MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first c...MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first cycles,and poor rate performance have deterred its practical implementation.Herein,electrodes comprised solely of few-layers 2D MoS_(2) nanosheets have been manufactured by scalable liquid-phase exfoliation and spray deposition methods.The long-standing controversy questioning the reversibility of conversion processes of MoS_(2)-based electrodes was addressed.Raman studies revealed that,in 2D MoS_(2) electrodes,conversion processes are indeed reversible,where nanostructure played a key role.Cycling of the electrodes at high current rates revealed an intriguing phenomenon consisting of a continuously increasing capacity after ca.100-200 cycles.This phenomenon was comprehensively addressed by a variety of electrochemical and microscopy methods that revealed underlying physical activation mechanisms that involved a range of profound electrode structural changes.Activation mechanisms delivered a capacitive electrode of a superior rate performance and cycling stability,as compared to the corresponding pristine electrodes,and to MoS_(2) electrodes previously reported.Herein,we have devised a methodology to overcome the problem of cycling stability of 2D MoS_(2) electrodes.Moreover,activation of electrodes constitutes a methodology that could be applied to enhance the energy storage performance of electrodes based on other 2D nanomaterials,or combinations thereof,strategically combining chemistries to engineer electrodes of superior energy storage properties.展开更多
Typical p-n junctions have emerged as a promising strategy for contending with charge carrier recombination in solar conversion.However,the photo-corrosion and unsuitable energy band positions still hinder their pract...Typical p-n junctions have emerged as a promising strategy for contending with charge carrier recombination in solar conversion.However,the photo-corrosion and unsuitable energy band positions still hinder their practical application for hydrogen production from water in photoelectrochemical systems.Here,an in-situ photo-oxidation method is proposed for achieving self-adapting activation of BiVO_(4)-based photoanodes with surface-encapsulated CuGaS_(2)particles by the ZnO layer.The self-adapting activation demotes the energy band positions of CuGaS_(2),establishing an S-scheme structure with BiVO_(4),resulting in an efficient p-n junction photoanode.The optimal sample exhibits enhanced photocurrent and an onset potential cathodically shifted by~300 mV compared with BiVO_(4),which is attributed to significantly enhanced charge transport and transfer efficiencies.As expected,it attains the highest photocurrent value of 5.87 mA·cm^(-2),aided by a hole scavenger at 1.23 V versus a reversible hydrogen electrode,which significantly surpasses that of BiVO_(4)(4.32 mA·cm^(-2)).展开更多
Porous carbon materials have been widely used for the removal of SO_(2) from flue gas.The main objective of this work is to clarify the effects of adsorption temperature on SO_(2) adsorption and desorption energy cons...Porous carbon materials have been widely used for the removal of SO_(2) from flue gas.The main objective of this work is to clarify the effects of adsorption temperature on SO_(2) adsorption and desorption energy consumption.Coal-based porous powdered activated coke(PPAC)prepared in the drop-tube reactor was used in this study.The N_(2) adsorption measurements and Fourier transform infrared spectrometer analysis show that PPAC exhibits a developed pore structure and rich functional groups.The experimental results show that with a decrease in adsorption temperature in the range of 50–150℃,the adsorption capacity of SO_(2) increases linearly;meanwhile,the adsorption capacity of H_(2)O increases,resulting in the increase in desorption energy consumption per unit mass of adsorbent.The processes of SO_(2) and H_(2)O desorption were determined by the temperature-programmed desorption test,and the desorption energies for each species were calculated.Considering the energy consumption per unit of desorption and the total amount of adsorbent,the optimal adsorption temperature yielding the minimum total energy consumption of regeneration is calculated.This study systematically demonstrates the effect of adsorption temperature on the adsorption–desorption process,providing a basis for energy saving and emission reduction in desulfurization system design.展开更多
