a paradigm for the design of next-generation photocatalysts.