Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimen...Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.展开更多
Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spine...Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.展开更多
The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we pr...The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we present high-entropy oxide(HEO,(Mg_(0.2)Mn_(0.2)Ni_(0.2)Co_(0.2)Zn_(0.2))Fe_(2)O_(4))nanofibers as catalytic host of sulfur.The HEO nanofibers show a synergistic effect among multiple metal cations in spinel structure that enables strong chemical confinement of soluble polysulfides and fast kinetics for polysulfide conversion.Consequently,the S/HEO composite displays the high gravimetric capacity of 1368.7 mAh g^(−1) at 0.1 C rate,excellent rate capability with the discharge capacity of 632.1 mAh g^(−1) at 5 C rate,and desirable cycle stability.Furthermore,the S/HEO composite shows desirable sulfur utilization and good cycle stability under a harsh operating condition of high sulfur loading(4.6 mg cm^(−2))or low electrolyte/sulfur ratio(5μL mg^(−1)).More impressively,the high volumetric capacity of 2627.9 mAh cm^(−3) is achieved simultaneously for the S/HEO composite due to the high tap density of 1.92 g cm^(−3),nearly 2.5 times of the conventional sulfur/carbon composite.Therefore,based on high-entropy oxide materials,this work affords a fresh concept of elevating the gravimetric/volumetric capacities of sulfur cathodes for lithium–sulfur batteries.展开更多
Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catal...Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.展开更多
Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific sur...Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific surface area testing, galvanostatic cycling and electrochemical impedance spectroscopy. The XRD analysis shows that the sample exhibits pure spinel phase. The substitution of Co, La for Mn and Cl for O in the LiMn2O4 stabilizes the structural integrity of the spinel host, which in turn increases the electrochemical cycleability. The electrochemical experiments confirm that the capacity of the LiCo0.02La0.01Mn1.97O3.98Cl0.02 electrode maintains 90.6% of the initial capacity at 180th cycle.展开更多
High-entropy metal spinel oxide(HEO)is proved to be a promising oxygen evolution reaction(OER)catalyst with high catalytic performance and stability.A short routine synthesis process based on solution combustion synth...High-entropy metal spinel oxide(HEO)is proved to be a promising oxygen evolution reaction(OER)catalyst with high catalytic performance and stability.A short routine synthesis process based on solution combustion synthesis was proposed to prepare(Co_(0.25)Ni_(0.25)Mn_(0.25)Zn_(0.25))Fe_(2)O_(4)spinel HEO in this work.During the process,the products were rapidly synthesized and melted due to the high-temperature reaction,and then quickly crystallized on the surface of nickel foam to form a nano-structure coating.With the aid of nano-scale spinel structure,the overpotential of non-activation HEO electrode reaches 276 mV at the current density of 10 mA·cm^(-2),and after 100 h i-t test,it can be further reduced to 230 mV,which proves the high activity of OER catalysis.The promotion of OER catalytic performance can be attributed to the surface reconstruction caused by the selective element leaching and the boost of oxygen vacancy,leading to the formation of nano-scale flocculation around spinel core after the long-term OER process.This work indicates a special casting process for functional materials and explores the application of rapid crystallization.展开更多
The magnetic and electronic properties of spinel oxide LiV2O4 have been systematically studied by using the spin-polarized first-principles electronic structure calculations.We find that a series of magnetic states,in...The magnetic and electronic properties of spinel oxide LiV2O4 have been systematically studied by using the spin-polarized first-principles electronic structure calculations.We find that a series of magnetic states,in which the ferromagnetic(FM)V4 tetrahedra are linked together through the corner-sharing antiferromagnetic(AFM)V4 tetrahedra,possess degenerate energies lower than those of other spin configurations.The large number of these energetically degenerated states being the magnetic ground state give rise to strong magnetic frustration as well as large magnetic entropy in LiV2O4.The corresponding band structure and density of states of such a typical magnetic state in this series,i.e.,the ditetrahedron(DT)AFM state,demonstrate that LiV2O4 is in the vicinity of a metal-insulator transition.Further analysis suggests that the t2g and eg orbitals of the V atoms play different roles in the magnetic exchange interactions.Our calculations are consistent with previous experimental measurements and shed light on understanding the exotic magnetism and the heavy-fermion behavior of LiV2O4.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
Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acet...Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD,TEM,ESR,UV\|DRS and XPS,and the interaction between Co and Bi was studied as well. It has been found that nano\|sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)\|containing spinel are still maintained. The shift of the binding energy of Bi\-\{\%4f\%\-\{7/2\}\} is related to the catalytic activity of these catalysts doped with bismuth oxide.展开更多
Kinetics and mechanism of oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction were researched in air using vertical high temperature thermal dilatometer from 25℃to 1...Kinetics and mechanism of oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction were researched in air using vertical high temperature thermal dilatometer from 25℃to 1400℃.It is shown that oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced Al4C3 in situ reaction is the common logarithm of oxidation time t and the oxygen partial pressure P inside MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction in air at 1400℃is as follows:P=F(-2.75×10^-4A+2.13×10^-3)lnt.The nonsteady diffusion kinetic equation of O2 at 1400℃inside the composites is as follows:J=De lnt.Acceleration of the total diffusional?flux of oxygen inside the composites at 1400℃is in inverse proportion to the oxidation time.The nonsteady state effective diffusion coefficient De of O2(g)inside the composites decreases in direct proportional to the increase of the amount of metallic aluminium.The method of preventing the oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction is to increase the amount of Al.The slag erosion index of MgO-Al2O3 spinel carbon composite reinforced by Al4C3 in situ reaction is 0.47 times that of MgO-CaO brick used in the lining above slag line area of a VOD stainless steel-making vessel.HMOR of MgO-Al2O3 spinel carbon composite reinforced by Al4C3 in situ reaction is 26.7 MPa,HMOR of the composite is 3.6 times the same as that of MgO-CaO brick used in the lining above slag line area of a VOD vessel.Its service life is two times as many as that of MgO-CaO brick.展开更多
Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants co...Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.展开更多
In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthes...In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthesis of spinel NiCo_(2)O_(4)/perovskite LaCoO_(3) nano-composite,and its individual oxides NiCo_(2)O_(4)and LaCoO_(3) for comparison.The detailed insights into the physio-chemical characteristics of formed NiCo_(2)O_(4)/LaCoO_(3) nano-composite were done based on various characterization analysis such as X-ray diffraction(XRD),Fourier transform infrared(FT-IR),N_(2) physiosorption,scanning electron microscopy-energy dispersive spectroscopy(SEM-EDX),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).The characterization analysis of NiCo_(2)O_(4)/LaCoO_(3) revealed the successful formation of a chemical interface possessing strong interfacial interaction,resulting in desirable physicochemical characteristics such as small crystallite size,abundant mesoporosity,high specific surface area and activation of surface lattice oxygen.Owing to the desirable characteristics,the activity results over NiCo_(2)O_(4)/LaCoO_(3) nano-composite showed the excellent CO oxidation performance and high soot oxidation activity,recyclability and thermal stability.This work mainly attempts to emphasize the effectiveness of the facile,inexpensive and conventionally used precipitation method for the successful formation of highly efficient nano-composites.展开更多
基金the National Natural Science Foundation of China(Nos.52074078 and 52374327)the Applied Fundamental Research Program of Liaoning Province(No.2023JH2/101600002)+2 种基金the Shenyang Young Middle-Aged Scientific and Technological Innovation Talent Support Program(No.RC220491)the Liaoning Province Steel Industry-University-Research Innovation Alliance Cooperation Project of Bensteel Group(No.KJBLM202202)the Fundamental Research Funds for the Central Universities(Nos.N2201023 and N2325009).
文摘Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.
基金financial support from the National Natural Science Foundation of China(52203070)the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2022005)+2 种基金the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing(STRZ202203)the financial support provided by the China Scholarship Council(CSC)Visiting Scholar Programfinancial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship。
文摘Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.
基金Financial supports from the National Natural Science Foundation of China(21935006 and 22008102)are gratefully acknowledged.