The dioxygen activation catalyzed by 4-hydorxylphenyl pyruvate dioxygenase(HPPD)were reinvestigated by using hybrid quantum mechanics/molecular mechanics(QM/MM)approaches at the B3LYP/6-311++G(d,p):AMBER level.These s...The dioxygen activation catalyzed by 4-hydorxylphenyl pyruvate dioxygenase(HPPD)were reinvestigated by using hybrid quantum mechanics/molecular mechanics(QM/MM)approaches at the B3LYP/6-311++G(d,p):AMBER level.These studies showed that this reaction consisted of two steps including the dioxygen addition/decarboxylation and hetero O-O bond cleavage,where the first step was found to be rate-determining.The former step initially runs on a septet potential energy surface(PES),then switches to a quintet PES after crossing a septet/quintet minimum energy crossing point(MECP)5-7M2,whereas the rest step runs on the quintet PES.The reliability of our theoretical predictions is supported by the excellent agreement of the calculated free-energy barrier value of 16.9 kcal/mol with available experimental value of 16-17 kcal/mol.The present study challenges the widely accepted view which holds that the O2activation catalyzed byα-keto glutamate(α-KG)dioxygenase mainly runs on the quintet PES and provides new insight into the catalytic mechanism ofα-KG dioxygenase and/or other related Fe(Ⅱ)-dependent oxygenase.展开更多
电导率是稀土矿渣玻璃陶瓷熔融过程中最重要的物性参数之一,研究电导率对玻璃熔体熔炼工艺优化有指导作用。为了研究尾矿玻璃陶瓷生产制造的熔融过程中稀土对熔体电导率的作用,使用分析纯试剂根据玻璃陶瓷主要化学成分制备玻璃陶瓷熔体...电导率是稀土矿渣玻璃陶瓷熔融过程中最重要的物性参数之一,研究电导率对玻璃熔体熔炼工艺优化有指导作用。为了研究尾矿玻璃陶瓷生产制造的熔融过程中稀土对熔体电导率的作用,使用分析纯试剂根据玻璃陶瓷主要化学成分制备玻璃陶瓷熔体样品,采用交流四电极法研究稀土对玻璃熔体电导率的影响规律,并结合红外光谱技术分析解释熔体电导率的变化机理。研究结果表明,硅酸盐熔体中添加La_(2)O_(3)或提高CaO/SiO_(2)比值会使熔体网络结构解聚,有效提高熔体电导率,且电导率的活化能(Activation energy of electrical conductivity)与La_(2)O_(3)含量和CaO/SiO_(2)比呈负相关关系;CaO/SiO_(2)比值较低时,La_(2)O_(3)含量对活化能影响更加显著,且红外光谱曲线硅酸盐结构带高波数段变化更明显,说明熔体结构发生更强烈的解聚效应;La_(2)O_(3)在CaO/SiO_(2)比值较低时对熔体网络结构和电导率的影响更大。展开更多
CeO2nanoparticles(NPs) were synthesized in alkaline medium via the homogeneous precipitation method and were subsequently calcined at 80 ℃/24 h(assigned as CeO2-80) and 500 ℃/2 h(assigned as CeO2-500). The as-prepar...CeO2nanoparticles(NPs) were synthesized in alkaline medium via the homogeneous precipitation method and were subsequently calcined at 80 ℃/24 h(assigned as CeO2-80) and 500 ℃/2 h(assigned as CeO2-500). The as-prepared materials and the commercial ceria(assigned as CeO2-com) were characterized using TGA-MS, XRD, SEM-EDX, UV-vis DRS and IEP techniques. The photocatalytic performances of all obtained photocatalysts were assessed by the degradation of Congo red azo-dye(CR) under UVAlight irradiation at various environmental key factors(e.g., reaction time and calcination temperature).Results reveal that CeO2compounds crystalize with cubic phase, CeO2-500 exhibits smaller crystallite size(9 nm vs 117 nm) than that of bare CeO2-com. SEM analysis shows that the materials are sphericallike in shape NPs with strong assembly of CeO2NPs observed in the CeO2-500 NPs. EDX analysis confirms the stoichiometry of CeO2NPs. UV-vis DRS measurement reveals that, CeO2-500 NPs exhibits a red-shift of absorption band and a more narrow bandgap(2.6 eV vs 3.20 eV) than that of bare CeO2-com. On the contrary, Urbach energy of Eu is found to be increased from 0.12 eV(CeO2-com) to 0.17 eV(CeO2-500),highlighting an increase of crystalline size and internal microstrain in the CeO2-500 NPs sample. Zeta potential(IEP) of CeO2-500 NPs is found to be 7.2. UVA-light-responsive photocatalytic activity is observed with CeO2-500 NPs at a rate constant of 10×10-3min-1, which is four times higher than that of CeO2-com(Kapp=2.4×10-3min-1) for the degradation of CR. Pseudo-first-order kinetic model gives the best fit. On the basis of the energy band diagram positions, the enhanced photocatalytic performance of CeO2-500 nano-catalyst can be ascribed to O2-, ’OH and R’+as the primary oxidative species involved in the degradation of RC under UVA-light irradiation.展开更多
