Co_(3)O_(4) is a promising catalyst for the chlorine evolution reaction(CER)in seawater;however,its CER selectivity is compromised by the adsorption of the competitive oxygen evolution reaction intermediate(OH^(-))at ...Co_(3)O_(4) is a promising catalyst for the chlorine evolution reaction(CER)in seawater;however,its CER selectivity is compromised by the adsorption of the competitive oxygen evolution reaction intermediate(OH^(-))at Co sites.Inspired by the hard-soft acid-base(HSAB)theory,this study proposes incorporating early transition metal sites(V)with a low degree of electron delocalization into Co_(3)O_(4) to modulate the selective adsorption of reactants on catalytic sites.Experimental and theoretical calculations reveal that V incorporation facilitates the electron accumulation at the Co site,significantly strengthening the interaction between Co and Cl^(-).Meanwhile,the loss of electrons from V sites generates a more localized electronic state that preferentially adsorbs OH^(-),thus reducing the Co-OH interaction and releasing more Co sites for Cl^(-)adsorption.Therefore,Co_(2)VO_(4) exhibits a high CER selectivity of 92.3%and maintains one of the highest stabilities over 300 h in natural seawater.The resulting half-flow cell achieves~100%disinfection efficiency in seawater,validating the HSAB theory-based design strategy and offering new guidance for developing highly selective seawater CER catalysts.展开更多
基金supported by the Guangxi Science and Technology Program(2023AB38061)the National Natural Science Foundation of China(22162004,22479031)the High-performance Computing Platform of Guangxi University。
文摘Co_(3)O_(4) is a promising catalyst for the chlorine evolution reaction(CER)in seawater;however,its CER selectivity is compromised by the adsorption of the competitive oxygen evolution reaction intermediate(OH^(-))at Co sites.Inspired by the hard-soft acid-base(HSAB)theory,this study proposes incorporating early transition metal sites(V)with a low degree of electron delocalization into Co_(3)O_(4) to modulate the selective adsorption of reactants on catalytic sites.Experimental and theoretical calculations reveal that V incorporation facilitates the electron accumulation at the Co site,significantly strengthening the interaction between Co and Cl^(-).Meanwhile,the loss of electrons from V sites generates a more localized electronic state that preferentially adsorbs OH^(-),thus reducing the Co-OH interaction and releasing more Co sites for Cl^(-)adsorption.Therefore,Co_(2)VO_(4) exhibits a high CER selectivity of 92.3%and maintains one of the highest stabilities over 300 h in natural seawater.The resulting half-flow cell achieves~100%disinfection efficiency in seawater,validating the HSAB theory-based design strategy and offering new guidance for developing highly selective seawater CER catalysts.
