摘要
Designing a highly reactive adsorbent material for the catalytic conversion of carbon dioxide(CO_(2))into valuable products to help ameliorate climate change and address the decreasing availability of fossil fuels is a widely explored application of two-dimensional(2D)nanomaterials.Herein,we present a 2D graphene-like monolayer(ML)of germanium(Ge)and carbon(C)atoms(2D GeC ML)for highly efficient CO_(2)adsorption and activation.We have employed first-principles calculations based on the density functional theory(DFT)to investigate the adsorption behavior of CO_(2)molecules at pristine GeC MLs and MLs containing defects/vacancies(C-vacancy VC,Ge-vacancy V_(Ge),and combined Ge-and C-vacancies V_(Ge/C)).We present a detailed description of the nature of the interaction and the mechanism of CO_(2)conversion via in-depth projected densities of states,electronic band structures,charge density analysis,and Bader charge transfer analysis.The results show that CO_(2)molecule weakly binds with the 2D GeC ML,with an adsorption energy(Eads)of only-0.13 eV,rendering 2D GeC ML unsuitable for the reduction of CO_(2).In contrast,CO_(2)gas molecules show strong chemisorption on vacancy-defected GeC MLs with significant Bader charge transfer.The CO_(2)@GeC_V_(Ge)ML system displays a maximum Eads of-4.46 eV,geometrical deformation,and a Bader charge transfer of-1.44 e-to the CO_(2)molecule.Thus,V_(Ge)is the most promising candidate among all considered GeC systems to enable the electrochemical CO_(2)reduction reaction.
基金
the Science and Engineering Research Board(SERB)for a state university research excellence(SURE)grant(SUR/2022/004935)
funded by EPSRC(EP/X035859)
the financial support,provided by UPES,Dehradun,India。
