Researching the dispersion as well as the stability of metals on the oxide surfaces is essentially important for understanding the interaction mecha-nisms at the metal/oxide interfaces and thus optimizing the activiti...Researching the dispersion as well as the stability of metals on the oxide surfaces is essentially important for understanding the interaction mecha-nisms at the metal/oxide interfaces and thus optimizing the activities of the heterogeneous catalysts.Here in this work,we have investigated the growth behavior of Pd particles on the polar surfaces of ZnO with scanning tunneling microscopy(STM).By systematically varying the coverages as well as the annealing temperatures,we found that at room temperature Pd tends to form three-dimensional(3D)round particles on the ZnO(000)surface but grow into monolayer two-dimensional(2D)hexagonal islands on the ZnO(0001)surface.During annealing processes,the Pd particles on ZnO(000)aggregate gently while maintaining the 3D morphology in the mild temperature range but then quickly transform in-to tall hexagonal islands at elevated temperatures.In contrast,the segregation of Pd islands on ZnO(0001)occurs gradually along with the temperature rising without changing the 2D morphology.These results directly reflect the different interaction strengths of Pd on the dis-tinct ZnO polar surfaces.They also provide important input for understanding the facet-de-pendent catalytic mechanisms of the Pd/ZnO catalytic systems.展开更多
The migration and transformation of hexavalent chromium(Cr(VI))in the environment are regulated by pyrite(FeS2).However,variations in pyrite crystal facets influence the adsorption behavior and electron transfer betwe...The migration and transformation of hexavalent chromium(Cr(VI))in the environment are regulated by pyrite(FeS2).However,variations in pyrite crystal facets influence the adsorption behavior and electron transfer between pyrite and Cr(VI),thereby impacting the Cr(VI)reduction performance.Herein,two naturally common facets of pyritewere synthesized hydrothermally to investigate the facet-dependent mechanisms of Cr(VI)reduction.The experimental results revealed that the{111}facet exhibited approximately 1.30–1.50 times higher efficiency in Cr(VI)reduction compared to the{100}facet.Surface analyses and electrochemical results indicated that{111}facet displayed a higher iron-sulfur oxidation level,which was affected by its superior electrochemical properties during the reaction with Cr(VI).Density functional theory(DFT)calculations demonstrated that the narrower band gap and lower work function on{111}facet were more favorable for the electron transfer between Fe(II)and Cr(VI).Furthermore,different adsorption configurations were observed on{100}and{111}surfaces due to the unique arrangements of Fe and S atoms.Specifically,O atoms in Cr_(2)O_(7)^(2−)directly bound with the S sites on{100}but the Fe sites on{111}.According to the density of states(DOS),the Fe site had better reactivity than the S site in the reaction,which appeared to be related to the fracture of S-S bonds.Additionally,the adsorption configuration of Cr_(2)O_(7)^(2−)on{111}surface showed a stronger adsorption energy and a more stable coordination mode,favoring subsequent Cr(VI)reduction process.These findings provide an in-depth analysis of facet-dependent mechanisms underlying Cr(VI)reduction behavior,offering new insights into studying environmental interactions between heavy metals and natural minerals.展开更多
Developing high-performance electrocatalysts for CO_(2) reduction reaction(CO_(2)RR)is crucial since it is beneficial for environmental protection and the resulting value-add chemical products can act as an alternativ...Developing high-performance electrocatalysts for CO_(2) reduction reaction(CO_(2)RR)is crucial since it is beneficial for environmental protection and the resulting value-add chemical products can act as an alternative to fossil feedstocks.Nonetheless,the direct reduction of CO_(2) into long-chain hydrocarbons and oxygenated hydrocarbons with high selectivity remains challenging.Copper(Cu)shows a distinctive advantage that it is the only pure metal catalyst for reducing CO_(2) into multi-carbon(C_(2+))products and the certain facets(e.g.,(100),(111),(111))of Cu nanocrystals exhibit relatively low energy barriers for the formation of specific products(e.g.,CO,HCOOH,CH_(4),C_(2)H_(4),C_(2)H_(5)OH,and other C_(2+) products).Therefore,extensive studies have been carried out to explore the relationship between the facets of Cu nanocrystals and corresponding catalytic products.In this review,we will discuss the crystal facet-dependent electrocatalytic CO_(2)RR performance in metallic Cu catalysts,meanwhile,the detailed reaction mechanisms will be systematically summarized.In addition,we will provide a personal perspective for the future research directions in this emerging field.We believe this review is helpful to guide the design of high-selectivity Cu-based electrocatalysts for CO_(2)RR.展开更多
Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispe...Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispersing functional nanomaterials into the LCs has emerged as a promising approach to achieve outstanding E-O properties. In this work, we report the facet-controlled E-O properties of a chiral nematic LC （N＊LC） doped with cubic, octahedral, and rhornbic dodecahedral Cu20. The outstanding E-O properties of the doped systems are related to the interaction between the liquid crystals and Cu20 dopants with different exposed crystal planes. Doping with octahedral and rhombic dodecahedral Cu20 reduces the stability of the planar state, as a result of both the surface abundance of active Cu atoms that interact with the polarized LC molecules, and the large amounts of vertexes and edges on the crystal surfaces, which accelerate the transition from the planar to the focal conic state under an applied electric field. Rhombic Cu20 is the most effective dopant for improving the E-O properties of the present LCs, resulting in a 65.31% reduction of the threshold voltage. The facet and morphology effects highlighted in this work provide a new pathway to develop excellent energy-saving meso-materials with exposed high-reactivity facets, improving their potential applications in electro-optical technologies and information displays.展开更多
Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interfa...Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interface remains an unexploited and promising area.Herein,we render the controlled growth of Pt nanoparticles(NPs)on Pd nanosheets(NSs)by regulating the reduction kinetics of Pt^(2+)with solvents.Specifically,the fast reduction kinetic makes the Pt NPs uniformly deposited on the Pd NSs(U-Pd@Pt HS),while the slow reduction kinetic leads to the preferential growth of Pt NPs on the edge of the Pd NSs(E-Pd@Pt HS).Density functional theory calculations demonstrate that Pd(111)-Pt interface in U-Pd@Pt HS induces the electron-deficient status of Pd substrates,triggering the d-band center downshift and amplifying the Pd-Pt intermetallic interaction.The synergy between the electronic effect and interfacial effect facilitates the removal of poisonous intermediates on U-Pd@Pt HS.By virtue of the Pd NSs@Pt NPs interface,the heterostructure achieves exceptional methanol oxidation reaction activity as well as improved durability.This study innovatively proposes heterostructure engineering with facetdependent interfacial modulation,offering instructive guidelines for the rational design of versatile heterocatalysts.展开更多
Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electr...Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electrosynthesis limits its implementation in industrially interesting processes.Herein,we report a composite structured catalyst composed of Ag and Cu_(2)O with different crystal faces to achieve highly efficient reduction of CO_(2)to C_(2)H_(4).The catalyst composed of Ag and octahedral Cu_(2)O enclosed with(111)facet exhibits the best CO_(2)electroreduction performance,with the Faradaic efficiency(FE)and partial current density reaching 66.8%and 17.8 mA cm2 for C_(2)H_(4)product at-1.2 VRHE in 0.5 M KHCO_(3),respectively.Physical characterization and electrochemical test analysis indicate that the high selectivity for C_(2)H_(4)product stems from the synergistic effect of crystal faces control engineering and tandem catalysis.Specifically,Ag can provide optimal availability of CO intermediate by suppressing hydrogen evolution;subsequently,C-C coupling is promoted on the intimate surface of Cu_(2)O with facetdependent selectivity.The insights gained from this work may be beneficial for designing efficient multicomponent catalysts for improving the selectivity of electrochemical CO_(2)reduction reaction to generate C2þproducts.展开更多