A simplified subregular solution model was developed for describing the activities of MgCl 2 in both KCl MgCl 2 LiCl and CaCl 2 MgCl 2 NaCl systems on the assumption that the electrolytes in the solution are ...A simplified subregular solution model was developed for describing the activities of MgCl 2 in both KCl MgCl 2 LiCl and CaCl 2 MgCl 2 NaCl systems on the assumption that the electrolytes in the solution are treated as independent particles in stead of their ion forms and the interchange energy between the KCl LiCl (or CaCl 2 NaCl) pair is ignored as compared to those of the KCl MgCl 2(or CaCl 2 MgCl 2) and MgCl 2 LiCl (or MgCl 2 NaCl) pairs. The calculating results on the model agree with the observed very well.展开更多
In this study,Ni catalysts supported on Pr-doped Ce O_(2) are studied for the CO_(2) methanation reaction and the effect of Pr doping on the physicochemical properties and the catalytic performance is thoroughly evalu...In this study,Ni catalysts supported on Pr-doped Ce O_(2) are studied for the CO_(2) methanation reaction and the effect of Pr doping on the physicochemical properties and the catalytic performance is thoroughly evaluated.It is shown,that Pr^(3+)ions can substitute Ce^(4+)ones in the support lattice,thereby introducing a high population of oxygen vacancies,which act as active sites for CO_(2) chemisorption.Pr doping can also act to reduce the crystallite size of metallic Ni,thus promoting the active metal dispersion.Catalytic performance evaluation evidences the promoting effect of low Pr loadings(5 at%and 10 at%)towards a higher catalytic activity and lower CO_(2) activation energy.On the other hand,higher Pr contents negate the positive effects on the catalytic activity by decreasing the oxygen vacancy population,thereby creating a volcano-type trend towards an optimum amount of aliovalent substitution.展开更多
The relation between catalytic reactivities and metal/metal oxide ratios,as well as the functions of the metal and the metal oxides were investigated in the CO_(2)hydrogenation reaction over highly active Co_x(CoO)_(1...The relation between catalytic reactivities and metal/metal oxide ratios,as well as the functions of the metal and the metal oxides were investigated in the CO_(2)hydrogenation reaction over highly active Co_x(CoO)_(1–x)catalysts in operando.The catalytic reactivity of the samples in the CO_(2)methanation improves with the increased Co O concentration.Strikingly,the sample with the highest concentration of CoO,i.e.,Co_(0.2)(CoO)_(0.8),shows activity at temperatures lower than 200°C where the other samples with less CoO are inactive.The origins of this improvement are the increased amount and moderate binding of adsorbed CO_(2)on CoO sites.The derivative adsorption species are found to be intermediates of the CH4 formation.The metallic Co functions as the electronically catalytic site which provides electrons for the hydrogenation steps.As a result,an abundant amount of CoO combined with Co is the optimal composition of the catalyst for achieving the highest reactivity for CO_(2)hydrogenation.展开更多
MgH_(2)与水反应产生大量氢气有利于氢能源在燃料电池领域的发展,但产氢速率慢及Mg(OH)_(2)致密层这一关键问题限制了其应用。本文采用浓度分别为0.3、0.9、1.7、2.5 mol/L的海盐溶液与0.1 g MgH_(2)进行多次水解实验,测定不同温度下的...MgH_(2)与水反应产生大量氢气有利于氢能源在燃料电池领域的发展,但产氢速率慢及Mg(OH)_(2)致密层这一关键问题限制了其应用。本文采用浓度分别为0.3、0.9、1.7、2.5 mol/L的海盐溶液与0.1 g MgH_(2)进行多次水解实验,测定不同温度下的水解动力学曲线;采用XRD和SEM扫描技术对水解产物进行物相和形貌分析,并讨论了水解机制以及不同浓度的海盐溶液对颗粒表面的影响;通过Avrami-Erofeev和Arrhenius公式线性拟合分析了水解动力学过程和活化能。研究发现:浓度为0.9 mol/L的海盐溶液与0.1 g MgH_(2)反应时的水解性能以及表观活性改善最佳,在高温下,0.3、0.9、1.7、2.5 mol/L海盐溶液的水解活化能分别测定为(33.1±0.4)、(26.1±0.5)、(36.3±0.8)、(40.1±0.2)kJ/mol,水解产氢速率最快分别为11.33、12、10.66、11.33 mL/(g·s),确定了浓度对水解动力学的影响。MgH_(2)的这些优异的水解性能对镁基合金的水解研究具有重要意义。展开更多
Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and ...Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and eco-friendly method,has been meticu-lously researched and scaled up from laboratory experiments to pilot tests,aiming to drastically cut CO_(2) emissions associated with ferro-manganese production.This innovative process could potentially reduce CO_(2) emissions by about 1.5 tonnes for every tonne of ferroman-ganese produced.In this study,a lab-scale vertical thermogravimetric furnace was used to carry out the pre-reduction of Nchwaning man-ganese ore,where direct reduction occurred with H_(2) gas under controlled isothermal conditions at 700,800,and 900℃.The results indic-ated that higher pre-reduction temperatures(800 and 900℃)effectively converted Fe_(2)O_(3) to metallic iron and Mn_(2)O_(3) to MnO.By continu-ously monitoring the mass changes during the reduction,both the rate and extent of reduction were assessed.A second-order reaction model was applied to validate the experimental outcomes of H_(2) reduction at various temperatures,showing apparent activation energies of 29.79 kJ/mol for dried ore and 61.71 kJ/mol for pre-calcined ore.The reduction kinetics displayed a strong dependence on temperature,with higher temperatures leading to quicker and more complete reductions.The kinetics analysis suggested that the chemical reaction at the gas-solid interface between hydrogen and the manganese ore is likely the rate-limiting step in this process.展开更多
Unmanaged wood waste,particularly in countries like Nepal,presents serious environmental concerns due to open burning and improper disposal,leading to carbon emissions,air pollution and land degradation.This study int...Unmanaged wood waste,particularly in countries like Nepal,presents serious environmental concerns due to open burning and improper disposal,leading to carbon emissions,air pollution and land degradation.This study introduces an environmentally sustainable strategy to upcycle Toona ciliata wood scrap—an abundant and underutilized lignocellulosic biomass—into high performance carbon electrodes for green energy storage applications.Activated carbon(TCWAC)was synthesized via single-step pyrolytic carbonization followed by phosphoric acid activation,yielding a material with high specific surface area,hierarchical porosity,and excellent electrical conductivity.Electrochemical measurements using a three-electrode configuration in 6 M KOH revealed optimized potential windows of -1.0 to -0.2 V(TCWAC),-1.2 to 0 V(TCWAC-Mn),and -1.15 to -0.4 V(TCWAC-Fe).TCWAC exhibited a specific capacitance of 156.3 Fg^(-1)at 1 Ag^(-1),with an energy density of 3.5 Whkg^(-1),and 80.2% capacity retention after 1000 charge-discharge cycles.Composites with MnO_(2)and Fe_(2)O_(3)were also evaluated.TWAC-Mn delivered 489.4 Fg^(-1),25.1 Whkg^(-1),and 99.1% retention,whereas,TWAC-Fe achieved 321.3 Fg^(-1),6.3 Whkg^(-1),and 90.3% retention.The superior performance of MnO_(2)is attributed to its multiple oxidation states,facilitating reversible faradaic redox and enhanced pseudocapacitance.This work offers the first direct,systematic comparison of MnO_(2)and Fe_(2)O_(3)composites on a common biomass-carbon matrix under identical synthesis and testing conditions.The finding provides mechanistic insight into charge storage behaviour and demonstrate a scalable route for converting biomass waste into sustainable electrode materials,contributing to cleaner energy solutions and improved biomass valorization.展开更多
基金financial support from the China Scholarship Council(CSC grant.201808330389)。
