Mei Guoliang, Lu Yanze, Yang Xiaoju, Chen Sanxia, Yang Xuan, Yang Li-Ming, Tang Conghui, Sun Yujie, Xia Bao Yu, You Bo
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, China.
Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, USA.
Angew Chem Int Ed Engl. 2024 Jan 8;63(2):e202314708. doi: 10.1002/anie.202314708. Epub 2023 Dec 4.
Direct CO electroreduction to valuable chemicals is critical for carbon neutrality, while its main products are limited to simple C /C compounds, and traditionally, the anodic O byproduct is not utilized. We herein report a tandem electrothermo-catalytic system that fully utilizes both cathodic (i.e., CO) and anodic (i.e., O ) products during overall CO electrolysis to produce valuable organic amides from arylboronic acids and amines in a separate chemical reactor, following the Pd(II)-catalyzed oxidative aminocarbonylation mechanism. Hexamethylenetetramine (HMT)-incorporated silver and nickel hydroxide carbonate electrocatalysts were prepared for efficient coproduction of CO and O with Faradaic efficiencies of 99.3 % and 100 %, respectively. Systematic experiments, operando attenuated total reflection surface-enhanced Fourier transform infrared spectroscopy characterizations and theoretical studies reveal that HMT promotes *CO hydrogenation/*CO desorption for accelerated CO -to-CO conversion, and O inhibits reductive deactivation of the Pd(II) catalyst for enhanced oxidative aminocarbonylation, collectively leading to efficient synthesis of 10 organic amides with high yields of above 81 %. This work demonstrates the effectiveness of a tandem electrothermo-catalytic strategy for economically attractive CO conversion and amide synthesis, representing a new avenue to explore the full potential of CO utilization.
将一氧化碳直接电还原为有价值的化学品对碳中和至关重要，但其主要产物仅限于简单的碳/碳化合物，而且传统上，阳极副产物氧气未得到利用。我们在此报告了一种串联电热催化系统，该系统在一氧化碳整体电解过程中充分利用阴极（即一氧化碳）和阳极（即氧气）产物，在一个单独的化学反应器中，按照钯（II）催化的氧化氨羰基化机理，由芳基硼酸和胺制备有价值的有机酰胺。制备了掺入六亚甲基四胺（HMT）的银和碳酸镍氢氧化物电催化剂，以分别以99.3%和100%的法拉第效率高效联产一氧化碳和氧气。系统实验、原位衰减全反射表面增强傅里叶变换红外光谱表征和理论研究表明，HMT促进*CO氢化/*CO脱附以加速一氧化碳到一氧化碳的转化，而氧气抑制钯（II）催化剂的还原失活以增强氧化氨羰基化，共同导致高效合成10种有机酰胺，产率高达81%以上。这项工作证明了串联电热催化策略在经济上有吸引力的一氧化碳转化和酰胺合成方面的有效性，代表了一条探索一氧化碳利用全部潜力的新途径。