The Au(100)surface has been a subject of intense studies due to excellent catalytic activities and its model character for surface science.However,the spontaneous surface reconstruction buries active Au(100)plane and ...The Au(100)surface has been a subject of intense studies due to excellent catalytic activities and its model character for surface science.However,the spontaneous surface reconstruction buries active Au(100)plane and limits practical applications,how to controllably eliminate the surface reconstruction over large scale remains challenging.Here,we experimentally and theoretically demonstrate that simple decoration of the Au(100)surface by tellurium(Te)atoms can uniquely lift its reconstruction over large scale.Scanning tunneling microscopy imaging reveals that the lifting of surface reconstruction preferentially starts from the boundaries of distinct domains and then extends progressively into the domains with the reconstruction rows perpendicular to the boundaries,leaving a Au(100)-(1×1)surface behind.The Au(100)-(1×1)is saturated at~84%±2%with respect to the whole surface at a Te coverage of 0.16 monolayer.With further increasing the Te coverage to 0.25 monolayer,the Au(100)-(1×1)surface becomes reduced and overlapped by a well-ordered(2×2)-Te superstructure.No similar behavior is found for Te-decorated Au(111),Cu(111),Cu(100)surfaces,nor for the decorated Au(100)with other elements.This result may pave the way to design Au-based catalysts and,as an intermediate step,even potentially open a new route to constructing complex transition metal dichalcogenides.展开更多
基金supported by the National Natural Science Foundation of China(No.22172152,No.21872130)the National Key R&D Program of China(No.2021YFA1502801).
文摘Researching the dispersion as well as the stability of metals on the oxide surfaces is essentially important for understanding the interaction mecha-nisms at the metal/oxide interfaces and thus optimizing the activities of the heterogeneous catalysts.Here in this work,we have investigated the growth behavior of Pd particles on the polar surfaces of ZnO with scanning tunneling microscopy(STM).By systematically varying the coverages as well as the annealing temperatures,we found that at room temperature Pd tends to form three-dimensional(3D)round particles on the ZnO(000)surface but grow into monolayer two-dimensional(2D)hexagonal islands on the ZnO(0001)surface.During annealing processes,the Pd particles on ZnO(000)aggregate gently while maintaining the 3D morphology in the mild temperature range but then quickly transform in-to tall hexagonal islands at elevated temperatures.In contrast,the segregation of Pd islands on ZnO(0001)occurs gradually along with the temperature rising without changing the 2D morphology.These results directly reflect the different interaction strengths of Pd on the dis-tinct ZnO polar surfaces.They also provide important input for understanding the facet-de-pendent catalytic mechanisms of the Pd/ZnO catalytic systems.
基金supported by the National Natural Science Foundation of China(No.42277256)the Natural Science Foundation of Hunan Province(No.2022JJ30710)+1 种基金Hunan Province Environmental Protection Research Program(No.HBKT-2021014)Guangdong Province Dabaoshan Mining Co.Ltd Technology Program(Semi-industrial test of 200T/time low-grade copper ore bio-heap leaching).
文摘The migration and transformation of hexavalent chromium(Cr(VI))in the environment are regulated by pyrite(FeS2).However,variations in pyrite crystal facets influence the adsorption behavior and electron transfer between pyrite and Cr(VI),thereby impacting the Cr(VI)reduction performance.Herein,two naturally common facets of pyritewere synthesized hydrothermally to investigate the facet-dependent mechanisms of Cr(VI)reduction.The experimental results revealed that the{111}facet exhibited approximately 1.30–1.50 times higher efficiency in Cr(VI)reduction compared to the{100}facet.Surface analyses and electrochemical results indicated that{111}facet displayed a higher iron-sulfur oxidation level,which was affected by its superior electrochemical properties during the reaction with Cr(VI).Density functional theory(DFT)calculations demonstrated that the narrower band gap and lower work function on{111}facet were more favorable for the electron transfer between Fe(II)and Cr(VI).Furthermore,different adsorption configurations were observed on{100}and{111}surfaces due to the unique arrangements of Fe and S atoms.Specifically,O atoms in Cr_(2)O_(7)^(2−)directly bound with the S sites on{100}but the Fe sites on{111}.According to the density of states(DOS),the Fe site had better reactivity than the S site in the reaction,which appeared to be related to the fracture of S-S bonds.Additionally,the adsorption configuration of Cr_(2)O_(7)^(2−)on{111}surface showed a stronger adsorption energy and a more stable coordination mode,favoring subsequent Cr(VI)reduction process.These findings provide an in-depth analysis of facet-dependent mechanisms underlying Cr(VI)reduction behavior,offering new insights into studying environmental interactions between heavy metals and natural minerals.
