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
The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral elec-trolytes,their efficie...The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral elec-trolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2)conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2)electrolysis.It commences with an overview of the latest advancements in acidic CO_(2)electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2)elec-trolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2)electrolysis are suggested.展开更多
Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst onl...Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2)product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.展开更多
Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has...Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.展开更多
The magnetization reduction of hematite using biomass waste can effectively utilize waste and reduce CO_(2) emission to achieve the goals of carbon peaking and carbon neutrality.The effects of temperatures on suspensi...The magnetization reduction of hematite using biomass waste can effectively utilize waste and reduce CO_(2) emission to achieve the goals of carbon peaking and carbon neutrality.The effects of temperatures on suspension magnetization roasting of hematite using biomass waste for evolved gases have been investigated using TG-FTIR,Py-GC/MS and gas composition analyzer.The mixture reduction process is divided into four stages.In the temperature range of 200-450℃ for mixture,the release of CO_(2),acids,and ketones is dominated in gases products.The yield and concentration of small molecules reducing gases increase when the temperature increases from 450 to 900℃.At 700℃,the volume concentrations of CO,H_(2) and CH_(4) peak at 8.91%,8.90% and 4.91%,respectively.During the suspension magnetization roasting process,an optimal iron concentrate with an iron grade of 70.86%,a recovery of 98.66% and a magnetic conversion of 45.70% is obtained at 700℃.Therefore,the magnetization reduction could react greatly in the temperature range of 600 to 700℃ owing to the suitable reducing gases.This study shows a detail gaseous evolution of roasting temperature and provides a new insight for studying the reduction process of hematite using biomass waste.展开更多
This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction pro...This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.展开更多
A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring sp...A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions （temperature 180 °C, initial KOH-to-ore mass ratio 4：1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min）, vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.展开更多
A modified shrinking unreacted-core model,based on thermogravimetric analysis,was developed to investigate CaSO4 decomposition in oxy-fuel combustion,especially under isothermal condition which is difficult to achieve...A modified shrinking unreacted-core model,based on thermogravimetric analysis,was developed to investigate CaSO4 decomposition in oxy-fuel combustion,especially under isothermal condition which is difficult to achieve in actual experiments due to high-temperature corrosion.A method was proposed to calculate the reaction rate constant for CaSO4 decomposition.Meanwhile,the diffusion of SO2 and O2,and the sintering of CaO were fully considered during the development of model.The results indicate that the model can precisely predict the decomposition of CaSO4 under high SO2 concentration（1100×10-6）.Concentrations of SO2 and O2 on the unreacted-core surface were found to increase first and then decrease with increasing temperature,and the average specific surface area and porosity of each CaO sintering layer decreased with increasing time.The increase of SO2 and/or O2 concentration inhibited CaSO4 decomposition.Moreover,the kinetics of CaSO4 decomposition had obvious dependence on temperature and the decomposition rate can be dramatically accelerated with increasing temperature.展开更多
Micro-arc oxidation （MAO） process was carried out in a dual electrolyte system of NaAlO 2 and Na 3 PO 4 to develop compact, smooth and corrosion-resistant coatings on ZK60 Mg alloy by single factor experiments. The ...Micro-arc oxidation （MAO） process was carried out in a dual electrolyte system of NaAlO 2 and Na 3 PO 4 to develop compact, smooth and corrosion-resistant coatings on ZK60 Mg alloy by single factor experiments. The microstructural characteristics of coatings were investigated by X-ray diffractometry （XRD） and scanning electron microscopy （SEM） coupled with energy dispersive X-ray spectroscopy （EDS）. Test of mass loss was conducted at a 3.5% NaCl solution to assess the resistance to corrosion. The effect of every element in the dual electrolyte system on voltage—time responses during MAO process and the coating characteristic were also analyzed and discussed systematically via single factor experiments. The results reveal that the main components of NaAlO 2 and Na 3 PO 4 as well as additives of NaOH, NaB4O7 and C6H5Na3O7 demonstrate different effects on MAO process and coating characteristics. By means of single factor experiments, an optimized dual electrolyte system was developed, containing 17.5 g/L NaAlO 2, 5.0 g/LNa3 PO4, 5.0 g/L NaOH, 3.0 g/L NaB4O7 and 4.2g/LC6H5Na3O7 .展开更多
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The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral elec-trolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2)conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2)electrolysis.It commences with an overview of the latest advancements in acidic CO_(2)electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2)elec-trolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2)electrolysis are suggested.
