Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution  

作　　者：Zhiyang Huang Miao Liao Shifan Zhang Lixia Wang Mingcheng Gao Zuyang Luo Tayirjan Taylor Isimjan Bao Wang Xiulin Yang 

机构地区：[1]Guangxi Key Laboratory of Low Carbon Energy Materials,School of Chemistry and Pharmaceutical Sciences,Guangxi Normal University,Gulin 541004,Guangxi,China [2]State Key Laboratory of Biochemical Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China [3]Saudi Arabia Basic Industries Corporation(SABIC)at King Abdullah University of Science and Technology(KAUST),Thuwal 23955-6900,Saudi Arabia

出　　处：《Journal of Energy Chemistry》2024年第3期244-252,I0007,共10页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(52363028,21965005);the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001);the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。

摘　　要：Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

关 键 词：Dy@Ni-MOF Dy incorporation Electronic interaction SUPERHYDROPHILICITY Oxygen evolution reaction 

分 类 号：TQ116.21[化学工程—无机化工] TQ426