Metal-organic-frameworks passivated CuBi_(2)O_(4)photocathodes boost CO_(2)reduction kinetics  

作　　者：Jiaqi Jin Guangming Cao Yanjie Liu Yingying Shu Zhiyuan Deng Wei Sun Xiaogang Yang 

机构地区：[1]Institute of Materials Science and Devices,School of Material Science and Engineering,Suzhou University of Science and Technology,Suzhou,215009,PR China [2]School of Computing and Artificial Intelligence,Southwest Jiaotong University,Chengdu,611756,PR China [3]Key Laboratory of Laser Technology and Optoelectronic Functional Materials of Hainan Province,Key Laboratory of Functional Materials and Photoelectrochemistry of Haikou,College of Chemistry and Chemical Engineering,Hainan Normal University,Haikou,571158,PR China

出　　处：《Materials Reports(Energy)》2023年第4期60-70,共11页材料导报（能源）（英文）

基　　金：supported by the National Natural Science Foundation of China(Project.U1604121)and Startup funding from Suzhou University of Science and Technology.

摘　　要：Photoelectrochemical reduction of CO_(2)to produce CO with metal-organic frameworks(MOFs)is recognized as a desirable technology to mitigate CO_(2)emission and generate sustainable energy.To achieve highly efficient electrocatalyst,it is essential to design a new material interface and uncover new reaction mechanisms or kinetics.Herein,we developed two metal-organic Cu-MOF and Bi-MOF layers using benzene tricarboxylic acid(H_(3)BTC)ligands on CuBi_(2)O_(4) photocathodes.Both MOF layers drastically improved the photoelectrochemical stability by suppressing the photo-corrosion through conformal surface passivation.The Cu-MOF modified CuBi_(2)O_(4) showed more significant charge separation and transfer efficiencies than the Bi-MOF modified control.Based on the transient photocurrent curves under the applied potential of 0.6 V vs.RHE,the rate-law analysis showed the CO_(2)photoreduction took place through a first-order reaction.Further,the photoelectrochemical impedance spectra(PEIS)revealed this reaction order,representing an“operando”analysis.Moreover,the reaction rate constant on Cu-MOF modified sample was higher than that on Bi-MOF modified one and bare CuBi_(2)O_(4).Combined with the density functional theory calculation,the surface absorption of CO_(2)and CO molecules and the higher energy barrier for*COOH intermediates could significantly determine the first order reaction.

关 键 词：Copper bismuth oxide Carbon dioxide photoelectrochemical reduction Metal-organic framework Rate-law kinetics 

分 类 号：O64[理学—物理化学]