Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transfor...Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.展开更多
Potassium-ion batteries(KIBs)have been seen as a competitive alternative to lithium-ion batteries(LIBs)due to their natural abundance,low cost and rocking chair-like operating mechanism similar to LIBs.Soft carbon has...Potassium-ion batteries(KIBs)have been seen as a competitive alternative to lithium-ion batteries(LIBs)due to their natural abundance,low cost and rocking chair-like operating mechanism similar to LIBs.Soft carbon has a lower voltage plateau compared to hard carbon and an easily modulated lattice structure compared to graphite,which provides particular advantages in KIBs anodes.Pitch has attracted much attention as a simple,readily available and inexpensive precursor for soft carbon,but its structure is easily damaged during cycling.Herein,the flexible film Pitch@CNF are prepared by uniformly winding reticulated carbon fibers on the surface of pitch-soft carbon via electrostatic spinning technique,which not only enables the pitch to maintain its structure well during cycling and withstand the volume expansion upon K^(+) insertion,but also is conducive to ionic transport of the three-dimensional reticulated structure.Meanwhile,the abundant pores on the carbon fibers can provide more K^(+) active sites.The prepared flexible self-supporting films can be used directly as electrodes without the addition of binders and conductive agents.The reversible capacity is 290 mAh·g^(-1)at a current density of 0.1 A·g^(-1),and the capacity retention rate is 83%after 500 cycles.展开更多
Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electro...Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.展开更多
Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like cov...Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.展开更多
Background,aim,and scope Yardang is a kind of typical wind-eroded landform in arid zones both on Earth and other planets.Their geomorphic process records the surface changes and climate,which may play a vital role in ...Background,aim,and scope Yardang is a kind of typical wind-eroded landform in arid zones both on Earth and other planets.Their geomorphic process records the surface changes and climate,which may play a vital role in exploring the coupled landform-atmosphere system in arid zones.Recently,significant progresses have been made in this research field,and a review is still absent,which is the aim of the paper.Materials and methods Previous studies on the distribution,composition,morphology,and climatic driving force of yardang landform were reviewed.Results Earth yardang’s three evolutionary models were generalized:morphology evolution model,altitude evolution model and climate driven evolution model.Extraterrestrial yardang and its evolution are also summarized:the morphology is dominated by long ridges on Venus and Titan,and three yardang evolution hypotheses and an indirect dating method based on stratigraphic contact have been studied on Mars.Discussion In this study,firstly,the definition and morphology of yardang were described to define its characteristics.Secondly,we argue that yardang evolution has two dimensions:short-term variation and longterm variation.In the short-term variation,the morphological evolution of yardang on earth can be divided into four stages:embryonic stage,juvenile stage,mature stage,and demise stage.In the long-term variation,the evolution of yardang on earth is climate-driven,i.e.,it is controlled by atmospheric circulation changes during glacial-interglacial periods.Thirdly,yardang research on extraterrestrial bodies was also summarized:yardang has been found on Mars,Venus,and Titan,and the research focus by far are on geomorphology only.Conclusions(1)Yardang landform is an erosion landform with alternating ridges and troughs,with main form of whale back shape and fluctuations in the range of aspect ratios;(2)the short-term variation of yardang is manifested in its morphological evolution and height change,while the long-term variation is climate-driven;(3)based on Earth yardang,extraterrestrial yardang research has been carried out on Mars,Venus,and Titan.Recommendations and perspectives We then proposed that:(1)yardang formation ages,due to the erosion characteristics,are difficult to constraint;(2)the wind erosion capacity in the yardang areas might have been severely underestimated,making it essential to re-evaluate the previous paleoclimate reconstruction in the closed basins with limited chronological data;(3)yardang evolution is driven by climate change,but the coupling relationship between the yardang geomorphy and the air circulation is still unclear.Finally,future research directions:(1)more chronological data are needed,as well as the wind erosion capacity for yardang initiation and development;(2)the co-evolution of mid-low latitude landforms involved in yardang long-term variation and its relationship with global atmospheric circulation.展开更多
Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional therm...Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional thermal reduction method for inducing SMSI processes is often accompanied by undesirable structural evolution of metal NPs.In this study,a mild electrochemical method has been developed as a new approach to induce SMSI,using the cable structured core@shell CNT@SnO_(2) loaded Pt NPs as a proof of concept.The induced SnO_(x) encapsulation layer on the surface of Pt NPs can protect Pt NPs from the poisoned of CO impurity in hydrogen oxidation reaction(HOR),and the HOR current density could still maintain 85% for 2000 s with 10,000 ppm CO in H_(2),while the commercial Pt/C is completely inactivated.In addition,the electrons transfer from SnO_(x) to Pt NPs improved the HOR activity of the E-Pt-CNT@SnO_(2),achieving the excellent exchange current density of 1.55 A·mgPt^(-1).In situ Raman spectra and theoretical calculations show that the key to the electrochemical-method-induced SMSI is the formation of defects and the migration of SnO_(x) caused by the electrochemical redox operation,and the weakening the SneO bond strength by Pt NPs.展开更多
文摘Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.
