The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
基于密度泛函理论的第一性原理方法,计算了Se掺杂单层MoS_2能带结构和光吸特性,并分析了对其光解水性质的影响。结果表明:本征单层MoS_2为直接带隙结构,禁带宽度为1.740 e V,导带底电位在H+/H2还原势之上0.430 e V,价带顶电位在O2/H2O...基于密度泛函理论的第一性原理方法,计算了Se掺杂单层MoS_2能带结构和光吸特性,并分析了对其光解水性质的影响。结果表明:本征单层MoS_2为直接带隙结构,禁带宽度为1.740 e V,导带底电位在H+/H2还原势之上0.430 e V,价带顶电位在O2/H2O的氧化势之下0.080 e V,具有可见光催化分解水的能力,但氧化和还原能力不均衡,导致单层MoS_2作为光催化剂分解水的效率不高。通过Se掺杂计算发现,单层MoS_2的禁带宽度变为1.727 e V,相应的光吸收谱变化幅度几乎不变,且体系的形成能较低,表明其热力学稳定性良好。然而,导带底电位调整到H+/H2还原势之上0.253 e V,价带顶电位处于O2/H2O的氧化势之下0.244e V,平衡了氧化与还原能力,单层MoS_2可见光催化分解水的效率得到提高。展开更多
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
文摘基于密度泛函理论的第一性原理方法,计算了Se掺杂单层MoS_2能带结构和光吸特性,并分析了对其光解水性质的影响。结果表明:本征单层MoS_2为直接带隙结构,禁带宽度为1.740 e V,导带底电位在H+/H2还原势之上0.430 e V,价带顶电位在O2/H2O的氧化势之下0.080 e V,具有可见光催化分解水的能力,但氧化和还原能力不均衡,导致单层MoS_2作为光催化剂分解水的效率不高。通过Se掺杂计算发现,单层MoS_2的禁带宽度变为1.727 e V,相应的光吸收谱变化幅度几乎不变,且体系的形成能较低,表明其热力学稳定性良好。然而,导带底电位调整到H+/H2还原势之上0.253 e V,价带顶电位处于O2/H2O的氧化势之下0.244e V,平衡了氧化与还原能力,单层MoS_2可见光催化分解水的效率得到提高。
