Hydrogen energy from electrocatalysis driven by sustainable energy has emerged as a solution against the background of carbon neutrality.Proton exchange membrane(PEM)-based electrocatalytic systems represent a promisi...Hydrogen energy from electrocatalysis driven by sustainable energy has emerged as a solution against the background of carbon neutrality.Proton exchange membrane(PEM)-based electrocatalytic systems represent a promising technology for hydrogen production,which is equipped to combine efficiently with intermittent electricity from renewable energy sources.In this review,PEM-based electrocatalytic systems for H2 production are summarized systematically from low to high operating temperature systems.When the operating temperature is below 130℃,the representative device is a PEM water electrolyzer;its core components and respective functions,research status,and design strategies of key materials especially in electrocatalysts are presented and discussed.However,strong acidity,highly oxidative operating conditions,and the sluggish kinetics of the anode reaction of PEM water electrolyzers have limited their further development and shifted our attention to higher operating temperature PEM systems.Increasing the temperature of PEM-based electrocatalytic systems can cause an increase in current density,accelerate reaction kinetics and gas transport and reduce the ohmic value,activation losses,ΔGH*,and power consumption.Moreover,further increasing the operating temperature(120-300℃)of PEM-based devices endows various hydrogen carriers(e.g.,methanol,ethanol,and ammonia)with electrolysis,offering a new opportunity to produce hydrogen using PEM-based electrocatalytic systems.Finally,several future directions and prospects for developing PEM-based electrocatalytic systems for H_(2) production are proposed through devoting more efforts to the key components of devices and reduction of costs.展开更多
Green and sustainable options are needed to ease the current energy and environmental crisis, and alleviate the greenhouse effect and energy shortage. As an alternative carbon–neutral synthetic fuel, ammonia shows gr...Green and sustainable options are needed to ease the current energy and environmental crisis, and alleviate the greenhouse effect and energy shortage. As an alternative carbon–neutral synthetic fuel, ammonia shows great potential due to its high energy density, non-toxic by-products, and mature related infrastructures. However, related practical applications have been severely hampered on ammoniaoxidation due to the high cost of catalysts and immature energy utilization systems. Here, we comprehensively summarized the efforts which have been made in recent years with the aim of providing a deep sight into the development and deficiencies in this territory and trying to establish a simple framework of basic knowledge for researchers. The exploration of mechanism is discussed first and then the relevant catalysts studied in recent years are summarized. Besides, the progress of direct ammonia fuel cells(DAFCs) is also presented and the challenges as well as perspectives on future developments of electrocatalysts for ammonia electro-oxidation and its practical application are provided at the end.展开更多
One of the fundamental driving forces in the materials science community is the hunt for new materials with specific properties that meet the requirements of rapidly evolving technology.
the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent p...the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.展开更多
Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the de...Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the dehydrogenation kinetics of hydrazine electrooxidation at Ni_(2)P is adjusted by Co as the(Ni_(0.6)Co_(0.4))_(2)P catalyzes HzOR effectively with onset potential of–45 mV and only 113 mV is needed to drive the current density of 50 mA cm^(‒2),showing over 60 mV lower than Ni_(2)P and Co_(2)P.It also delivers the maximum power density of 263.0 mW cm^(-2) for direct hydrazine fuel cell.Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N_(2)H_(4) on Ni sites,lowering the energy barrier for dehydrogenation,but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics.This work represents a breakthrough in improving the catalytic performance of non‐precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy‐saving electrochemical hydrogen production method.展开更多
Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(...Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.展开更多
