Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with th...Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.展开更多
Herein,we demonstrated the integration of BiVO_(4)-based photoanode with metallic Zn cathode for high-performance CO_(2)reduction,and a record CO production rate of 113.32μmol cm^(−2)h^(−1)with a FECO of 90.57%has be...Herein,we demonstrated the integration of BiVO_(4)-based photoanode with metallic Zn cathode for high-performance CO_(2)reduction,and a record CO production rate of 113.32μmol cm^(−2)h^(−1)with a FECO of 90.57%has been achieved under simulated sunlight(AM 1.5 G,100 mW),accompanying with an excellent stability.More importantly,the direct observation of spatial charge separation/transfer and dynamic surface catalysis for both H_(2)O oxidation and CO_(2)reduction has been firstly achieved by the combination of in situ X-ray photoelectron spectroscopy(IS-XPS)with Fourier transform infrared reflection(IS-FTIR).Under light irradiation,the electron-hole pairs have been generated on BiVO_(4) photoanode,and holes rapidly transfer to photoanode surfaces for participating in oxygen evolution reaction(OER)through the formation of*OH and*OOH intermediates.Simultaneously,the proton-coupled electron transfer to the Zn cathode surfaces drive the reduction of adsorbed CO_(2)molecules into CO via the formation*COOH and*CO intermediates.Thereby,this work offers new insights into fundamental understanding of CO_(2)reduction process,which facilitates the future development of highly efficient carbon fixation systems.展开更多
Effects of noise on rate oscillations during CO oxidation on Pt（110） surface were investigated, both theoretically and numerically, by focusing on the interplay of internal noise （IN） due to stochasticity in react...Effects of noise on rate oscillations during CO oxidation on Pt（110） surface were investigated, both theoretically and numerically, by focusing on the interplay of internal noise （IN） due to stochasticity in reaction events, and external noise （EN） resulting from parameter perturbation. The surface is divided into cells of variable size which are assumed to be well mixed, and we consider the behavior inside a single cell. Attention is paid to parameter regions subthreshold of the deterministic Hopf bifurcation, where noise can induce stochastic oscillations, the signal-to-noise ratio （SNR） of which shows a maximum with the variation of noise intensity, known as coherent resonance （CR）. By stochastic normal theory, we show that IN and EN contribute in a weighted additive way to an effective noise that lead to CR, such that SNR shows a ridge shape in the D-1/√N plane, where D and 1/√N measures the strength of EN and IN, respectively. It is shown that for too large IN （EN）, CR behavior with EN （IN） no longer exists. Numerical simulations show good agreements with the theoretical results.展开更多
Surface chemistry focuses on the investigation of the adsorption,migration,assembly,activation,reaction,and desorption of atoms and molecules at surfaces.Surface chemistry plays the pivotal roles in both fundamental s...Surface chemistry focuses on the investigation of the adsorption,migration,assembly,activation,reaction,and desorption of atoms and molecules at surfaces.Surface chemistry plays the pivotal roles in both fundamental science and applied technology.This review will summarize the recent progresses on surface assembly,synthesis and catalysis investigated mainly by scanning tunneling microscopy and atomic force microscopy.Surface assemblies of water and small biomolecules,construction of Sierpin′ski triangles and surface chirality are summarized.On-surface synthesis of conjugated carbo-and heterocycles and other kinds of carbon nanostructures are surveyed.Surface model catalysis,including single-atom catalysis and electrochemical catalysis,are discussed at the single-atom level.展开更多
Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on...Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.展开更多
文摘Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.
基金supported by the National Natural Science Foundation of China(21832005,22372181,22072168,22002175)Major Program of the Lanzhou Institute of Chemical Physics,CAS(ZYFZFX-3),Major Science and Technology Projects in Gansu Province(22ZD6GA003)the CAS“Light of West China”Program and West Light Foundation of The Chinese Academy of Sciences(xbzg-zdsys-202209).
文摘Herein,we demonstrated the integration of BiVO_(4)-based photoanode with metallic Zn cathode for high-performance CO_(2)reduction,and a record CO production rate of 113.32μmol cm^(−2)h^(−1)with a FECO of 90.57%has been achieved under simulated sunlight(AM 1.5 G,100 mW),accompanying with an excellent stability.More importantly,the direct observation of spatial charge separation/transfer and dynamic surface catalysis for both H_(2)O oxidation and CO_(2)reduction has been firstly achieved by the combination of in situ X-ray photoelectron spectroscopy(IS-XPS)with Fourier transform infrared reflection(IS-FTIR).Under light irradiation,the electron-hole pairs have been generated on BiVO_(4) photoanode,and holes rapidly transfer to photoanode surfaces for participating in oxygen evolution reaction(OER)through the formation of*OH and*OOH intermediates.Simultaneously,the proton-coupled electron transfer to the Zn cathode surfaces drive the reduction of adsorbed CO_(2)molecules into CO via the formation*COOH and*CO intermediates.Thereby,this work offers new insights into fundamental understanding of CO_(2)reduction process,which facilitates the future development of highly efficient carbon fixation systems.
文摘Effects of noise on rate oscillations during CO oxidation on Pt（110） surface were investigated, both theoretically and numerically, by focusing on the interplay of internal noise （IN） due to stochasticity in reaction events, and external noise （EN） resulting from parameter perturbation. The surface is divided into cells of variable size which are assumed to be well mixed, and we consider the behavior inside a single cell. Attention is paid to parameter regions subthreshold of the deterministic Hopf bifurcation, where noise can induce stochastic oscillations, the signal-to-noise ratio （SNR） of which shows a maximum with the variation of noise intensity, known as coherent resonance （CR）. By stochastic normal theory, we show that IN and EN contribute in a weighted additive way to an effective noise that lead to CR, such that SNR shows a ridge shape in the D-1/√N plane, where D and 1/√N measures the strength of EN and IN, respectively. It is shown that for too large IN （EN）, CR behavior with EN （IN） no longer exists. Numerical simulations show good agreements with the theoretical results.
基金supported by the National Natural Science Foundation of China(Nos.22225202,92356309,22132007,21991132,22172002)。
文摘Surface chemistry focuses on the investigation of the adsorption,migration,assembly,activation,reaction,and desorption of atoms and molecules at surfaces.Surface chemistry plays the pivotal roles in both fundamental science and applied technology.This review will summarize the recent progresses on surface assembly,synthesis and catalysis investigated mainly by scanning tunneling microscopy and atomic force microscopy.Surface assemblies of water and small biomolecules,construction of Sierpin′ski triangles and surface chirality are summarized.On-surface synthesis of conjugated carbo-and heterocycles and other kinds of carbon nanostructures are surveyed.Surface model catalysis,including single-atom catalysis and electrochemical catalysis,are discussed at the single-atom level.
基金financially supported by the National Natural Science Foundation of China(21222305,11079005,20923001)the National Basic Research Program of China(2011CBA00503,2013CB933100)
文摘Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.