文摘MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first cycles,and poor rate performance have deterred its practical implementation.Herein,electrodes comprised solely of few-layers 2D MoS_(2) nanosheets have been manufactured by scalable liquid-phase exfoliation and spray deposition methods.The long-standing controversy questioning the reversibility of conversion processes of MoS_(2)-based electrodes was addressed.Raman studies revealed that,in 2D MoS_(2) electrodes,conversion processes are indeed reversible,where nanostructure played a key role.Cycling of the electrodes at high current rates revealed an intriguing phenomenon consisting of a continuously increasing capacity after ca.100-200 cycles.This phenomenon was comprehensively addressed by a variety of electrochemical and microscopy methods that revealed underlying physical activation mechanisms that involved a range of profound electrode structural changes.Activation mechanisms delivered a capacitive electrode of a superior rate performance and cycling stability,as compared to the corresponding pristine electrodes,and to MoS_(2) electrodes previously reported.Herein,we have devised a methodology to overcome the problem of cycling stability of 2D MoS_(2) electrodes.Moreover,activation of electrodes constitutes a methodology that could be applied to enhance the energy storage performance of electrodes based on other 2D nanomaterials,or combinations thereof,strategically combining chemistries to engineer electrodes of superior energy storage properties.
基金supported by the open fund from Key Lab of Eco-restoration of Regional Contaminated Environment(Shenyang University),Ministry of Education(No.KF-22-08)the National Natural Science Foundation of China(Nos.22003074 and 42177406)+1 种基金the Youth Innovation Promotion Association CAS,Guangdong Basic and Applied Basic Research Foundation(No.2023A1515011410)S.Liu gratefully acknowledges the financial support by the National Natural Science Foundation of China(No.52302223).
文摘Typical p-n junctions have emerged as a promising strategy for contending with charge carrier recombination in solar conversion.However,the photo-corrosion and unsuitable energy band positions still hinder their practical application for hydrogen production from water in photoelectrochemical systems.Here,an in-situ photo-oxidation method is proposed for achieving self-adapting activation of BiVO_(4)-based photoanodes with surface-encapsulated CuGaS_(2)particles by the ZnO layer.The self-adapting activation demotes the energy band positions of CuGaS_(2),establishing an S-scheme structure with BiVO_(4),resulting in an efficient p-n junction photoanode.The optimal sample exhibits enhanced photocurrent and an onset potential cathodically shifted by~300 mV compared with BiVO_(4),which is attributed to significantly enhanced charge transport and transfer efficiencies.As expected,it attains the highest photocurrent value of 5.87 mA·cm^(-2),aided by a hole scavenger at 1.23 V versus a reversible hydrogen electrode,which significantly surpasses that of BiVO_(4)(4.32 mA·cm^(-2)).
基金supported by the National Key Research and Development Program of China(2017YFB0602901).
文摘Porous carbon materials have been widely used for the removal of SO_(2) from flue gas.The main objective of this work is to clarify the effects of adsorption temperature on SO_(2) adsorption and desorption energy consumption.Coal-based porous powdered activated coke(PPAC)prepared in the drop-tube reactor was used in this study.The N_(2) adsorption measurements and Fourier transform infrared spectrometer analysis show that PPAC exhibits a developed pore structure and rich functional groups.The experimental results show that with a decrease in adsorption temperature in the range of 50–150℃,the adsorption capacity of SO_(2) increases linearly;meanwhile,the adsorption capacity of H_(2)O increases,resulting in the increase in desorption energy consumption per unit mass of adsorbent.The processes of SO_(2) and H_(2)O desorption were determined by the temperature-programmed desorption test,and the desorption energies for each species were calculated.Considering the energy consumption per unit of desorption and the total amount of adsorbent,the optimal adsorption temperature yielding the minimum total energy consumption of regeneration is calculated.This study systematically demonstrates the effect of adsorption temperature on the adsorption–desorption process,providing a basis for energy saving and emission reduction in desulfurization system design.
