Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-d...Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-doped Ni_(2)P catalyst as a research model and found that the introduction of heterogeneous Co reconstructed the charge distribution around the P site,which effectively enhanced the hydrogen evolution reaction(HER)activity of the pure Ni_(2)P.Based on in-situ Raman real-time monitoring technology,we monitored for the first time that Co doping triggered a switch of the active site(from the original Co-active site to the P-active site),which promoted the adsorption of H_(2)O to enhance the HER activity.The density functional theory(DFT)calculations indicated that the P site of Co-Ni_(2)P expressed the highest activity and the Ni site of pure Ni_(2)P expressed the highest activity,which further confirms the in-situ Raman monitoring results.The active site turnover mechanism discovered in this study will undoubtedly provide more rational and targeted ideas for future catalyst design.展开更多
基金financial support from the National Natural Science Foundation of China(No.52302098,52336003,52176076,51676103)China Postdoctoral Science Foundation(2023M731855)+3 种基金Taishan Scholar Project of Shandong Province(China)(No.ts20190937)Natural Science Foundation of Shandong Province(China)(No.ZR2023QE344,ZR2021LFG003)Qingdao Postdoctoral Science Foundation(No.QDBSH20220201021,QDBSH20220202084)The Youth Innovation Project for Universities of Shandong Province(2023KJ102)。
文摘Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-doped Ni_(2)P catalyst as a research model and found that the introduction of heterogeneous Co reconstructed the charge distribution around the P site,which effectively enhanced the hydrogen evolution reaction(HER)activity of the pure Ni_(2)P.Based on in-situ Raman real-time monitoring technology,we monitored for the first time that Co doping triggered a switch of the active site(from the original Co-active site to the P-active site),which promoted the adsorption of H_(2)O to enhance the HER activity.The density functional theory(DFT)calculations indicated that the P site of Co-Ni_(2)P expressed the highest activity and the Ni site of pure Ni_(2)P expressed the highest activity,which further confirms the in-situ Raman monitoring results.The active site turnover mechanism discovered in this study will undoubtedly provide more rational and targeted ideas for future catalyst design.
