Finding appropriate photocatalysts for solar-driven water(H_(2)O)splitting to generate hydrogen(H_(2))fuel is a challenging task,particularly when guided by conventional trial-and-error experimental methods.Here,densi...Finding appropriate photocatalysts for solar-driven water(H_(2)O)splitting to generate hydrogen(H_(2))fuel is a challenging task,particularly when guided by conventional trial-and-error experimental methods.Here,density functional theory(DFT)is used to explore the MXenes photocatalytic properties,an emerging family of two-dimensional(2D)transition metal carbides and nitrides with chemical formula M_(n+1)X_(n)T_(x),known to be semiconductors when having T_(x)terminations.More than 4,000 MXene structures have been screened,considering different compositional(M,X,T_(x),and n)and structural(stacking and termination position)factors,to find suitable MXenes with a bandgap in the visible region and band edges that align with the water-splitting half-reaction potentials.Results from bandgap analysis show how,in general,MXenes with n=1 and transition metals from group III present the most cases with bandgap and promising sizes,with C-MXenes being superior to N-MXenes.From band alignment calculations of candidate systems with a bandgap larger than 1.23 eV,the minimum required for a water-splitting process,Sc_(2)CT_(2),Y_(2)CT_(2)(T_(x)=Cl,Br,S,and Se)and Y_(2)CI_(2)are highlighted as adequate photocatalysts.展开更多
基金the Spanish Ministerio de Ciencia e Innovación through grants PID2021-126076NB-I00 and TED2021-129506B-C22the unit of excellence María de Maeztu CEX2021-001202-M granted to the IQTCUB+2 种基金the Generalitat de Catalunya 2021SGR00079 grantComputational resources have been provided by the Red Española de Supercomputación(RES)QHS-2023-2-0017 and QHS-2023-3-0012 projectsAlso,F.V.thanks the ICREA Academia Award 2023 Ref.Ac2216561.
文摘Finding appropriate photocatalysts for solar-driven water(H_(2)O)splitting to generate hydrogen(H_(2))fuel is a challenging task,particularly when guided by conventional trial-and-error experimental methods.Here,density functional theory(DFT)is used to explore the MXenes photocatalytic properties,an emerging family of two-dimensional(2D)transition metal carbides and nitrides with chemical formula M_(n+1)X_(n)T_(x),known to be semiconductors when having T_(x)terminations.More than 4,000 MXene structures have been screened,considering different compositional(M,X,T_(x),and n)and structural(stacking and termination position)factors,to find suitable MXenes with a bandgap in the visible region and band edges that align with the water-splitting half-reaction potentials.Results from bandgap analysis show how,in general,MXenes with n=1 and transition metals from group III present the most cases with bandgap and promising sizes,with C-MXenes being superior to N-MXenes.From band alignment calculations of candidate systems with a bandgap larger than 1.23 eV,the minimum required for a water-splitting process,Sc_(2)CT_(2),Y_(2)CT_(2)(T_(x)=Cl,Br,S,and Se)and Y_(2)CI_(2)are highlighted as adequate photocatalysts.
