Photoelectrochemical(PEC)water splitting is considered as an ideal technology to produce hydrogen.Photogenerated carrier migration is one of the most important roles in the whole process of PEC water splitting.It incl...Photoelectrochemical(PEC)water splitting is considered as an ideal technology to produce hydrogen.Photogenerated carrier migration is one of the most important roles in the whole process of PEC water splitting.It includes bulk transfer inside of the photoelectrode and the exchange at the solid-liquid interface.The energy barriers during the migration process lead to the dramatic recombination of photogenerated hot carrier and the reducing of their redox capacity.Thus,an applied bias voltage should be provided to overcome these energy barriers,which brings the additional loss of energy.Plentiful researches indicate that some methods for the regulation of photogenerated hot carrier,such as p-n junction,unique transfer nanochannel,tandem nanostructure and Z-Scheme transfer structure et al.,show great potential to achieve high-efficient PEC water overall splitting without any applied bias voltage.Up to now,many reviews have summarized and analyzed the methods to enhance the PEC or photocatalysis water splitting from the perspectives of materials,nanostructures and surface modification etc.However,few of them focus on the topic of photogenerated carrier transfer regulation,which is an important and urgent developing technique.For this reason,this review focuses on the regulation of photogenerated carriers generated by the photoelectrodes and summarizes different advanced methods for photogenerated carrier regulation developed in recent years.Some comments and outlooks are also provided at the end of this review.展开更多
WTe2 has attracted a great deal of attention because it exhibits extremely large and non-saturating magnetore- sistance. The underlying origin of such a giant magnetoresistance is still under debate. Utilizing laser-b...WTe2 has attracted a great deal of attention because it exhibits extremely large and non-saturating magnetore- sistance. The underlying origin of such a giant magnetoresistance is still under debate. Utilizing laser-based angle-resolved photoemission spectroscopy with high energy and momentum resolutions, we reveal the complete electronic structure of WTe2. This makes it possible to determine accurately the electron and hole concentrations and their temperature dependence. We find that, with increasing the temperature, the overall electron concen- tration increases while the total hole concentration decreases. It indicates that the electron-hole compensation, if it exists, can only occur in a narrow temperature range,and in most of the temperature range there is an electron-hole imbalance. Our results are not consistent with the perfect electron-hole compensation picture that is commonly considered to be the cause of the unusual magnetoresistance in WTe2. We identify a fiat band near the Brillouin zone center that is close to the Fermi level and exhibits a pronounced temperature dependence. Such a fiat band can play an important role in dictating the transport properties of WTe2. Our results provide new insight on understanding the origin of the unusual magnetoresistance in WTe2.展开更多
Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
Geometry optimization of p-C_(6)H_(4)-connected cyclo[20]carbon(p-C_(6)H_(4)-C_(20))was carried out at M062X/6-311G(d,p)level,three kinds of bond orders(Mayer,Laplacian,and Wiberg),electron-hole distributions,localize...Geometry optimization of p-C_(6)H_(4)-connected cyclo[20]carbon(p-C_(6)H_(4)-C_(20))was carried out at M062X/6-311G(d,p)level,three kinds of bond orders(Mayer,Laplacian,and Wiberg),electron-hole distributions,localized orbital locators(LOL),and infrared(IR)spectrum were also performed at the same level.Based on TD-DFT M062X/6-311G(d,p)method,the first 20 excited states and ultraviolet(UV)spectra of p-C_(6)H_(4)-C_(20) were calculated.Calculation results of π-electron delocalization analyses prove thatπ-electron delocalization of p-C_(6)H_(4)-C_(20) is more likely to occur on shorter C-C bonds rather than longer C-C bonds,and inside/outside of the ring plane rather than above/below the ring plane.Two absorption peaks of p-C_(6)H_(4)-C_(20) locate at about 319 nm and 236 nm,respectively.展开更多
On the basis of the ideal gas model, the polarization of charges in the mantle was obtained, a physical and mathematical model was constructed, and estimated calculations of the dipole mode of the Earth’s magnetic fi...On the basis of the ideal gas model, the polarization of charges in the mantle was obtained, a physical and mathematical model was constructed, and estimated calculations of the dipole mode of the Earth’s magnetic field were performed, taking into account the speed of its angular rotation, the parameters of density and temperature, the chemical composition, the ionization potential, the dielectric constant and the percentage of the main chemical compounds of the mantle substance.展开更多
In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconduct...In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.展开更多
