The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for cataly...The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.展开更多
基金supported by the National Natural Science Foundation of China(No.U24A20550,52273264)Youth Science Foundation Project ofChina(No.22409056)+1 种基金the Key Project of the Heilongjiang Provincial Natural Science Foundation(No.ZD2024B001)the Excellent Youth Project ofHeilongjiang Provincial Natural Science Foundation of China(No.LH2019B020).
文摘The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.
