Constructing hetero-structured catalyst is promising but still challenging to achieve overall water splitting for hydrogen production with high efficiency.Herein,we developed a sulfide-based MoS_(2)/Co_(l-x)S@C hetero...Constructing hetero-structured catalyst is promising but still challenging to achieve overall water splitting for hydrogen production with high efficiency.Herein,we developed a sulfide-based MoS_(2)/Co_(l-x)S@C hetero-structure for highly efficient electrochemical hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The carbon derived from the filter paper acts as a conducting carrier to ensure adequate exposure of the active sites guaranteed with improved catalytic stability.The unique hierarchical nano-sheets facilitate the charge and ion transfer by shortening the diffusion path during electro-catalysis.Meanwhile,the robust hetero-interfaces in MoS_(2)/Co_(1-x)S@C can expose rich electrochemical active sites and facilitate the charge transfer,which further cooperates synergistically toward electro-catalytic reactions.Consequently,the optimal MoS_(2)/Co_(1-x)S@C hetero-structures present small over-potentials toward HER(135 mV@10 mA·cm^(-2))and OER(230 mV@10 mA·cm^(-2)).The MoS_(2)/Co_(1-x)S@C electrolyzer requires an ultralow voltage of 1.6 V at the current density of 10 mA·cm^(-2)with excellent durability,outperforming the state-of-the-art electro-catalysts.This work sheds light on the design of the hetero-structured catalysts with interfacial engineering toward large-scale water splitting.展开更多
The catalyst innovation that aims at noble-metal-free substitutes is one key aspect for future sustainable hydrogen energy deployment.In this paper,a nickel cobalt sulfoselenide/black phosphorus heterostructure(NiCoSe...The catalyst innovation that aims at noble-metal-free substitutes is one key aspect for future sustainable hydrogen energy deployment.In this paper,a nickel cobalt sulfoselenide/black phosphorus heterostructure(NiCoSe|S/BP)was fabricated to realize the highly active and durable water electrolysis through interface and valence dual-engineering.The NiCoSe|S/BP nanostructure was constructed by in-situ growing NiCo hydroxide nanosheet arrays on few-layer BP and subsequently one-step sulfoselenization by SeS2.Besides the conductive merit of BP substrate,holes in p-type BP are capable of oxidizing the Co^(2+)to high-valence and electron-accepting Co^(3+),benefiting the oxygen evolution reaction(OER).Meanwhile,Ni^(3+)/Ni^(2+)ratio in the heterostructure is reduced to maintain the electrical neutrality,which corresponds to the increased electron-donating character for boosting hydrogen evolution reaction(HER).As for HER and OER,the heterostructured NiCoSe|S/BP electrocatalyst exhibits small overpotentials of 172 and 285 mV at 10 mA cm^(-2)(η_(10))in alkaline media,respectively.And overall water splitting has been achieved at a low cell potential of 1.67 V at η_(10) with high stability.Molecular sensing and density functional theory(DFT)calculations are further proposed for understanding the rate-determine steps and enhanced catalytic mechanism.The investigation presents a deep-seated perception for the electrocatalytic performance enhancement of BP-based heterostructure.展开更多
基金supported by the National Natural Science Foundation of China(51871119,22075141,and 22101132)Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province(BK20220039)+3 种基金Jiangsu Provincial Founds for Natural Science Foundation(BK20180015 and BK20210311)China Postdoctoral Science Foundation(2021M691561 and 2021T140319)Jiangsu Postdoctoral Research Fund(2021K547C)the Fundamental Research Funds for the Central Universities(kfjj20180605)。
文摘Constructing hetero-structured catalyst is promising but still challenging to achieve overall water splitting for hydrogen production with high efficiency.Herein,we developed a sulfide-based MoS_(2)/Co_(l-x)S@C hetero-structure for highly efficient electrochemical hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The carbon derived from the filter paper acts as a conducting carrier to ensure adequate exposure of the active sites guaranteed with improved catalytic stability.The unique hierarchical nano-sheets facilitate the charge and ion transfer by shortening the diffusion path during electro-catalysis.Meanwhile,the robust hetero-interfaces in MoS_(2)/Co_(1-x)S@C can expose rich electrochemical active sites and facilitate the charge transfer,which further cooperates synergistically toward electro-catalytic reactions.Consequently,the optimal MoS_(2)/Co_(1-x)S@C hetero-structures present small over-potentials toward HER(135 mV@10 mA·cm^(-2))and OER(230 mV@10 mA·cm^(-2)).The MoS_(2)/Co_(1-x)S@C electrolyzer requires an ultralow voltage of 1.6 V at the current density of 10 mA·cm^(-2)with excellent durability,outperforming the state-of-the-art electro-catalysts.This work sheds light on the design of the hetero-structured catalysts with interfacial engineering toward large-scale water splitting.
基金jointly supported by the National Natural Science Foundation of China(Grant No.51802252)Natural Science Foundation of Shaanxi Province(Nos.2020JM-032,2019TD-020)+3 种基金111 project 2.0(BP0618008)the fund of the State Key Laboratory of Solidification Processing in NPU(Grant No.SKLSP202116)supported by Yunnan Provincial Key Laboratory of Energy Saving in Phosphorus Chemical Engineering and New Phosphorus Materials(LHG-2020-0003)China Postdoctoral Science Foundation(2019M663698)。
文摘The catalyst innovation that aims at noble-metal-free substitutes is one key aspect for future sustainable hydrogen energy deployment.In this paper,a nickel cobalt sulfoselenide/black phosphorus heterostructure(NiCoSe|S/BP)was fabricated to realize the highly active and durable water electrolysis through interface and valence dual-engineering.The NiCoSe|S/BP nanostructure was constructed by in-situ growing NiCo hydroxide nanosheet arrays on few-layer BP and subsequently one-step sulfoselenization by SeS2.Besides the conductive merit of BP substrate,holes in p-type BP are capable of oxidizing the Co^(2+)to high-valence and electron-accepting Co^(3+),benefiting the oxygen evolution reaction(OER).Meanwhile,Ni^(3+)/Ni^(2+)ratio in the heterostructure is reduced to maintain the electrical neutrality,which corresponds to the increased electron-donating character for boosting hydrogen evolution reaction(HER).As for HER and OER,the heterostructured NiCoSe|S/BP electrocatalyst exhibits small overpotentials of 172 and 285 mV at 10 mA cm^(-2)(η_(10))in alkaline media,respectively.And overall water splitting has been achieved at a low cell potential of 1.67 V at η_(10) with high stability.Molecular sensing and density functional theory(DFT)calculations are further proposed for understanding the rate-determine steps and enhanced catalytic mechanism.The investigation presents a deep-seated perception for the electrocatalytic performance enhancement of BP-based heterostructure.