文摘Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2)product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.
文摘Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.
基金Project(52022019)supported by the National Natural Science Foundation of China。
文摘The magnetization reduction of hematite using biomass waste can effectively utilize waste and reduce CO_(2) emission to achieve the goals of carbon peaking and carbon neutrality.The effects of temperatures on suspension magnetization roasting of hematite using biomass waste for evolved gases have been investigated using TG-FTIR,Py-GC/MS and gas composition analyzer.The mixture reduction process is divided into four stages.In the temperature range of 200-450℃ for mixture,the release of CO_(2),acids,and ketones is dominated in gases products.The yield and concentration of small molecules reducing gases increase when the temperature increases from 450 to 900℃.At 700℃,the volume concentrations of CO,H_(2) and CH_(4) peak at 8.91%,8.90% and 4.91%,respectively.During the suspension magnetization roasting process,an optimal iron concentrate with an iron grade of 70.86%,a recovery of 98.66% and a magnetic conversion of 45.70% is obtained at 700℃.Therefore,the magnetization reduction could react greatly in the temperature range of 600 to 700℃ owing to the suitable reducing gases.This study shows a detail gaseous evolution of roasting temperature and provides a new insight for studying the reduction process of hematite using biomass waste.
基金Fiscal Year 2023-2024 High-Level and Growth Research and Development Subsidy for supporting the research and development activities for small and medium-size enterprise(SMEs),which is administered by Chiba Industry Advancement Center(Grant No.2066 and 2027)。
文摘This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.
基金Project(2013CB632605)supported by the National Basic Research Development Program of ChinaProjects(51274178,51274179)supported by the National Natural Science Foundation of China
文摘A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions （temperature 180 °C, initial KOH-to-ore mass ratio 4：1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min）, vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.
基金Project(51276074)supported by the National Natural Science Foundation of ChinaProject(2014NY008)supported by Innovation Research Foundation of Huazhong University of Science and Technology,China
文摘A modified shrinking unreacted-core model,based on thermogravimetric analysis,was developed to investigate CaSO4 decomposition in oxy-fuel combustion,especially under isothermal condition which is difficult to achieve in actual experiments due to high-temperature corrosion.A method was proposed to calculate the reaction rate constant for CaSO4 decomposition.Meanwhile,the diffusion of SO2 and O2,and the sintering of CaO were fully considered during the development of model.The results indicate that the model can precisely predict the decomposition of CaSO4 under high SO2 concentration（1100×10-6）.Concentrations of SO2 and O2 on the unreacted-core surface were found to increase first and then decrease with increasing temperature,and the average specific surface area and porosity of each CaO sintering layer decreased with increasing time.The increase of SO2 and/or O2 concentration inhibited CaSO4 decomposition.Moreover,the kinetics of CaSO4 decomposition had obvious dependence on temperature and the decomposition rate can be dramatically accelerated with increasing temperature.
基金Project(JSAWT-09-02)supported by the Key Laboratory of Advanced Welding Technology of Jiangsu Province,ChinaProject supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘Micro-arc oxidation （MAO） process was carried out in a dual electrolyte system of NaAlO 2 and Na 3 PO 4 to develop compact, smooth and corrosion-resistant coatings on ZK60 Mg alloy by single factor experiments. The microstructural characteristics of coatings were investigated by X-ray diffractometry （XRD） and scanning electron microscopy （SEM） coupled with energy dispersive X-ray spectroscopy （EDS）. Test of mass loss was conducted at a 3.5% NaCl solution to assess the resistance to corrosion. The effect of every element in the dual electrolyte system on voltage—time responses during MAO process and the coating characteristic were also analyzed and discussed systematically via single factor experiments. The results reveal that the main components of NaAlO 2 and Na 3 PO 4 as well as additives of NaOH, NaB4O7 and C6H5Na3O7 demonstrate different effects on MAO process and coating characteristics. By means of single factor experiments, an optimized dual electrolyte system was developed, containing 17.5 g/L NaAlO 2, 5.0 g/LNa3 PO4, 5.0 g/L NaOH, 3.0 g/L NaB4O7 and 4.2g/LC6H5Na3O7 .
