Polar O-Co-P Surface for Bimolecular Activation in Catalytic Hydrogen Generation  

作　　者：Huanhuan Zhang Ke Zhang Saima Ashraf Yanping Fan Shuyan Guan Xianli Wu Yushan Liu Baozhong Liu Baojun Li 

机构地区：[1]Research Center of Green Catalysis,College of Chemistry,Zhengzhou University,100 Science Road,Zhengzhou 450001,China [2]College of Chemistry and Chemical Engineering,Henan Polytechnic University,2001 Century Avenue,Jiaozuo 454000,China

出　　处：《Energy & Environmental Materials》2023年第1期224-233,共10页能源与环境材料（英文）

基　　金：H.Z.and K.Z.contributed equally to this work.Financial supports from the National Natural Science Foundation of China (nos.22075254,52071135,51871090,U1804135,21805071,51671080,and 21401168);Plan for Scientific Inno-vation Talent of Henan Province (no.194200510019);Key Project of Educa-tional Commission of Henan Province (no.19A150025)are acknowledged.

摘　　要：Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst.Accelerating bimolecular activation kinetics is the key to designing cost-effective catalysts for borohydride hydrolysis.In this study,the bimolecular activation of a polar O-Co-P site demonstrated superior hydrogen-generation kinetics(turnover frequency,TOF=37 min−1,298 K)and low activation energy(41.0 kJ mol^(−1))close to that of noble-metal-based catalysts.Through a combination of experiments and theoretical calculations,it was revealed that the activated dangling oxygen atom in the Co–O precursor effectively replaced via surface-phosphorization because of strong electronic interactions between the dangling oxygen and P atoms.This substitution modulated the local coordination environment and electronegativity around the surface Co sites and formed a new polar O-Co-P active site for optimizing the activation kinetics of ammonia borane and water.This strategy based on bimolecular activation may create new avenues in the field of catalysis.

关 键 词：bimolecular activation borohydride hydrolysis hydrogen generation noble-metal-free catalysts polar site 

分 类 号：TQ426[化学工程]