We introduce a novel numerical method for solving two-sided space fractional partial differential equations in two-dimensional case.The approximation of the space fractional Riemann-Liouville derivative is based on th...We introduce a novel numerical method for solving two-sided space fractional partial differential equations in two-dimensional case.The approximation of the space fractional Riemann-Liouville derivative is based on the approximation of the Hadamard finite-part integral which has the convergence order O(h^3-a),where h is the space step size and α∈(1,2)is the order of Riemann-Liouville fractional derivative.Based on this scheme,we introduce a shifted finite difference method for solving space fractional partial differential equations.We obtained the error estimates with the convergence orders O(τ+h^3-a+h^β),where τ is the time step size and β>0 is a parameter which measures the smoothness of the fractional derivatives of the solution of the equation.Unlike the numerical methods for solving space fractional partial differential equations constructed using the standard shifted Griinwald-Letnikov formula or higher order Lubich's methods which require the solution of the equation to satisfy the homogeneous Dirichlet boundary condition to get the firstorder convergence,the numerical method for solving the space fractional partial differential equation constructed using the Hadamard finite-part integral approach does not require the solution of the equation to satisfy the Dirichlet homogeneous boundary condition.Numerical results show that the experimentally determined convergence order obtained using the Hadamard finite-part integral approach for solving the space fractional partial differential equation with non-homogeneous Dirichlet boundary conditions is indeed higher than the convergence order obtained using the numerical methods constructed with the standard shifted Griinwald-Letnikov formula or Lubich's higher order approximation schemes.展开更多
High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface a...High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface atoms which usually shows a positive correlation. Excellenet stability of HEOs leads to their surface atoms with relative poor reactivity, limiting the applications for electrocatalysis. Therefore, it is significant to activate surface atoms of HEOs. Constructing amorphous structure, introducing oxygen defects and leaching are very effective strategies to improve the reactivity of surface atoms. Herein, to remove chemical inert, low-crystallinity(Fe, Co, Ni, Mn, Zn)_(3)O_(4) (HEO-Origin) nanosheets with abundant oxygen vacancies was synthesized, showing an excellent catalytic activity with an overpotential of 265 mV at 10 mA/cm^(2), which outperforms as-synthesized HEO-500℃-air(335 mV). The excellent catalytic performance of HEO-Origin can be attributed to high activity surface atoms, the introduction of oxygen defects efficiently altered electron distribution on the surface of HEO-Origin. Apart from, HEO-Origin also exhibits an outstanding electrochemical stability for oxygen evolution reaction(OER).展开更多
In this study, 6-hydroxydopamine was stereotaxically injected into the right substantia nigra compact and ventral tegmental area of rats to establish Parkinson＇s disease models. The rats then received a transplantati...In this study, 6-hydroxydopamine was stereotaxically injected into the right substantia nigra compact and ventral tegmental area of rats to establish Parkinson＇s disease models. The rats then received a transplantation of bone marrow stromal cells that were previously isolated, cultured and labeled with 5-bromo-2＇-deoxyuridine in vitro. Transplantation of the bone marrow stromal cells significantly decreased apomorphine-induced rotation time and the escape latency in the Morris water maze test as compared with rats with untreated Parkinson＇s disease. Immunohistochemical staining showed that, 5-bromo-2＇-deoxyuridine-immunoreactive cells were present in the lateral ventricular wall and the choroid plexus 1 day after transplantation. These immunoreactive cells migrated to the surrounding areas of the lateral cerebral ventricle along the corpus callosum. The results indicated that bone marrow stromal cells could migrate to tissues surround the cerebral ventricle via the cerebrospinal fluid circulation and fuse with cells in the brain, thus altering the phenotype of cells or forming neuron-like cells or astrocytes capable of expressing neuron-specific proteins. Taken together, the present findings indicate that bone marrow stromal cells transplanted intracerebroventricularly could survive, migrate and significantly improve the rotational behavior and cognitive function of rats with experimentally induced Parkinson＇s disease.展开更多
1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key fa...1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key factors to the practical application of hydrogen energy.As the scientific and technological understanding of the electrochemical devices was advancing in the past few decades,water electrolyzers based on the proton exchange membrane (PEM) have attracted much focus for its huge potential on the production of hydrogen via water splitting.PEM electrolyzers use perfluorinated sulfonic acid (PFSA) based membranes as the electrolyte.展开更多
Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property...Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property relationship at the atomic level remains a challenge due to the inherent polydispersity of catalysts,which hinders a comprehensive understanding of the defect catalysts.Atomically precise metal nanoclusters can serve as model catalysts because of their perfect monodispersity and well-defined structure.While,the understanding about defects in atomically precise metal nanoclusters is insufficient.This review encompasses various types of defects(such as heteroatom incorporation,vacancies,ligand deficiencies,etc.)in atomically precise coingage metal clusters,characterization methods,and their applications within the realm of catalysis.At the conclusion of this review,we propose several prospects,including the controllable construction of defects,further enhancement of the performance of clusters with defects,and monitoring the in-situ evolution of defects in clusters during catalysis.The purpose of this review is to deepen the understanding of defects in atomically precise clusters,establish the relationship between defect structure and catalytic performance,and offer valuable insights for the designing and developing of efficient defect-rich cluster catalysts.展开更多
Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear s...Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.展开更多
Gas-involving electrochemical reactions,like oxygen reduction reaction (ORR),oxygen evolution reaction (OER),and hydrogen evolution reaction (HER),are critical processes for energy-saving,environment-friendly energy c...Gas-involving electrochemical reactions,like oxygen reduction reaction (ORR),oxygen evolution reaction (OER),and hydrogen evolution reaction (HER),are critical processes for energy-saving,environment-friendly energy conversion and storage technologies which gain increasing attention.The development of according electrocatalysts is key to boost their electrocatalytic performances.Dramatic efforts have been put into the development of advanced electrocatalysts to overcome sluggish kinetics.On the other hand,the electrode interfaces-architecture construction plays an equally important role for practical applications because these imperative electrode reactions generally proceed at triple-phase interfaces of gas,liquid electrolyte,and solid electrocatalyst.A desirable architecture should facilitate the complicate reactions occur at the triple-phase interfaces,which including mass diffusion,surface reaction and electron transfer.In this review,we will summarize some design principles and synthetic strategies for optimizing triple-phase interfaces of gas-involving electrocatalysis systematically,based on the electrode reaction process at the three-phase interfaces.It can be divided into three main optimization directions:exposure of active sites,promotion of mass diffusion and acceleration of electron transfer.Furthermore,we especially highlight several remarkable works with comprehensive optimization about specific energy conversion devices,including metal-air batteries,fuel cells,and water-splitting devices are demonstrated with superb efficiency.In the last section,the perspectives and challenges in the future are proposed.展开更多
The oxygen evolution reaction(OER)with sluggish reaction kinetics and large overpotential is the critical reaction in water splitting that is promising for energy storage and conversion.Layered double hydroxides(LDHs)...The oxygen evolution reaction(OER)with sluggish reaction kinetics and large overpotential is the critical reaction in water splitting that is promising for energy storage and conversion.Layered double hydroxides(LDHs),due to their unique lamellar structure and flexibility of chemical component,are very competing material candidates for OER.Herein,the morphology structure and the electronic structure of LDHs were simultaneously tuned to improve the OER catalytic activity by mild solvothermal reduction using ethylene glycol.The increased surface area,the introduction of oxygen vacancies and the construction of hierarchical structure greatly enhanced the electro-catalytic activity of LDHs for OER.The as-prepared LDHs showed a lower over-potential as low as 276 mV at a current density of 10 mA cm-2,and a small Tafel slope of 40.3 mV dec-1 accompanied with good stability.This work provides an efficient way to the design and optimization of advanced catalysts in the future.展开更多
Oxygen reduction reaction(ORR)is key to fuel cells and metal-air batteries which are considered as the al-ternative clean energy.Various carbon materials have been widely researched as ORR electrocatalysts.It has been...Oxygen reduction reaction(ORR)is key to fuel cells and metal-air batteries which are considered as the al-ternative clean energy.Various carbon materials have been widely researched as ORR electrocatalysts.It has been ac-cepted that heteroatom doping and exposure of the edge sites can effectively improve the activity of carbon materials.In this work,we used a simple method to prepare a novel N,P-dual doped carbon-based catalyst with many holes on the surface.In addition,trace level Co doping in the carbon material forming Co-N-C active species can further enhance the ORR performance.On one hand,the doping can adjust the elec-tronic structure of carbon atoms,which would induce more active sites for ORR.And on the other hand,the holes formed on the surface of carbon nanosheets would expose more edge sites and can improve the intrinsic activity of carbon.Due to the heteroatom doping and the exposed edge sites,the pre-pared carbon materials showed highly excellent ORR perfor-mance,dose to that of commercial Pt/C.展开更多
