Oxygen Vacancy-induced Electron Density Tuning of Fe_(3)O_(4) for Enhanced Oxygen Evolution Catalysis

摘要

Despite the tremendous efforts devoted to enhancing the activity of oxygen evolution reaction(OER)catalysts,there is still a huge challenge to deeply understand the electronic structure characteristics of transition metal oxide to guide the design of more active catalysts.Herein,Fe_(3)O_(4)with oxygen vacancies(Fe_(3)O_(4)-Vac)was synthesized via Ar ion irradiation method and its OER activity was greatly improved by properly modulating the electron density around Fe atoms.The electron density of Fe_(3)O_(4)-Vac around Fe atoms increased compared to that of Fe_(3)O_(4)according to the characterization of synchrotron-based X-ray absorption near-edge structure(XANES),extended X-ray absorption fine structure(EXAFS)spectra,and density functional theory(DFT)calculation.Moreover,the DFT results indicate the enhancement of the desorption of HOO^(*)groups which significantly reduced the OER reaction barrier.Fe_(3)O_(4)-Vac catalyst shows an overpotential of 353 m V,lower than that of Fe OOH(853 m V)and Fe_(3)O_(4)(415 m V)at 10 m A cm^(-2),and a low Tafel slope of 50 m V dec^(-1)in 1 M KOH,which was even better than commercial RuO_(2)at high potential.This modulation approach provides us with valuable insights for exploring efficient and robust water-splitting electrocatalysts.