基金financially supported by the National Natural Science Foundation of China(No.92061119)the Beijing NOVA program(No.Z201100006820066)the Fundamental Research Funds for the Central Universities(No.FRF-DF-20-03,No.06500113,No.06500119)。
文摘Developing high-performance electrocatalysts for CO_(2) reduction reaction(CO_(2)RR)is crucial since it is beneficial for environmental protection and the resulting value-add chemical products can act as an alternative to fossil feedstocks.Nonetheless,the direct reduction of CO_(2) into long-chain hydrocarbons and oxygenated hydrocarbons with high selectivity remains challenging.Copper(Cu)shows a distinctive advantage that it is the only pure metal catalyst for reducing CO_(2) into multi-carbon(C_(2+))products and the certain facets(e.g.,(100),(111),(111))of Cu nanocrystals exhibit relatively low energy barriers for the formation of specific products(e.g.,CO,HCOOH,CH_(4),C_(2)H_(4),C_(2)H_(5)OH,and other C_(2+) products).Therefore,extensive studies have been carried out to explore the relationship between the facets of Cu nanocrystals and corresponding catalytic products.In this review,we will discuss the crystal facet-dependent electrocatalytic CO_(2)RR performance in metallic Cu catalysts,meanwhile,the detailed reaction mechanisms will be systematically summarized.In addition,we will provide a personal perspective for the future research directions in this emerging field.We believe this review is helpful to guide the design of high-selectivity Cu-based electrocatalysts for CO_(2)RR.
基金This work was mainly supported by National Basic Research Program of China (No.2014CB931802),the Major Project of International Cooperation of the Ministry of Science and Technology (No.2013DFB50340),National Natural Science Foundations of China (Nos.51272012,21471013,51532001,51333001,51173003,51402006 and 51303007),the Major Program of Chinese Ministry of Education (No.313002),the Beijing Natural Science Foundation (No.2163052) and China Postdoctoral Science Foundation Funded Project (No.2015M570916).
文摘Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispersing functional nanomaterials into the LCs has emerged as a promising approach to achieve outstanding E-O properties. In this work, we report the facet-controlled E-O properties of a chiral nematic LC （N＊LC） doped with cubic, octahedral, and rhornbic dodecahedral Cu20. The outstanding E-O properties of the doped systems are related to the interaction between the liquid crystals and Cu20 dopants with different exposed crystal planes. Doping with octahedral and rhombic dodecahedral Cu20 reduces the stability of the planar state, as a result of both the surface abundance of active Cu atoms that interact with the polarized LC molecules, and the large amounts of vertexes and edges on the crystal surfaces, which accelerate the transition from the planar to the focal conic state under an applied electric field. Rhombic Cu20 is the most effective dopant for improving the E-O properties of the present LCs, resulting in a 65.31% reduction of the threshold voltage. The facet and morphology effects highlighted in this work provide a new pathway to develop excellent energy-saving meso-materials with exposed high-reactivity facets, improving their potential applications in electro-optical technologies and information displays.