基金financially supported by the National Natural Science Foundation of China,China(Grant Nos.41506093)。
文摘Photoelectrochemical(PEC)water splitting is considered as an ideal technology to produce hydrogen.Photogenerated carrier migration is one of the most important roles in the whole process of PEC water splitting.It includes bulk transfer inside of the photoelectrode and the exchange at the solid-liquid interface.The energy barriers during the migration process lead to the dramatic recombination of photogenerated hot carrier and the reducing of their redox capacity.Thus,an applied bias voltage should be provided to overcome these energy barriers,which brings the additional loss of energy.Plentiful researches indicate that some methods for the regulation of photogenerated hot carrier,such as p-n junction,unique transfer nanochannel,tandem nanostructure and Z-Scheme transfer structure et al.,show great potential to achieve high-efficient PEC water overall splitting without any applied bias voltage.Up to now,many reviews have summarized and analyzed the methods to enhance the PEC or photocatalysis water splitting from the perspectives of materials,nanostructures and surface modification etc.However,few of them focus on the topic of photogenerated carrier transfer regulation,which is an important and urgent developing technique.For this reason,this review focuses on the regulation of photogenerated carriers generated by the photoelectrodes and summarizes different advanced methods for photogenerated carrier regulation developed in recent years.Some comments and outlooks are also provided at the end of this review.
基金Supported by the National Natural Science Foundation of China under Grant No 11574367the National Basic Research Program of China under Grant Nos 2013CB921904 and 2015CB921300+2 种基金the National Key Research and Development Program of China under Grant No 2016YFA0300600the Strategic Priority Research Program(B)of the Chinese Academy of Sciences under Grant No XDB07020300the US Department of Energy under Grant No DE-SC0014208
文摘WTe2 has attracted a great deal of attention because it exhibits extremely large and non-saturating magnetore- sistance. The underlying origin of such a giant magnetoresistance is still under debate. Utilizing laser-based angle-resolved photoemission spectroscopy with high energy and momentum resolutions, we reveal the complete electronic structure of WTe2. This makes it possible to determine accurately the electron and hole concentrations and their temperature dependence. We find that, with increasing the temperature, the overall electron concen- tration increases while the total hole concentration decreases. It indicates that the electron-hole compensation, if it exists, can only occur in a narrow temperature range,and in most of the temperature range there is an electron-hole imbalance. Our results are not consistent with the perfect electron-hole compensation picture that is commonly considered to be the cause of the unusual magnetoresistance in WTe2. We identify a fiat band near the Brillouin zone center that is close to the Fermi level and exhibits a pronounced temperature dependence. Such a fiat band can play an important role in dictating the transport properties of WTe2. Our results provide new insight on understanding the origin of the unusual magnetoresistance in WTe2.
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
文摘Geometry optimization of p-C_(6)H_(4)-connected cyclo[20]carbon(p-C_(6)H_(4)-C_(20))was carried out at M062X/6-311G(d,p)level,three kinds of bond orders(Mayer,Laplacian,and Wiberg),electron-hole distributions,localized orbital locators(LOL),and infrared(IR)spectrum were also performed at the same level.Based on TD-DFT M062X/6-311G(d,p)method,the first 20 excited states and ultraviolet(UV)spectra of p-C_(6)H_(4)-C_(20) were calculated.Calculation results of π-electron delocalization analyses prove thatπ-electron delocalization of p-C_(6)H_(4)-C_(20) is more likely to occur on shorter C-C bonds rather than longer C-C bonds,and inside/outside of the ring plane rather than above/below the ring plane.Two absorption peaks of p-C_(6)H_(4)-C_(20) locate at about 319 nm and 236 nm,respectively.
文摘On the basis of the ideal gas model, the polarization of charges in the mantle was obtained, a physical and mathematical model was constructed, and estimated calculations of the dipole mode of the Earth’s magnetic field were performed, taking into account the speed of its angular rotation, the parameters of density and temperature, the chemical composition, the ionization potential, the dielectric constant and the percentage of the main chemical compounds of the mantle substance.
基金This work is supported by the Trans-Century Training Program Foundation for Talents of Natural Science by the State Education Commission, Key Project of Chinese Ministry of Education (No. 105041)National Natural Science & Foundation Committee of China (NSFC) (Nos. 90401006, 10434030 and 90301004)State Key Project of Basic Research (2003CB314707).
文摘In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.
