Zhang Xiaofeng, Qiu Aoqian, Ran Pan, Ding Mengning, Cheng Xu
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
J Am Chem Soc. 2025 Jul 9;147(27):23797-23808. doi: 10.1021/jacs.5c06034. Epub 2025 Jun 25.
Owing to the ready formation of an insulating oxide layer, there is an intrinsic obstacle to the use of aluminum material as the cathode in the electrocatalytic reaction. In this report, a new Al-based material with a surface aluminum oxide/chloride nanolayer (nAlClO@Al) is prepared. Via the quantum tunneling effect, this material realizes conductivity through the nano-Al-O layer. This material exhibits unusual inertness toward the hydrogen evolution reaction, leaving a wide reduction window for the substrate. Primed with the native Lewis acidity of the Al-Cl structure, this material achieves the electrocatalytic hydrogenation of thiophenes with up to >95% conversion, >95% selectivity, and 90% Faraday efficiency. This catalysis is applicable to heteroarene and benzene rings. In particular, the chemoselectivity is controlled by the nAlClO@Al catalyst instead of the substrate, which is complementary to electrochemical Birch chemistry.
由于绝缘氧化层易于形成，铝材料在电催化反应中用作阴极存在固有障碍。在本报告中，制备了一种具有表面氧化铝/氯化物纳米层（nAlClO@Al）的新型铝基材料。通过量子隧穿效应，该材料通过纳米Al-O层实现导电。这种材料对析氢反应表现出异常的惰性，为底物留下了较宽的还原窗口。基于Al-Cl结构的固有路易斯酸性，这种材料实现了噻吩的电催化氢化，转化率高达>95%，选择性>95%，法拉第效率为90%。这种催化适用于杂芳烃和苯环。特别是，化学选择性由nAlClO@Al催化剂而非底物控制，这与电化学伯奇化学互补。