基金supported by the National Key R&D Program(No.2021YFD1700100)National Natural Science Foundation of China(Nos.21837001,21273089)+2 种基金the Open Project Fund of the Key Laboratory of the Pesticides and Chemical Biology of Central China Normal University(No.2018-A01)the Fundamental Research Funds for the Central Universitiesthe Fundamental Research Funds for the South-Central University for Nationalities(No.CZW20020)。
文摘The dioxygen activation catalyzed by 4-hydorxylphenyl pyruvate dioxygenase(HPPD)were reinvestigated by using hybrid quantum mechanics/molecular mechanics(QM/MM)approaches at the B3LYP/6-311++G(d,p):AMBER level.These studies showed that this reaction consisted of two steps including the dioxygen addition/decarboxylation and hetero O-O bond cleavage,where the first step was found to be rate-determining.The former step initially runs on a septet potential energy surface(PES),then switches to a quintet PES after crossing a septet/quintet minimum energy crossing point(MECP)5-7M2,whereas the rest step runs on the quintet PES.The reliability of our theoretical predictions is supported by the excellent agreement of the calculated free-energy barrier value of 16.9 kcal/mol with available experimental value of 16-17 kcal/mol.The present study challenges the widely accepted view which holds that the O2activation catalyzed byα-keto glutamate(α-KG)dioxygenase mainly runs on the quintet PES and provides new insight into the catalytic mechanism ofα-KG dioxygenase and/or other related Fe(Ⅱ)-dependent oxygenase.
文摘电导率是稀土矿渣玻璃陶瓷熔融过程中最重要的物性参数之一,研究电导率对玻璃熔体熔炼工艺优化有指导作用。为了研究尾矿玻璃陶瓷生产制造的熔融过程中稀土对熔体电导率的作用,使用分析纯试剂根据玻璃陶瓷主要化学成分制备玻璃陶瓷熔体样品,采用交流四电极法研究稀土对玻璃熔体电导率的影响规律,并结合红外光谱技术分析解释熔体电导率的变化机理。研究结果表明,硅酸盐熔体中添加La_(2)O_(3)或提高CaO/SiO_(2)比值会使熔体网络结构解聚,有效提高熔体电导率,且电导率的活化能(Activation energy of electrical conductivity)与La_(2)O_(3)含量和CaO/SiO_(2)比呈负相关关系;CaO/SiO_(2)比值较低时,La_(2)O_(3)含量对活化能影响更加显著,且红外光谱曲线硅酸盐结构带高波数段变化更明显,说明熔体结构发生更强烈的解聚效应;La_(2)O_(3)在CaO/SiO_(2)比值较低时对熔体网络结构和电导率的影响更大。
文摘CeO2nanoparticles(NPs) were synthesized in alkaline medium via the homogeneous precipitation method and were subsequently calcined at 80 ℃/24 h(assigned as CeO2-80) and 500 ℃/2 h(assigned as CeO2-500). The as-prepared materials and the commercial ceria(assigned as CeO2-com) were characterized using TGA-MS, XRD, SEM-EDX, UV-vis DRS and IEP techniques. The photocatalytic performances of all obtained photocatalysts were assessed by the degradation of Congo red azo-dye(CR) under UVAlight irradiation at various environmental key factors(e.g., reaction time and calcination temperature).Results reveal that CeO2compounds crystalize with cubic phase, CeO2-500 exhibits smaller crystallite size(9 nm vs 117 nm) than that of bare CeO2-com. SEM analysis shows that the materials are sphericallike in shape NPs with strong assembly of CeO2NPs observed in the CeO2-500 NPs. EDX analysis confirms the stoichiometry of CeO2NPs. UV-vis DRS measurement reveals that, CeO2-500 NPs exhibits a red-shift of absorption band and a more narrow bandgap(2.6 eV vs 3.20 eV) than that of bare CeO2-com. On the contrary, Urbach energy of Eu is found to be increased from 0.12 eV(CeO2-com) to 0.17 eV(CeO2-500),highlighting an increase of crystalline size and internal microstrain in the CeO2-500 NPs sample. Zeta potential(IEP) of CeO2-500 NPs is found to be 7.2. UVA-light-responsive photocatalytic activity is observed with CeO2-500 NPs at a rate constant of 10×10-3min-1, which is four times higher than that of CeO2-com(Kapp=2.4×10-3min-1) for the degradation of CR. Pseudo-first-order kinetic model gives the best fit. On the basis of the energy band diagram positions, the enhanced photocatalytic performance of CeO2-500 nano-catalyst can be ascribed to O2-, ’OH and R’+as the primary oxidative species involved in the degradation of RC under UVA-light irradiation.
