Interfacial Differentiated Recoordination Trigger Asymmetric Bi (δ ⁺ )—Bi (δ ⁻ ) Regions for Robust CO ₂ Photosynthesis to CH ₃ COOH

Direct solar‐driven conversion of CO 2 and H 2 O into high‐value‐added C 2 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 Bi 24 O 31 Br 10 (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 CO 2 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.