Shuttle effect is one of the most serious disadvantages in lithium-sulfur battery which results in poor cycle performance and hinders the commercialization of Li-S battery.To reduce the dissolution of polysulfides int...Shuttle effect is one of the most serious disadvantages in lithium-sulfur battery which results in poor cycle performance and hinders the commercialization of Li-S battery.To reduce the dissolution of polysulfides into the electrolyte and prolong the cycling stability,nanoparticle-stacked metal nitride derived from layered double hydroxides(LDHs)as an interlayer was inserted between sulfur cathode and separator to confine polysulfides by physical and chemical interactions.Meanwhile,the surface of metal nitride will form an oxide passivation layer.The passivation layer possesses hydrophilic metal-O group and provides a polar surface for strong binding with polysulfide.What’s more,the nanoparticlesstacked structure could immerge and retain electrolyte well,which could enhance the ability of promoting the electron exchange rate.The sulfur electrode with nanoparticle-stacked metal nitride interlayer has an excellent cycle performance owing to the interactions between metal nitride and polysulfides.The battery delivered an initial capacity of 764.6 m Ahg^(-1) and still possesses a capacity of 477.5 mAhg^(-1) with the retention of 62.4% after 800 cycles.展开更多
Electrocatalytic reduction reactions play a crucial role in electrochemical energy conversion and storage technology,which are emerging technologies to ameliorate environmental problems.Spinel oxides are widely explor...Electrocatalytic reduction reactions play a crucial role in electrochemical energy conversion and storage technology,which are emerging technologies to ameliorate environmental problems.Spinel oxides are widely explored in electrocatalytic oxidation reactions but have a poor intrinsic ability to reduction reactions,making their electrocatalytic ability less effective.To improve this,defect engineering is a valuable method for regulating the electronic structure and coordination environment.Herein,this manuscript discusses the use of defect spinel oxides in electrocatalytic reduction reactions,including the different types of defects,construction methods,and characterization techniques.It also outlines the various applications of defect spinel oxides in different electrocatalytic reduction reactions.Finally,it goes over the challenges and future outlooks for defect spinels.This review aims to thoroughly explain how defect spinels work in electrocatalytic reduction reactions and serve as a helpful guide for creating effective electrocatalysts.展开更多
Seawater uranium extraction is of significant strategic importance for ensuring a continuous supply of uranium resources and the sustainable development of nuclear energy.However,the capacity,selectivity,and sustainab...Seawater uranium extraction is of significant strategic importance for ensuring a continuous supply of uranium resources and the sustainable development of nuclear energy.However,the capacity,selectivity,and sustainability of this process have been notably impacted by factors such as the low concentration of uranium in seawater,the presence of complex competing ions,and inevitable marine interference.Over the past decade,substantial progress has been achieved in the development of materials and methods for uranium extraction.Notably,the electrochemical uranium extraction method has garnered widespread attention for its green,efficient,and modular development benefits.In this review,we summarize the latest advancements in the field of electrochemical uranium extraction.Firstly,we introduce the application of various electrochemical methods and different electrode materials in the extraction of uranium from seawater.Second,we analyze the mechanism of electrochemical uranium reduction and the existing new systems for uranium extraction.In the final part,we point out the limitations,challenges,and future prospects of electrochemical uranium extraction from seawater.展开更多
基金National Key R&D Program of China,Grant/Award Number:2021YFA1500900Basic and Applied Basic Research Foundation of Guangdong Province-Regional Joint Fund Project,Grant/Award Number:2021B1515120024+9 种基金Science Funds of the Education Office of Jiangxi Province,Grant/Award Number:GJJ2201324Science Funds of Jiangxi Province,Grant/Award Numbers:20242BAB25168,20224BAB213018Doctoral Research Start-up Funds of JXSTNU,Grant/Award Number:2022BSQD05China Postdoctoral Science Foundation,Grant/Award Number:2023M741121National Natural Science Foundation of China,Grant/Award Number:22172047Provincial Natural Science Foundation of Hunan,Grant/Award Number:2021JJ30089Shenzhen Science and Technology Program,Grant/Award Number:JCYJ20210324122209025Changsha Municipal Natural Science Foundation,Grant/Award Number:kq2107008Hunan Province of Huxiang Talent project,Grant/Award Number:2023rc3118Natural Science Foundation of Hunan Province,Grant/Award Number:2022JJ10006.
