Black phosphorus(BP)exhibits a significant chemical reactivity toward transition metals,which is strongly dependent on its electronic and morphological features.Using as a case study metal Co atoms deposited by physic...Black phosphorus(BP)exhibits a significant chemical reactivity toward transition metals,which is strongly dependent on its electronic and morphological features.Using as a case study metal Co atoms deposited by physical vapor deposition on chemically exfoliated BP thinfilms,we document that environmentally oxidized BP edges react immediately with the formation of Co(Ⅱ)-POx species,but later also the basal plane strongly reacts,already at room temperature,to form an interfacial phosphide.Atomically resolved scanning tunneling microscopy data reveal the formation of a Co_(2)P(112)layer,upon which the further growth of metal Co nanoparticles takes place.X-ray photoemission spectroscopy data show similar inter facial reactions also for atomic W,suggesting a quite general behavior.The electrochemical and photo electrocatalytic properties of the resulting metal-BP nanohybrids are investigated by linear sweep voltam metry and electrochemical impedance spectroscopy.The Co-BP nanohybrid shows a marked stability in acid media and a significant increase of the electrocatalytic activity for the hydrogen evolution reaction with respect to bare BP,due to the formation of a very stable phosphide phase,and even an interesting photoactivity connected to the formation of p-n junction between BP and Co_(2)P.On the other hand,the W-BP nanohybrid exhibits a modest performance in the electrocatalytic production of hydrogen because of the formation of less active oxide phases as a consequence of environmental oxidation.展开更多
基金supported by the following projects:financial support from the Italian MIUR(PRIN 2015:SMARTNESS,2015K7FZLH,PRIN2017:Multi-e,20179337R7)MAECI Italy-China bilateral project(GINSENG,PGR00953)+1 种基金The Cariparo foundation is acknowledged for funding(project Synergy,Progetti di Eccellenza 2018)Thanks are also expressed to the European Research Council(ERC)under the European Union’s Horizon 2020 research and inno vation program(Grant Agreement No.670173)for funding the project PHOSFUN“Phosphorene functionalization:a new plat form for advanced multifunctional materials”through an ERC Advanced Grant to MP.
文摘Black phosphorus(BP)exhibits a significant chemical reactivity toward transition metals,which is strongly dependent on its electronic and morphological features.Using as a case study metal Co atoms deposited by physical vapor deposition on chemically exfoliated BP thinfilms,we document that environmentally oxidized BP edges react immediately with the formation of Co(Ⅱ)-POx species,but later also the basal plane strongly reacts,already at room temperature,to form an interfacial phosphide.Atomically resolved scanning tunneling microscopy data reveal the formation of a Co_(2)P(112)layer,upon which the further growth of metal Co nanoparticles takes place.X-ray photoemission spectroscopy data show similar inter facial reactions also for atomic W,suggesting a quite general behavior.The electrochemical and photo electrocatalytic properties of the resulting metal-BP nanohybrids are investigated by linear sweep voltam metry and electrochemical impedance spectroscopy.The Co-BP nanohybrid shows a marked stability in acid media and a significant increase of the electrocatalytic activity for the hydrogen evolution reaction with respect to bare BP,due to the formation of a very stable phosphide phase,and even an interesting photoactivity connected to the formation of p-n junction between BP and Co_(2)P.On the other hand,the W-BP nanohybrid exhibits a modest performance in the electrocatalytic production of hydrogen because of the formation of less active oxide phases as a consequence of environmental oxidation.