文摘A simplified subregular solution model was developed for describing the activities of MgCl 2 in both KCl MgCl 2 LiCl and CaCl 2 MgCl 2 NaCl systems on the assumption that the electrolytes in the solution are treated as independent particles in stead of their ion forms and the interchange energy between the KCl LiCl (or CaCl 2 NaCl) pair is ignored as compared to those of the KCl MgCl 2(or CaCl 2 MgCl 2) and MgCl 2 LiCl (or MgCl 2 NaCl) pairs. The calculating results on the model agree with the observed very well.
基金support of this work by the project“Development of new innovative low carbon energy technologies to improve excellence in the Region of Western Macedonia”(MIS 5047197)which is implemented under the Action“Reinforcement of the Research and Innovation Infrastructure”funded by the Operational Program“Competitiveness,Entrepreneurship and Innovation”(NSRF 2014-2020)co-financed by Greece and the European Union(European Regional Development Fund)。
文摘In this study,Ni catalysts supported on Pr-doped Ce O_(2) are studied for the CO_(2) methanation reaction and the effect of Pr doping on the physicochemical properties and the catalytic performance is thoroughly evaluated.It is shown,that Pr^(3+)ions can substitute Ce^(4+)ones in the support lattice,thereby introducing a high population of oxygen vacancies,which act as active sites for CO_(2) chemisorption.Pr doping can also act to reduce the crystallite size of metallic Ni,thus promoting the active metal dispersion.Catalytic performance evaluation evidences the promoting effect of low Pr loadings(5 at%and 10 at%)towards a higher catalytic activity and lower CO_(2) activation energy.On the other hand,higher Pr contents negate the positive effects on the catalytic activity by decreasing the oxygen vacancy population,thereby creating a volcano-type trend towards an optimum amount of aliovalent substitution.
基金financially supported by Innosuisse,the Swiss Innovation Agency,is gratefully acknowledgedThe NAPXPS system is funded by the SNSF R’EQUIP project(No.170736)+1 种基金the financial support from SNSF(Ambizione Project PZ00P2_179989)the China Scholarship Council for the PhD grant(Grant No.201506060156)。
文摘The relation between catalytic reactivities and metal/metal oxide ratios,as well as the functions of the metal and the metal oxides were investigated in the CO_(2)hydrogenation reaction over highly active Co_x(CoO)_(1–x)catalysts in operando.The catalytic reactivity of the samples in the CO_(2)methanation improves with the increased Co O concentration.Strikingly,the sample with the highest concentration of CoO,i.e.,Co_(0.2)(CoO)_(0.8),shows activity at temperatures lower than 200°C where the other samples with less CoO are inactive.The origins of this improvement are the increased amount and moderate binding of adsorbed CO_(2)on CoO sites.The derivative adsorption species are found to be intermediates of the CH4 formation.The metallic Co functions as the electronically catalytic site which provides electrons for the hydrogenation steps.As a result,an abundant amount of CoO combined with Co is the optimal composition of the catalyst for achieving the highest reactivity for CO_(2)hydrogenation.