基金supported by the National Natural Science Foundation of China(Grant numbers 52274304,52073199)。
文摘Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interface remains an unexploited and promising area.Herein,we render the controlled growth of Pt nanoparticles(NPs)on Pd nanosheets(NSs)by regulating the reduction kinetics of Pt^(2+)with solvents.Specifically,the fast reduction kinetic makes the Pt NPs uniformly deposited on the Pd NSs(U-Pd@Pt HS),while the slow reduction kinetic leads to the preferential growth of Pt NPs on the edge of the Pd NSs(E-Pd@Pt HS).Density functional theory calculations demonstrate that Pd(111)-Pt interface in U-Pd@Pt HS induces the electron-deficient status of Pd substrates,triggering the d-band center downshift and amplifying the Pd-Pt intermetallic interaction.The synergy between the electronic effect and interfacial effect facilitates the removal of poisonous intermediates on U-Pd@Pt HS.By virtue of the Pd NSs@Pt NPs interface,the heterostructure achieves exceptional methanol oxidation reaction activity as well as improved durability.This study innovatively proposes heterostructure engineering with facetdependent interfacial modulation,offering instructive guidelines for the rational design of versatile heterocatalysts.
基金This work was supported by the University of Science and Technology Beijing.DG acknowledges the financial support from 111 Project(no.B170003)Foshan Science and Technology Innovation Project(no.2018IT100363).
文摘Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electrosynthesis limits its implementation in industrially interesting processes.Herein,we report a composite structured catalyst composed of Ag and Cu_(2)O with different crystal faces to achieve highly efficient reduction of CO_(2)to C_(2)H_(4).The catalyst composed of Ag and octahedral Cu_(2)O enclosed with(111)facet exhibits the best CO_(2)electroreduction performance,with the Faradaic efficiency(FE)and partial current density reaching 66.8%and 17.8 mA cm2 for C_(2)H_(4)product at-1.2 VRHE in 0.5 M KHCO_(3),respectively.Physical characterization and electrochemical test analysis indicate that the high selectivity for C_(2)H_(4)product stems from the synergistic effect of crystal faces control engineering and tandem catalysis.Specifically,Ag can provide optimal availability of CO intermediate by suppressing hydrogen evolution;subsequently,C-C coupling is promoted on the intimate surface of Cu_(2)O with facetdependent selectivity.The insights gained from this work may be beneficial for designing efficient multicomponent catalysts for improving the selectivity of electrochemical CO_(2)reduction reaction to generate C2þproducts.
基金the National Natural Science Foundation of China(No.1210040808)the Natural Science Foundation of Jiangsu Province(Nos.BK20210312 and BK20212008)+3 种基金the National Key Research and Development Program of China(No.2019YFA0705400)the Fundamental Research Funds for the Central Universities(Nos.NJ2022002,NZ2020001,and NS2022014)the Program for Innovative Talents and Entrepreneur in Jiangsu,Research Fund of State Key Laboratory of Mechanics and Control of Mechanical Structures(Nos.MCMS-I-0419G02 and MCMS-I-0421K01)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘The Au(100)surface has been a subject of intense studies due to excellent catalytic activities and its model character for surface science.However,the spontaneous surface reconstruction buries active Au(100)plane and limits practical applications,how to controllably eliminate the surface reconstruction over large scale remains challenging.Here,we experimentally and theoretically demonstrate that simple decoration of the Au(100)surface by tellurium(Te)atoms can uniquely lift its reconstruction over large scale.Scanning tunneling microscopy imaging reveals that the lifting of surface reconstruction preferentially starts from the boundaries of distinct domains and then extends progressively into the domains with the reconstruction rows perpendicular to the boundaries,leaving a Au(100)-(1×1)surface behind.The Au(100)-(1×1)is saturated at~84%±2%with respect to the whole surface at a Te coverage of 0.16 monolayer.With further increasing the Te coverage to 0.25 monolayer,the Au(100)-(1×1)surface becomes reduced and overlapped by a well-ordered(2×2)-Te superstructure.No similar behavior is found for Te-decorated Au(111),Cu(111),Cu(100)surfaces,nor for the decorated Au(100)with other elements.This result may pave the way to design Au-based catalysts and,as an intermediate step,even potentially open a new route to constructing complex transition metal dichalcogenides.