文摘Hydrogen energy from electrocatalysis driven by sustainable energy has emerged as a solution against the background of carbon neutrality.Proton exchange membrane(PEM)-based electrocatalytic systems represent a promising technology for hydrogen production,which is equipped to combine efficiently with intermittent electricity from renewable energy sources.In this review,PEM-based electrocatalytic systems for H2 production are summarized systematically from low to high operating temperature systems.When the operating temperature is below 130℃,the representative device is a PEM water electrolyzer;its core components and respective functions,research status,and design strategies of key materials especially in electrocatalysts are presented and discussed.However,strong acidity,highly oxidative operating conditions,and the sluggish kinetics of the anode reaction of PEM water electrolyzers have limited their further development and shifted our attention to higher operating temperature PEM systems.Increasing the temperature of PEM-based electrocatalytic systems can cause an increase in current density,accelerate reaction kinetics and gas transport and reduce the ohmic value,activation losses,ΔGH*,and power consumption.Moreover,further increasing the operating temperature(120-300℃)of PEM-based devices endows various hydrogen carriers(e.g.,methanol,ethanol,and ammonia)with electrolysis,offering a new opportunity to produce hydrogen using PEM-based electrocatalytic systems.Finally,several future directions and prospects for developing PEM-based electrocatalytic systems for H_(2) production are proposed through devoting more efforts to the key components of devices and reduction of costs.
基金supported by the National Natural Science Foundation of China (Grant Nos. 21905088, 21902047, 21573066, 21825201, 2187350, and 51402100)the Provincial Natural Science Foundation of Hunan (2020JJ5045)。
文摘Green and sustainable options are needed to ease the current energy and environmental crisis, and alleviate the greenhouse effect and energy shortage. As an alternative carbon–neutral synthetic fuel, ammonia shows great potential due to its high energy density, non-toxic by-products, and mature related infrastructures. However, related practical applications have been severely hampered on ammoniaoxidation due to the high cost of catalysts and immature energy utilization systems. Here, we comprehensively summarized the efforts which have been made in recent years with the aim of providing a deep sight into the development and deficiencies in this territory and trying to establish a simple framework of basic knowledge for researchers. The exploration of mechanism is discussed first and then the relevant catalysts studied in recent years are summarized. Besides, the progress of direct ammonia fuel cells(DAFCs) is also presented and the challenges as well as perspectives on future developments of electrocatalysts for ammonia electro-oxidation and its practical application are provided at the end.
基金supported by the National Natural Science Foundation of China(Grant Nos.21701043,21825201 and U19A2017)the Provincial Natural Science Foundation of Hunan(2019GK2031)+1 种基金the Open Project Program of Key Laboratory of Low Dimensional Materials&Application Technology(Xiangtan University),Ministry of Education,China(No.KF20180202)the China Postdoctoral Science Foundation(Grant Nos.2019 M662766,2019 M662759,2020 M682549,and 2020 M672473)。
文摘One of the fundamental driving forces in the materials science community is the hunt for new materials with specific properties that meet the requirements of rapidly evolving technology.
基金supported by grants from the National Natural Science Foundation of China (Grant Nos. 21573066, 21825201, 2187350, 51402100 and 21905088)。
文摘the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.
文摘Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the dehydrogenation kinetics of hydrazine electrooxidation at Ni_(2)P is adjusted by Co as the(Ni_(0.6)Co_(0.4))_(2)P catalyzes HzOR effectively with onset potential of–45 mV and only 113 mV is needed to drive the current density of 50 mA cm^(‒2),showing over 60 mV lower than Ni_(2)P and Co_(2)P.It also delivers the maximum power density of 263.0 mW cm^(-2) for direct hydrazine fuel cell.Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N_(2)H_(4) on Ni sites,lowering the energy barrier for dehydrogenation,but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics.This work represents a breakthrough in improving the catalytic performance of non‐precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy‐saving electrochemical hydrogen production method.
基金support from the National Natural Science Foundation of China(51402100,21905088,21573066 and U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5044,2022JJ10006)。
文摘Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.
基金Y.Wang's research was supported by the Natural Science Foundation of Luliang University(XN201510).
文摘We introduce a novel numerical method for solving two-sided space fractional partial differential equations in two-dimensional case.The approximation of the space fractional Riemann-Liouville derivative is based on the approximation of the Hadamard finite-part integral which has the convergence order O(h^3-a),where h is the space step size and α∈(1,2)is the order of Riemann-Liouville fractional derivative.Based on this scheme,we introduce a shifted finite difference method for solving space fractional partial differential equations.We obtained the error estimates with the convergence orders O(τ+h^3-a+h^β),where τ is the time step size and β>0 is a parameter which measures the smoothness of the fractional derivatives of the solution of the equation.Unlike the numerical methods for solving space fractional partial differential equations constructed using the standard shifted Griinwald-Letnikov formula or higher order Lubich's methods which require the solution of the equation to satisfy the homogeneous Dirichlet boundary condition to get the firstorder convergence,the numerical method for solving the space fractional partial differential equation constructed using the Hadamard finite-part integral approach does not require the solution of the equation to satisfy the Dirichlet homogeneous boundary condition.Numerical results show that the experimentally determined convergence order obtained using the Hadamard finite-part integral approach for solving the space fractional partial differential equation with non-homogeneous Dirichlet boundary conditions is indeed higher than the convergence order obtained using the numerical methods constructed with the standard shifted Griinwald-Letnikov formula or Lubich's higher order approximation schemes.