文摘The exploration of new catalytic hosts is highly important to tackle the sluggish electrochemical kinetics of sulfur redox for achieving high energy density of lithium–sulfur batteries.Herein,for the first time,we present high-entropy oxide(HEO,(Mg_(0.2)Mn_(0.2)Ni_(0.2)Co_(0.2)Zn_(0.2))Fe_(2)O_(4))nanofibers as catalytic host of sulfur.The HEO nanofibers show a synergistic effect among multiple metal cations in spinel structure that enables strong chemical confinement of soluble polysulfides and fast kinetics for polysulfide conversion.Consequently,the S/HEO composite displays the high gravimetric capacity of 1368.7 mAh g^(−1) at 0.1 C rate,excellent rate capability with the discharge capacity of 632.1 mAh g^(−1) at 5 C rate,and desirable cycle stability.Furthermore,the S/HEO composite shows desirable sulfur utilization and good cycle stability under a harsh operating condition of high sulfur loading(4.6 mg cm^(−2))or low electrolyte/sulfur ratio(5μL mg^(−1)).More impressively,the high volumetric capacity of 2627.9 mAh cm^(−3) is achieved simultaneously for the S/HEO composite due to the high tap density of 1.92 g cm^(−3),nearly 2.5 times of the conventional sulfur/carbon composite.Therefore,based on high-entropy oxide materials,this work affords a fresh concept of elevating the gravimetric/volumetric capacities of sulfur cathodes for lithium–sulfur batteries.
基金the National Natural Science Foundation of China(U21A20286,22206054 and 21805069)Natural Science Foundation of Hubei(2021CFB094)the Fundamental Research Funds for the Central China Normal University(CCNU)for financial support。
文摘Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.
基金Project(20273047) supported by the National Natural Science Foundation of China
文摘Multidoped spinel LiCo0.02La0.01Mn1.97O3.98Cl0.02 was synthesized by solid-state method. The structure and electrochemical performance were characterized by XRD, ESEM, particle size distribution analysis, specific surface area testing, galvanostatic cycling and electrochemical impedance spectroscopy. The XRD analysis shows that the sample exhibits pure spinel phase. The substitution of Co, La for Mn and Cl for O in the LiMn2O4 stabilizes the structural integrity of the spinel host, which in turn increases the electrochemical cycleability. The electrochemical experiments confirm that the capacity of the LiCo0.02La0.01Mn1.97O3.98Cl0.02 electrode maintains 90.6% of the initial capacity at 180th cycle.
基金supported by the Research Fund of Jiangsu Key Laboratory for Advanced Metallic Materials,Southeast University(No.AMM2021A02).
文摘High-entropy metal spinel oxide(HEO)is proved to be a promising oxygen evolution reaction(OER)catalyst with high catalytic performance and stability.A short routine synthesis process based on solution combustion synthesis was proposed to prepare(Co_(0.25)Ni_(0.25)Mn_(0.25)Zn_(0.25))Fe_(2)O_(4)spinel HEO in this work.During the process,the products were rapidly synthesized and melted due to the high-temperature reaction,and then quickly crystallized on the surface of nickel foam to form a nano-structure coating.With the aid of nano-scale spinel structure,the overpotential of non-activation HEO electrode reaches 276 mV at the current density of 10 mA·cm^(-2),and after 100 h i-t test,it can be further reduced to 230 mV,which proves the high activity of OER catalysis.The promotion of OER catalytic performance can be attributed to the surface reconstruction caused by the selective element leaching and the boost of oxygen vacancy,leading to the formation of nano-scale flocculation around spinel core after the long-term OER process.This work indicates a special casting process for functional materials and explores the application of rapid crystallization.
基金Project supported by the National Key R&D Program of China(Grant Nos.2017YFA0302903 and 2019YFA0308603)the National Natural Science Foundation of China(Grant Nos.11774422,11774424,and 11674374)+1 种基金the CAS Interdisciplinary Innovation Team,the Fundamental Research Funds for the Central Universities,Chinathe Research Funds of Renmin University of China(Grant No.19XNLG13).
文摘The magnetic and electronic properties of spinel oxide LiV2O4 have been systematically studied by using the spin-polarized first-principles electronic structure calculations.We find that a series of magnetic states,in which the ferromagnetic(FM)V4 tetrahedra are linked together through the corner-sharing antiferromagnetic(AFM)V4 tetrahedra,possess degenerate energies lower than those of other spin configurations.The large number of these energetically degenerated states being the magnetic ground state give rise to strong magnetic frustration as well as large magnetic entropy in LiV2O4.The corresponding band structure and density of states of such a typical magnetic state in this series,i.e.,the ditetrahedron(DT)AFM state,demonstrate that LiV2O4 is in the vicinity of a metal-insulator transition.Further analysis suggests that the t2g and eg orbitals of the V atoms play different roles in the magnetic exchange interactions.Our calculations are consistent with previous experimental measurements and shed light on understanding the exotic magnetism and the heavy-fermion behavior of LiV2O4.
