Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization  

作　　者：Fan He Yingnan Liu Xiaoxuan Yang Yaqi Chen Cheng‑Chieh Yang Chung‑Li Dong Qinggang He Bin Yang Zhongjian Li Yongbo Kuang Lecheng Lei Liming Dai Yang Hou 

机构地区：[1]Key Laboratory of Biomass Chemical Engineering of Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,People’s Republic of China [2]Institute of Zhejiang University-Quzhou,Quzhou 324000,People’s Republic of China [3]Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo 315201,People’s Republic of China [4]School of Biological and Chemical Engineering,NingboTech University,Ningbo 315100,People’s Republic of China [5]Department of Physics,Tamkang University,New Taipei 25137,Taiwan,People’s Republic of China [6]Australian Carbon Materials Centre(A‑CMC),School of Chemical Engineering,University of New South Wales,Sydney,NSW 2051,Australia

出　　处：《Nano-Micro Letters》2024年第9期279-290,共12页纳微快报（英文版）

基　　金：supported by the National Key Research and Development Program of China (2022YFB4002100);the development project of Zhejiang Province's "Jianbing" and "Lingyan" (2023C01226);the National Natural Science Foundation of China (22278364, U22A20432, 22238008, 22211530045, and 22178308);the Fundamental Research Funds for the Central Universities (226-2022-00044 and 226-2022-00055);the Science Foundation of Donghai Laboratory (DH-2022ZY0009);the Startup Foundation for Hundred-Talent Program of Zhejiang University;Scientific Research Fund of Zhejiang Provincial Education Department.

摘　　要：Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

关 键 词：Metal-organic frameworks Bond length adjustment Spin state transition Orbitals hybridization Water splitting 

分 类 号：TQ116.2[化学工程—无机化工] O643.36[理学—物理化学]