基金supported by the National Natural Science Foundation of China(Nos.U19A2017,21902047,51402100,21825201,21573066,and 21905088)the Provincial Natural Science Foundation of Hunan(Nos.2020JJ5044,2022JJ10006)。
文摘High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface atoms which usually shows a positive correlation. Excellenet stability of HEOs leads to their surface atoms with relative poor reactivity, limiting the applications for electrocatalysis. Therefore, it is significant to activate surface atoms of HEOs. Constructing amorphous structure, introducing oxygen defects and leaching are very effective strategies to improve the reactivity of surface atoms. Herein, to remove chemical inert, low-crystallinity(Fe, Co, Ni, Mn, Zn)_(3)O_(4) (HEO-Origin) nanosheets with abundant oxygen vacancies was synthesized, showing an excellent catalytic activity with an overpotential of 265 mV at 10 mA/cm^(2), which outperforms as-synthesized HEO-500℃-air(335 mV). The excellent catalytic performance of HEO-Origin can be attributed to high activity surface atoms, the introduction of oxygen defects efficiently altered electron distribution on the surface of HEO-Origin. Apart from, HEO-Origin also exhibits an outstanding electrochemical stability for oxygen evolution reaction(OER).
基金supported by the Natural Science Foundation of Hebei Province,No.C2008000993
文摘In this study, 6-hydroxydopamine was stereotaxically injected into the right substantia nigra compact and ventral tegmental area of rats to establish Parkinson＇s disease models. The rats then received a transplantation of bone marrow stromal cells that were previously isolated, cultured and labeled with 5-bromo-2＇-deoxyuridine in vitro. Transplantation of the bone marrow stromal cells significantly decreased apomorphine-induced rotation time and the escape latency in the Morris water maze test as compared with rats with untreated Parkinson＇s disease. Immunohistochemical staining showed that, 5-bromo-2＇-deoxyuridine-immunoreactive cells were present in the lateral ventricular wall and the choroid plexus 1 day after transplantation. These immunoreactive cells migrated to the surrounding areas of the lateral cerebral ventricle along the corpus callosum. The results indicated that bone marrow stromal cells could migrate to tissues surround the cerebral ventricle via the cerebrospinal fluid circulation and fuse with cells in the brain, thus altering the phenotype of cells or forming neuron-like cells or astrocytes capable of expressing neuron-specific proteins. Taken together, the present findings indicate that bone marrow stromal cells transplanted intracerebroventricularly could survive, migrate and significantly improve the rotational behavior and cognitive function of rats with experimentally induced Parkinson＇s disease.
基金supported by the National Key R&D Program of China(2021YFA1500900,2020YFA0710000)the National Natural Science Foundation of China(22172047,22002039,21825201 and U19A2017)+3 种基金the Provincial Natural Science Foundation of Hunan(2021JJ30089,2016TP1009 and 2020JJ5045)the China Postdoctoral Science Foundation(2019M662759,2020M682541 and 2020M682549)the Shenzhen Science and Technology Program(JCYJ20210324122209025)the Changsha Municipal Natural Science Foundation(kq2107008 and kq2007009)。
文摘1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key factors to the practical application of hydrogen energy.As the scientific and technological understanding of the electrochemical devices was advancing in the past few decades,water electrolyzers based on the proton exchange membrane (PEM) have attracted much focus for its huge potential on the production of hydrogen via water splitting.PEM electrolyzers use perfluorinated sulfonic acid (PFSA) based membranes as the electrolyte.