文摘Potassium-ion batteries(KIBs)have been seen as a competitive alternative to lithium-ion batteries(LIBs)due to their natural abundance,low cost and rocking chair-like operating mechanism similar to LIBs.Soft carbon has a lower voltage plateau compared to hard carbon and an easily modulated lattice structure compared to graphite,which provides particular advantages in KIBs anodes.Pitch has attracted much attention as a simple,readily available and inexpensive precursor for soft carbon,but its structure is easily damaged during cycling.Herein,the flexible film Pitch@CNF are prepared by uniformly winding reticulated carbon fibers on the surface of pitch-soft carbon via electrostatic spinning technique,which not only enables the pitch to maintain its structure well during cycling and withstand the volume expansion upon K^(+) insertion,but also is conducive to ionic transport of the three-dimensional reticulated structure.Meanwhile,the abundant pores on the carbon fibers can provide more K^(+) active sites.The prepared flexible self-supporting films can be used directly as electrodes without the addition of binders and conductive agents.The reversible capacity is 290 mAh·g^(-1)at a current density of 0.1 A·g^(-1),and the capacity retention rate is 83%after 500 cycles.
文摘Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.
文摘Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.
文摘Background,aim,and scope Yardang is a kind of typical wind-eroded landform in arid zones both on Earth and other planets.Their geomorphic process records the surface changes and climate,which may play a vital role in exploring the coupled landform-atmosphere system in arid zones.Recently,significant progresses have been made in this research field,and a review is still absent,which is the aim of the paper.Materials and methods Previous studies on the distribution,composition,morphology,and climatic driving force of yardang landform were reviewed.Results Earth yardang’s three evolutionary models were generalized:morphology evolution model,altitude evolution model and climate driven evolution model.Extraterrestrial yardang and its evolution are also summarized:the morphology is dominated by long ridges on Venus and Titan,and three yardang evolution hypotheses and an indirect dating method based on stratigraphic contact have been studied on Mars.Discussion In this study,firstly,the definition and morphology of yardang were described to define its characteristics.Secondly,we argue that yardang evolution has two dimensions:short-term variation and longterm variation.In the short-term variation,the morphological evolution of yardang on earth can be divided into four stages:embryonic stage,juvenile stage,mature stage,and demise stage.In the long-term variation,the evolution of yardang on earth is climate-driven,i.e.,it is controlled by atmospheric circulation changes during glacial-interglacial periods.Thirdly,yardang research on extraterrestrial bodies was also summarized:yardang has been found on Mars,Venus,and Titan,and the research focus by far are on geomorphology only.Conclusions(1)Yardang landform is an erosion landform with alternating ridges and troughs,with main form of whale back shape and fluctuations in the range of aspect ratios;(2)the short-term variation of yardang is manifested in its morphological evolution and height change,while the long-term variation is climate-driven;(3)based on Earth yardang,extraterrestrial yardang research has been carried out on Mars,Venus,and Titan.Recommendations and perspectives We then proposed that:(1)yardang formation ages,due to the erosion characteristics,are difficult to constraint;(2)the wind erosion capacity in the yardang areas might have been severely underestimated,making it essential to re-evaluate the previous paleoclimate reconstruction in the closed basins with limited chronological data;(3)yardang evolution is driven by climate change,but the coupling relationship between the yardang geomorphy and the air circulation is still unclear.Finally,future research directions:(1)more chronological data are needed,as well as the wind erosion capacity for yardang initiation and development;(2)the co-evolution of mid-low latitude landforms involved in yardang long-term variation and its relationship with global atmospheric circulation.
基金the“National Natural Science Foundation of China(No.22122202)”.
文摘Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional thermal reduction method for inducing SMSI processes is often accompanied by undesirable structural evolution of metal NPs.In this study,a mild electrochemical method has been developed as a new approach to induce SMSI,using the cable structured core@shell CNT@SnO_(2) loaded Pt NPs as a proof of concept.The induced SnO_(x) encapsulation layer on the surface of Pt NPs can protect Pt NPs from the poisoned of CO impurity in hydrogen oxidation reaction(HOR),and the HOR current density could still maintain 85% for 2000 s with 10,000 ppm CO in H_(2),while the commercial Pt/C is completely inactivated.In addition,the electrons transfer from SnO_(x) to Pt NPs improved the HOR activity of the E-Pt-CNT@SnO_(2),achieving the excellent exchange current density of 1.55 A·mgPt^(-1).In situ Raman spectra and theoretical calculations show that the key to the electrochemical-method-induced SMSI is the formation of defects and the migration of SnO_(x) caused by the electrochemical redox operation,and the weakening the SneO bond strength by Pt NPs.
