Zhou Yiyang, Duan Ruizhi, Liu Linqi, Ding Chunmei, Li Can
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences Dalian 116023 China
University of Chinese Academy of Sciences Beijing 100049 China.
Chem Sci. 2025 Aug 22. doi: 10.1039/d5sc04641f.
Electrocatalytic coreduction of nitrate and CO provides an opportunity for the synthesis of organonitrogen chemicals. The major challenge is to realize the simultaneous reduction of nitrate and CO into active intermediates for C-N bond formation. In this work, methylamine is synthesized from nitrate and CO on a polyphthalocyanine electrocatalyst with heterometal centers (CoCuPPc). Notably, it is found that the Co and Cu centers coordinated with the conjugated macrocyclic network of polyphthalocyanine can catalyze CO reduction to formaldehyde and nitrate reduction to hydroxylamine, respectively. The nucleophilic attack of hydroxylamine on formaldehyde generates a formaldoxime intermediate, which is then further reduced to methylamine. The overreduction reactions of hydroxylamine and formaldehyde intermediates are suppressed by CoCuPPc. This bifunctional catalyst with heteronuclear active centers simultaneously catalyzes nitrate and CO reduction to key intermediates for C-N bond formation.
硝酸盐和一氧化碳的电催化共还原为有机氮化学品的合成提供了契机。主要挑战在于实现硝酸盐和一氧化碳同时还原为用于形成碳 - 氮键的活性中间体。在这项工作中，在具有异金属中心（CoCuPPc）的聚酞菁电催化剂上由硝酸盐和一氧化碳合成了甲胺。值得注意的是，发现与聚酞菁的共轭大环网络配位的钴和铜中心可分别催化一氧化碳还原为甲醛以及硝酸盐还原为羟胺。羟胺对甲醛的亲核进攻产生甲肟中间体，然后该中间体进一步还原为甲胺。CoCuPPc抑制了羟胺和甲醛中间体的过度还原反应。这种具有异核活性中心的双功能催化剂同时催化硝酸盐和一氧化碳还原为用于形成碳 - 氮键的关键中间体。
