Pichaimuthu, K.K.PichaimuthuJena, A.A.JenaChang, H.H.ChangSu, C.C.SuRU-SHI LIU2021-01-272021-01-272020https://www.scopus.com/inward/record.url?eid=2-s2.0-85095600227&partnerID=40&md5=3cdbfe1ea5b092c4e509a7897e4443dehttps://scholars.lib.ntu.edu.tw/handle/123456789/543338The production of hydrogen using solar energy via a photoelectrochemical system is an effective technique for meeting present clean energy needs. Owing to the small bandgap and highly negative conduction band edge (-0.46 V) of Si, it is considered a promising photocathode material for solar hydrogen evolution reaction (HER). However, because of sluggish HER kinetics on the Si surface, bare Si electrodes have a high overpotential. Molybdenum disulfide (MoS2) has attracted wide interest as a promising alternative to Pt-based catalysts for producing hydrogen. Nevertheless, it suffers from sluggish kinetics for driving the process of HER because of its inert basal plane. Herein, HER performance was enhanced by doping a metal (cobalt) and a nonmetal (phosphorus) into MoS2. Doping MoS2 (CoPO-MoS2) on Si photocathodes with cobalt and phosphorous provides a current density of about 21.6 mA cm-2 at 0 V (vs. RHE) and a reduced Tafel value of 54.3 mV dec-1. The doped catalyst shows good stability up to 3 h with retention of about 85%. The flat surface of the Si photocathode has been chemically etched into pyramidal structures (SiMP) to reduce the loss due to reflection and enhance the catalytically active surface. Raman, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure reveal that Co and P strongly coordinated with the MoS2 materials. Furthermore, the catalytic performance was enhanced by the defect sites on MoS2, thereby stimulating more S vacancies on the basal planes and S-edge sites. Defect engineering will hopefully provide a new research direction for the innovation and development of more active sites of CoPO-MoS2. This journal is © 2020 The Royal Society of Chemistry.[SDGs]SDG7[SDGs]SDG9Catalysts; Cobalt; Cobalt metallography; Energy gap; Extended X ray absorption fine structure spectroscopy; Field emission cathodes; Hydrogen evolution reaction; Hydrogen production; Layered semiconductors; Molybdenum compounds; Phosphorus; Photocathodes; Silicon; Solar energy; Sulfur; X ray absorption; X ray photoelectron spectroscopy; Catalytic performance; Conduction band edge; Defect engineering; Extended X-ray absorption fine structures; Molybdenum disulfide; Photoelectrochemical system; Production of hydrogen; Pyramidal structures; Sulfur compoundsjournal article10.1039/d0cy01205j2-s2.0-85095600227WOS:000579632900011