Uncovering the structure evolution and real active species of energy catalytic materials under reaction conditions is important for both understanding structure–activity relationship and constructing electrocatalysts for CO₂ electroreduction (CO₂ER). And integrating CO₂ER with an anodic organic transformation to replace the oxygen evolution reaction is highly desirable. Here, In₂O₃ is selected as the model material to reveal the surface reconstruction under CO₂ER condition. In situ and ex situ results reveal that the electrochemical in situ reconstruction of crystalline In₂O₃ leads to the formation of crystalline-In/amorphous-In₂O_3−x heterostructure (In/In₂O_3−x). In/In₂O_3−x acts as the real active phase with Faradaic efficiency of ~ 89.2% for the formate, outperforming In (~67.5%). The improved performance can be ascribed to electron-rich In rectified by Schottky effect of In/In₂O_3−x heterostructure. Impressively, formate and high-value octanenitrile can be simultaneously achieved by integrating CO₂ER with octylamine oxidation in an In/In₂O_3−x‖Ni₂P two-electrode electrolyzer.

揭示反应条件下能源催化材料的结构演变和实际活性物质对于理解结构-活性关系和构建用于 CO ₂电还原 (CO ₂ ER) 的电催化剂都很重要。并且非常需要将 CO ₂ ER 与阳极有机转化相结合以取代析氧反应。此处，选择 In ₂ O ₃作为模型材料以揭示 CO ₂ ER 条件下的表面重建。原位和非原位结果表明，结晶 In ₂ O的电化学原位重构₃导致形成结晶-In/非晶-In ₂ O _{3- x}异质结构（In/In ₂ O _{3- x}）。In/In ₂ O _{3− x}作为真正的活性相，甲酸盐的法拉第效率为 ~ 89.2%，优于 In (~67.5%)。改进的性能可归因于通过 In/In ₂ O _{3− x}异质结构的肖特基效应整流的富电子 In。令人印象深刻的是，通过在 In/In ₂ O _{3− x} ‖Ni 中将CO ₂ ER 与辛胺氧化结合，可以同时获得甲酸盐和高价值的辛腈₂ P 二电极电解槽。