Hydrogen evolution reaction activity enhancement from active site turnover mechanism

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.

Cl^(-)ions accelerating interface charge transfer in a Si/In_(2)S_(3) Faradaic junction photocathode for solar seawater splitting

Photoelectrocatalytic seawater splitting is a promising low-cost method to produce green hydrogen in a large scale.The effects of Cl^(-)ions in seawater on the performance of a photoanode have been reported in previous studies.However,few researches have been done on the roles of Cl^(-)ions in a photocathode.Herein,for the first time,we find that Cl^(-)ions in the electrolyte improve the photocurrent of a Si/In_(2)S_(3) photocathode by 50% at-0.6 V_(RHE).An in-situ X-ray photoelectron spectroscopy(XPS)characterization combined with the time-of-flight secondary-ion mass spectrometry by simulating photoelectrochemical conditions was used to investigate the interface charge transfer mechanism.The results suggest that there is an In_(2)^(+3)S_(3-x)(OH)_(2x)layer on the surface of In_(2)S_(3) in the phosphate buffer solution(PBS)electrolyte,which plays a role as an interface charge transfer mediator in the Si/In_(2)S_(3) photocathode.The In_(2)^(+3)S_(3-x)(OH)_(2x)surface layer becomes In_(2)^(+3)S_(3-x)(Cl)_(2x)in the PBS electrolyte with NaCl and accelerates the charge transfer rate at the In_(2)S_(3)/electrolyte interface.These results offer a new concept of regulating interface charge transfer mediator to enhance the performance of photoelectrocatalytic seawater splitting for hydrogen production.