Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electr...Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.展开更多
With the discovery of graphene,black phosphorus(BP)has been rediscovered as a two-dimensional(2 D)layered material.Since its first preparation in 2014,2 D BP has elicited immense interest,and has exhibited excellent p...With the discovery of graphene,black phosphorus(BP)has been rediscovered as a two-dimensional(2 D)layered material.Since its first preparation in 2014,2 D BP has elicited immense interest,and has exhibited excellent properties,such as distinct pleated structures in layers,adjustable direct bandgap,high carrier mobility,moderate on/off ratio,large specific surface area,and various interesting in-layer anisotropies.However,the realization of these excellent properties depends on the preparation of highquality 2 D BP sheets.Electrochemical exfoliation methods are typically performed under mild conditions,thus,these methods are convenient,controllable,and can produce high-quality 2 D BP sheets.This review summarizes research progress in BP sheets preparation through anodic,cathodic,and electrolyte exfoliation in recent years.Different exfoliating methods affect the quality of 2 D BP sheets.Moreover,possible exfoliating mechanisms and the potential applications of different exfoliating methods are summarized and discussed in detail.Lastly,the shortcomings of existing research on electrochemical exfoliation are presented,and suggestions and prospects for future research on the electrochemical exfoliation of 2 D BP are proposed.展开更多
基金funded by the National Natural Science Foundation of China(61701288,51706128)the Natural Science Basic Research Program of Shaanxi Province(2021JM-485)+2 种基金the Key Scientific Research Project of Shaanxi Provincial Education Department(20JS019)the High-level Achievement Cultivation Project of Collaborative Innovation Center for Comprehensive Development of Qinba Biological Resources(QBXT-17-8)the Postgraduate Innovation Project of Shaanxi University of Technology(SLGYCX2410).
文摘Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.
基金financially supported by the Youth talent support program of science and technology association of colleges of Shaanxi Province(Grant No.20190609)the Special scientific research plan of education department of Shaanxi province(Grant No.19JK0190 and 19JK0186)+3 种基金the Natural Science Foundation of Shaanxi Province(Grant No.2019JM508)the Open project of Key laboratory of catalytic foundation and application of Shaanxi province(Grant No.SLGPT2019KF01-23)the Opening Foundation of Shaanxi Key Laboratory of Industrial Automation(No.SLGPT2019KF01-10)the School-level project of Shaanxi University of Technology(Grant No.SLGRC03,SLGRC02)。
文摘With the discovery of graphene,black phosphorus(BP)has been rediscovered as a two-dimensional(2 D)layered material.Since its first preparation in 2014,2 D BP has elicited immense interest,and has exhibited excellent properties,such as distinct pleated structures in layers,adjustable direct bandgap,high carrier mobility,moderate on/off ratio,large specific surface area,and various interesting in-layer anisotropies.However,the realization of these excellent properties depends on the preparation of highquality 2 D BP sheets.Electrochemical exfoliation methods are typically performed under mild conditions,thus,these methods are convenient,controllable,and can produce high-quality 2 D BP sheets.This review summarizes research progress in BP sheets preparation through anodic,cathodic,and electrolyte exfoliation in recent years.Different exfoliating methods affect the quality of 2 D BP sheets.Moreover,possible exfoliating mechanisms and the potential applications of different exfoliating methods are summarized and discussed in detail.Lastly,the shortcomings of existing research on electrochemical exfoliation are presented,and suggestions and prospects for future research on the electrochemical exfoliation of 2 D BP are proposed.
