Zou Haiyuan, Shu Siyan, Yang Wenqiang, Chu You-Chiuan, Cheng Minglun, Dong Hongliang, Liu Hong, Li Fan, Hu Junhui, Wang Zhenbin, Liu Wei, Chen Hao Ming, Duan Lele
Department of Chemistry, Southern University of Science and Technology, Shenzhen, China.
Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, Hangzhou, China.
Nat Commun. 2024 Dec 30;15(1):10818. doi: 10.1038/s41467-024-55116-x.
Natural enzymes feature distinctive second spheres near their active sites, leading to exquisite catalytic reactivity. However, incumbent synthetic strategies offer limited versatility in functionalizing the second spheres of heterogeneous catalysts. Here, we prepare an enzyme-mimetic single Co-N atom catalyst with an elaborately configured pendant amine group in the second sphere via 1,3-dipolar cycloaddition, which switches the oxygen reduction reaction selectivity from the 4e to the 2e pathway under acidic conditions. Proton inventory studies and theoretical calculations reveal that the introduced pendant amine acts as a proton relay and promotes the protonation of *O to *OOH on the Co-N active site, facilitating HO production. The second sphere-tailored Co-N sites reach optima HO selectivity of 97% ± 1.13%, showing a 3.46-fold enhancement to bare Co-N catalyst (28% ± 1.75%). This work provides an appealed approach for enzyme-like catalyst design, bridging the gap between enzymatic and heterogeneous catalysis.
天然酶在其活性位点附近具有独特的第二配位层，从而产生出色的催化反应活性。然而，现有的合成策略在使多相催化剂的第二配位层功能化方面的通用性有限。在此，我们通过1,3-偶极环加成反应制备了一种在第二配位层中具有精心配置的侧链胺基的类酶单Co-N原子催化剂，该催化剂在酸性条件下将氧还原反应的选择性从4e途径转变为2e途径。质子存量研究和理论计算表明，引入的侧链胺充当质子中继体，并促进Co-N活性位点上O质子化为OOH，从而促进HO的生成。经第二配位层定制的Co-N位点实现了97%±1.13%的最佳HO选择性，比裸Co-N催化剂（28%±1.75%）提高了3.46倍。这项工作为类酶催化剂设计提供了一种有吸引力的方法，弥合了酶催化和多相催化之间的差距。