基金This work was supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property relationship at the atomic level remains a challenge due to the inherent polydispersity of catalysts,which hinders a comprehensive understanding of the defect catalysts.Atomically precise metal nanoclusters can serve as model catalysts because of their perfect monodispersity and well-defined structure.While,the understanding about defects in atomically precise metal nanoclusters is insufficient.This review encompasses various types of defects(such as heteroatom incorporation,vacancies,ligand deficiencies,etc.)in atomically precise coingage metal clusters,characterization methods,and their applications within the realm of catalysis.At the conclusion of this review,we propose several prospects,including the controllable construction of defects,further enhancement of the performance of clusters with defects,and monitoring the in-situ evolution of defects in clusters during catalysis.The purpose of this review is to deepen the understanding of defects in atomically precise clusters,establish the relationship between defect structure and catalytic performance,and offer valuable insights for the designing and developing of efficient defect-rich cluster catalysts.
基金supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.
基金The authors acknowledge support from the National Natural Science Foundation of China(Nos.51402100 and 21573066)the Provincial Natural Science Foundation of Hunan(Nos.2016JJ1006 and 2016TP1009).
文摘Gas-involving electrochemical reactions,like oxygen reduction reaction (ORR),oxygen evolution reaction (OER),and hydrogen evolution reaction (HER),are critical processes for energy-saving,environment-friendly energy conversion and storage technologies which gain increasing attention.The development of according electrocatalysts is key to boost their electrocatalytic performances.Dramatic efforts have been put into the development of advanced electrocatalysts to overcome sluggish kinetics.On the other hand,the electrode interfaces-architecture construction plays an equally important role for practical applications because these imperative electrode reactions generally proceed at triple-phase interfaces of gas,liquid electrolyte,and solid electrocatalyst.A desirable architecture should facilitate the complicate reactions occur at the triple-phase interfaces,which including mass diffusion,surface reaction and electron transfer.In this review,we will summarize some design principles and synthetic strategies for optimizing triple-phase interfaces of gas-involving electrocatalysis systematically,based on the electrode reaction process at the three-phase interfaces.It can be divided into three main optimization directions:exposure of active sites,promotion of mass diffusion and acceleration of electron transfer.Furthermore,we especially highlight several remarkable works with comprehensive optimization about specific energy conversion devices,including metal-air batteries,fuel cells,and water-splitting devices are demonstrated with superb efficiency.In the last section,the perspectives and challenges in the future are proposed.
基金supported by the Fundamental Research Funds for the Central Universities (531107051102)the National Natural Science Foundation of China (51402100, 21573066, 21522305)+1 种基金the Provincial Natural Science Foundation of Hunan (2016TP1009)the Shenzhen Discovery Funding (JCYJ20170306141659388)
文摘The oxygen evolution reaction(OER)with sluggish reaction kinetics and large overpotential is the critical reaction in water splitting that is promising for energy storage and conversion.Layered double hydroxides(LDHs),due to their unique lamellar structure and flexibility of chemical component,are very competing material candidates for OER.Herein,the morphology structure and the electronic structure of LDHs were simultaneously tuned to improve the OER catalytic activity by mild solvothermal reduction using ethylene glycol.The increased surface area,the introduction of oxygen vacancies and the construction of hierarchical structure greatly enhanced the electro-catalytic activity of LDHs for OER.The as-prepared LDHs showed a lower over-potential as low as 276 mV at a current density of 10 mA cm-2,and a small Tafel slope of 40.3 mV dec-1 accompanied with good stability.This work provides an efficient way to the design and optimization of advanced catalysts in the future.
基金supported by the National Natural Science Foundation of China (21701043, 21573066, and 51402100)the Provincial Natural Science Foundation of Hunan (2016JJ1006 and 2016TP1009)the Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province and Shenzhen Science and Technology Program (JCYJ20170306141659388)
文摘Oxygen reduction reaction(ORR)is key to fuel cells and metal-air batteries which are considered as the al-ternative clean energy.Various carbon materials have been widely researched as ORR electrocatalysts.It has been ac-cepted that heteroatom doping and exposure of the edge sites can effectively improve the activity of carbon materials.In this work,we used a simple method to prepare a novel N,P-dual doped carbon-based catalyst with many holes on the surface.In addition,trace level Co doping in the carbon material forming Co-N-C active species can further enhance the ORR performance.On one hand,the doping can adjust the elec-tronic structure of carbon atoms,which would induce more active sites for ORR.And on the other hand,the holes formed on the surface of carbon nanosheets would expose more edge sites and can improve the intrinsic activity of carbon.Due to the heteroatom doping and the exposed edge sites,the pre-pared carbon materials showed highly excellent ORR perfor-mance,dose to that of commercial Pt/C.