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.
文摘Two series of cobalt(Ⅲ)\|containing spinel catalysts were prepared by the decomposition of the corresponding nitrates. The catalysts doped with bismuth oxide exhibit a higher activity in the wet air oxidation of acetic acid than those without dopant bismuth oxide. The catalysts were investigated by XRD,TEM,ESR,UV\|DRS and XPS,and the interaction between Co and Bi was studied as well. It has been found that nano\|sized bismuth oxide is paved on the surface of cobalt spinel crystal and the structures of cobalt(Ⅲ)\|containing spinel are still maintained. The shift of the binding energy of Bi\-\{\%4f\%\-\{7/2\}\} is related to the catalytic activity of these catalysts doped with bismuth oxide.
基金Funded by the National Torch Plan of China(No.2005EB031110)the National Scientific and Technique Program of Ninth-five Year Plan(96-22-01-19)。
文摘Kinetics and mechanism of oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction were researched in air using vertical high temperature thermal dilatometer from 25℃to 1400℃.It is shown that oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced Al4C3 in situ reaction is the common logarithm of oxidation time t and the oxygen partial pressure P inside MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction in air at 1400℃is as follows:P=F(-2.75×10^-4A+2.13×10^-3)lnt.The nonsteady diffusion kinetic equation of O2 at 1400℃inside the composites is as follows:J=De lnt.Acceleration of the total diffusional?flux of oxygen inside the composites at 1400℃is in inverse proportion to the oxidation time.The nonsteady state effective diffusion coefficient De of O2(g)inside the composites decreases in direct proportional to the increase of the amount of metallic aluminium.The method of preventing the oxidation induced contraction of MgAl2O4 spinel carbon composites reinforced by Al4C3 in situ reaction is to increase the amount of Al.The slag erosion index of MgO-Al2O3 spinel carbon composite reinforced by Al4C3 in situ reaction is 0.47 times that of MgO-CaO brick used in the lining above slag line area of a VOD stainless steel-making vessel.HMOR of MgO-Al2O3 spinel carbon composite reinforced by Al4C3 in situ reaction is 26.7 MPa,HMOR of the composite is 3.6 times the same as that of MgO-CaO brick used in the lining above slag line area of a VOD vessel.Its service life is two times as many as that of MgO-CaO brick.
基金financial support by DST-SERB (Grant No.SRG/2021/001182)DRDO (Grant No.ARMREB/HEM/2021/241)is gratefully acknowledged。
文摘Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.
文摘In the quest for the development of thermally stable,highly active and low-cost catalysts for use in catalyzed diesel particulate filter,nano-composites are new areas of research.Therefore,we reported the easy synthesis of spinel NiCo_(2)O_(4)/perovskite LaCoO_(3) nano-composite,and its individual oxides NiCo_(2)O_(4)and LaCoO_(3) for comparison.The detailed insights into the physio-chemical characteristics of formed NiCo_(2)O_(4)/LaCoO_(3) nano-composite were done based on various characterization analysis such as X-ray diffraction(XRD),Fourier transform infrared(FT-IR),N_(2) physiosorption,scanning electron microscopy-energy dispersive spectroscopy(SEM-EDX),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).The characterization analysis of NiCo_(2)O_(4)/LaCoO_(3) revealed the successful formation of a chemical interface possessing strong interfacial interaction,resulting in desirable physicochemical characteristics such as small crystallite size,abundant mesoporosity,high specific surface area and activation of surface lattice oxygen.Owing to the desirable characteristics,the activity results over NiCo_(2)O_(4)/LaCoO_(3) nano-composite showed the excellent CO oxidation performance and high soot oxidation activity,recyclability and thermal stability.This work mainly attempts to emphasize the effectiveness of the facile,inexpensive and conventionally used precipitation method for the successful formation of highly efficient nano-composites.