文摘MgH_(2)与水反应产生大量氢气有利于氢能源在燃料电池领域的发展,但产氢速率慢及Mg(OH)_(2)致密层这一关键问题限制了其应用。本文采用浓度分别为0.3、0.9、1.7、2.5 mol/L的海盐溶液与0.1 g MgH_(2)进行多次水解实验,测定不同温度下的水解动力学曲线;采用XRD和SEM扫描技术对水解产物进行物相和形貌分析,并讨论了水解机制以及不同浓度的海盐溶液对颗粒表面的影响;通过Avrami-Erofeev和Arrhenius公式线性拟合分析了水解动力学过程和活化能。研究发现:浓度为0.9 mol/L的海盐溶液与0.1 g MgH_(2)反应时的水解性能以及表观活性改善最佳,在高温下,0.3、0.9、1.7、2.5 mol/L海盐溶液的水解活化能分别测定为(33.1±0.4)、(26.1±0.5)、(36.3±0.8)、(40.1±0.2)kJ/mol,水解产氢速率最快分别为11.33、12、10.66、11.33 mL/(g·s),确定了浓度对水解动力学的影响。MgH_(2)的这些优异的水解性能对镁基合金的水解研究具有重要意义。
基金the financial support from European Union’s Horizon Europe program HAlMan project (No. 101091936)
文摘Replacing solid carbon with hydrogen gas in ferromanganese production presents a forward-thinking,sustainable solution to re-ducing the ferro-alloy industry’s carbon emissions.The HAlMan process,a groundbreaking and eco-friendly method,has been meticu-lously researched and scaled up from laboratory experiments to pilot tests,aiming to drastically cut CO_(2) emissions associated with ferro-manganese production.This innovative process could potentially reduce CO_(2) emissions by about 1.5 tonnes for every tonne of ferroman-ganese produced.In this study,a lab-scale vertical thermogravimetric furnace was used to carry out the pre-reduction of Nchwaning man-ganese ore,where direct reduction occurred with H_(2) gas under controlled isothermal conditions at 700,800,and 900℃.The results indic-ated that higher pre-reduction temperatures(800 and 900℃)effectively converted Fe_(2)O_(3) to metallic iron and Mn_(2)O_(3) to MnO.By continu-ously monitoring the mass changes during the reduction,both the rate and extent of reduction were assessed.A second-order reaction model was applied to validate the experimental outcomes of H_(2) reduction at various temperatures,showing apparent activation energies of 29.79 kJ/mol for dried ore and 61.71 kJ/mol for pre-calcined ore.The reduction kinetics displayed a strong dependence on temperature,with higher temperatures leading to quicker and more complete reductions.The kinetics analysis suggested that the chemical reaction at the gas-solid interface between hydrogen and the manganese ore is likely the rate-limiting step in this process.
文摘Unmanaged wood waste,particularly in countries like Nepal,presents serious environmental concerns due to open burning and improper disposal,leading to carbon emissions,air pollution and land degradation.This study introduces an environmentally sustainable strategy to upcycle Toona ciliata wood scrap—an abundant and underutilized lignocellulosic biomass—into high performance carbon electrodes for green energy storage applications.Activated carbon(TCWAC)was synthesized via single-step pyrolytic carbonization followed by phosphoric acid activation,yielding a material with high specific surface area,hierarchical porosity,and excellent electrical conductivity.Electrochemical measurements using a three-electrode configuration in 6 M KOH revealed optimized potential windows of -1.0 to -0.2 V(TCWAC),-1.2 to 0 V(TCWAC-Mn),and -1.15 to -0.4 V(TCWAC-Fe).TCWAC exhibited a specific capacitance of 156.3 Fg^(-1)at 1 Ag^(-1),with an energy density of 3.5 Whkg^(-1),and 80.2% capacity retention after 1000 charge-discharge cycles.Composites with MnO_(2)and Fe_(2)O_(3)were also evaluated.TWAC-Mn delivered 489.4 Fg^(-1),25.1 Whkg^(-1),and 99.1% retention,whereas,TWAC-Fe achieved 321.3 Fg^(-1),6.3 Whkg^(-1),and 90.3% retention.The superior performance of MnO_(2)is attributed to its multiple oxidation states,facilitating reversible faradaic redox and enhanced pseudocapacitance.This work offers the first direct,systematic comparison of MnO_(2)and Fe_(2)O_(3)composites on a common biomass-carbon matrix under identical synthesis and testing conditions.The finding provides mechanistic insight into charge storage behaviour and demonstrate a scalable route for converting biomass waste into sustainable electrode materials,contributing to cleaner energy solutions and improved biomass valorization.