基金supported by the National Natural Science Foundation of China(21701043,51402100,50702020,21573066 and 81171461)the Provincial Natural Science Foundation of Hunan(2016JJ1006,2016TP1009 and 11JJ4013)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province
文摘Shuttle effect is one of the most serious disadvantages in lithium-sulfur battery which results in poor cycle performance and hinders the commercialization of Li-S battery.To reduce the dissolution of polysulfides into the electrolyte and prolong the cycling stability,nanoparticle-stacked metal nitride derived from layered double hydroxides(LDHs)as an interlayer was inserted between sulfur cathode and separator to confine polysulfides by physical and chemical interactions.Meanwhile,the surface of metal nitride will form an oxide passivation layer.The passivation layer possesses hydrophilic metal-O group and provides a polar surface for strong binding with polysulfide.What’s more,the nanoparticlesstacked structure could immerge and retain electrolyte well,which could enhance the ability of promoting the electron exchange rate.The sulfur electrode with nanoparticle-stacked metal nitride interlayer has an excellent cycle performance owing to the interactions between metal nitride and polysulfides.The battery delivered an initial capacity of 764.6 m Ahg^(-1) and still possesses a capacity of 477.5 mAhg^(-1) with the retention of 62.4% after 800 cycles.
基金financially supported by the National Key R&D Program of China (2021YFA1500900)the National Natural Science Foundation of China (22102053, 21825201 and U19A2017)+5 种基金the Provincial Natural Science Foundation of Hunan (2016TP1009, 2020JJ5045 and 2022JJ10006)the Science and Technology Innovation Program of Hunan Province (2022RC1036)the Major Program of the Natural Science Foundation of Hunan Province (2021JC0006)Hunan Graduate Education Innovation Project and Professional Ability Improvement Project (CX20210400)the Basic and Applied Basic Research Foundation of Guangdong Province-Regional joint fund project (2021B1515120024)Shenzhen Science and Technology Programs (JCYJ20200109110416441)。
基金supported by National Natural Science Foundation of China(Nos.22272047,21905088,22102155)the China Postdoctoral Science Foundation(Nos.2021M692909,2022T150587)the Provincial Natural Science Foundation of Hunan(No.2022JJ10006).
文摘Electrocatalytic reduction reactions play a crucial role in electrochemical energy conversion and storage technology,which are emerging technologies to ameliorate environmental problems.Spinel oxides are widely explored in electrocatalytic oxidation reactions but have a poor intrinsic ability to reduction reactions,making their electrocatalytic ability less effective.To improve this,defect engineering is a valuable method for regulating the electronic structure and coordination environment.Herein,this manuscript discusses the use of defect spinel oxides in electrocatalytic reduction reactions,including the different types of defects,construction methods,and characterization techniques.It also outlines the various applications of defect spinel oxides in different electrocatalytic reduction reactions.Finally,it goes over the challenges and future outlooks for defect spinels.This review aims to thoroughly explain how defect spinels work in electrocatalytic reduction reactions and serve as a helpful guide for creating effective electrocatalysts.
基金supported by the National Natural Science Foundation of China (22425021,22272047,21905088)the National Key R&D Program of China (SQ2021YFA1500020)the Provincial Natural Science Foundation of Hunan (2022JJ10006)。
文摘Seawater uranium extraction is of significant strategic importance for ensuring a continuous supply of uranium resources and the sustainable development of nuclear energy.However,the capacity,selectivity,and sustainability of this process have been notably impacted by factors such as the low concentration of uranium in seawater,the presence of complex competing ions,and inevitable marine interference.Over the past decade,substantial progress has been achieved in the development of materials and methods for uranium extraction.Notably,the electrochemical uranium extraction method has garnered widespread attention for its green,efficient,and modular development benefits.In this review,we summarize the latest advancements in the field of electrochemical uranium extraction.Firstly,we introduce the application of various electrochemical methods and different electrode materials in the extraction of uranium from seawater.Second,we analyze the mechanism of electrochemical uranium reduction and the existing new systems for uranium extraction.In the final part,we point out the limitations,challenges,and future prospects of electrochemical uranium extraction from seawater.
