Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semicond...Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.展开更多
Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demon...Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.展开更多
Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculate...Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.展开更多
Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical cap...Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
The Panzhihua mafic intrusion,which hosts a world-class Fe-Ti-V ore deposit,is in the western Emeishan region,SW China.The formation age(~260 Ma),and Sr and Nd isotopes indicate that the Panzhihua intrusion is part of...The Panzhihua mafic intrusion,which hosts a world-class Fe-Ti-V ore deposit,is in the western Emeishan region,SW China.The formation age(~260 Ma),and Sr and Nd isotopes indicate that the Panzhihua intrusion is part of the Emeishan large igneous province and has little crustal contamination.To assess ore genesis of the Panzhihua Fe-Ti-V ore deposit,two different models have been provided to explain the formation,namely silicate immiscibility and normal fractional crystallization.Silicate immiscibility occurring around 1,000℃at the late stage of basaltic magma evolution argues against the silicate immiscibility model.Apatite-hosted melt inclusion research indicates that silicate immiscibility occurred at the late stage of Panzhihua magma evolution,which may not have offered potential to form such large ore deposits as Panzhihua.Alternatively,continuous compositional variations of the Panzhihua intrusion and calculations using thermodynamic modelling software support the hypothesis that the Panzhihua deposit was formed by normal fractional crystallization.Reciprocal trace element patterns of the Panzhihua intrusion and nearby felsic rocks also coincide with the fractional crystallization model.Normal fractional crystallization of high-Ti basaltic magma played a key role in the formation of the Panzhihua Fe-Ti-V ore deposit.展开更多
Potassium-ion batteries(PIBs)have been considered as promising candidates in the post-lithium-ion battery era.Till now,a large number of materials have been used as electrode materials for PIBs,among which vanadium ox...Potassium-ion batteries(PIBs)have been considered as promising candidates in the post-lithium-ion battery era.Till now,a large number of materials have been used as electrode materials for PIBs,among which vanadium oxides exhibit great potentiality.Vanadium oxides can provide multiple electron transfers during electrochemical reactions because vanadium possesses a variety of oxidation states.Meanwhile,their relatively low cost and superior material,structural,and physicochemical properties endow them with strong competitiveness.Although some inspiring research results have been achieved,many issues and challenges remain to be further addressed.Herein,we systematically summarize the research progress of vanadium oxides for PIBs.Then,feasible improvement strategies for the material properties and electrochemical performance are introduced.Finally,the existing challenges and perspectives are discussed with a view to promoting the development of vanadium oxides and accelerating their practical applications.展开更多
Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite ox...Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC.展开更多
High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This r...High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This review presents fundamental preparations,incidental characterizations,and typical structures of HEOs.The prospective applications of HEOs in various electrochemical aspects of electrocatalysis and energy conversion-storage are also summarized,including recent developments and the general trend of HEO structure design in the catalysis containing oxygen evolution reaction(OER)and oxygen reduction reaction(ORR),supercapacitors(SC),lithium-ion batteries(LIBs),solid oxide fuel cells(SOFCs),and so forth.Moreover,this review notes some apparent challenges and multiple opportunities for the use of HEOs in the wide field of energy to further guide the development of practical applications.The influence of entropy is significant,and high-entropy oxides are expected to drive the improvement of energy science and technology in the near future.展开更多
Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal ...Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.展开更多
Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anod...Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anode of the Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies(Ov-BMO-Cu)are in-situ generated by phase separation and hydrogen etching using nanoporous Cu-Mn alloy as selfsacrificial templates.On this basis,we have elucidated the relationship between the phase evolution,oxygen vacancies and sodium-ion storage mechanisms,further demonstrating the evolution of oxygen vacancies and the inhibition effect of manganese oxides as an“anchor”on grain aggregation of copper oxides.The kinetic analyses confirm that the expanded lattice space and increased oxygen vacancies of cycled Ov-BMO-Cu synergistically guarantee effective sodium-ion diffusion and storage mechanisms.Therefore,the Ov-BMO-Cu electrode exhibits higher reversible capacities of 4.04 mA h cm^(-2)at 0.2 mA cm^(-2)after 100 cycles and 2.20 m A h cm^(-2)at 1.0 mA cm^(-2)after 500 cycles.Besides,the presodiated Ov-BMO-Cu anode delivers a considerable reversible capacity of 0.79 m A h cm^(-2)at 1.0 mA cm^(-2)after 60 cycles in full cells with Na_(3)V_(2)(PO_(4))_(3)cathode,confirming its outstanding practicality.Thus,this work is expected to provide enlightenment for designing high-capacity bimetallic oxide anodes.展开更多
A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isotherm...A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.展开更多
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i...Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.展开更多
In this work,the CuAl-LDO/c-CNTs catalyst was fabricated via in situ oriented assembly of layered-double hydroxides(LDHs)and citric acid-modified carbon nanotubes(c-CNTs)followed by annealing treatment,and evaluated i...In this work,the CuAl-LDO/c-CNTs catalyst was fabricated via in situ oriented assembly of layered-double hydroxides(LDHs)and citric acid-modified carbon nanotubes(c-CNTs)followed by annealing treatment,and evaluated in the selective catalytic oxidation(SCO)of NH_(3)to N_(2).The CuAl-LDO/c-CNTs catalyst presented better catalytic performance(98%NH_(3)conversion with nearly 90%N_(2)selectivity at 513 K)than other catalysts,such as CuAlO_(x)/CNTs,CuAlO_(x)/c-CNTs and CuAl-LDO/CNTs.Multiple characterizations were utilized to analyze the difference of physicochemical properties among four catalysts.XRD,TEM and XPS analyses manifested that CuO and Cu_(2)O nanoparticles dispersed well on the surface of the Cu Al-LDO/c-CNTs catalyst.Compared with other catalysts,larger specific surface area and better dispersion of CuAl-LDO/c-CNTs catalyst were conducive to the exposure of more active sites,thus improving the redox capacity of the active site and NH_(3)adsorption capacity.In-situ DRIFTS results revealed that the internal selective catalytic reduction(iSCR)mechanism was found over CuAl-LDO/c-CNTs catalyst.展开更多
In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
Cholesterol and cholesterol oxides impact on the functional properties of cells, in respect of the intracellular and extracellular distribution of compounds across cell membranes, carcinogenesis and drug resistance. A...Cholesterol and cholesterol oxides impact on the functional properties of cells, in respect of the intracellular and extracellular distribution of compounds across cell membranes, carcinogenesis and drug resistance. Abnormal levels of cholesterol oxides and steroids in cancerous tissues promote interest in steroid receptor cross-talk during cell-signalling and the steroid metabolome of cancer patients. The research literature links the cytotoxic properties of oxysterols to interference with the NO/cGMP pathway. cGMP participates in cell-signalling and has a molecular structure that relates to cancer-inducing and cancer-preventing agents. This study uses a molecular modelling approach to compare the structures of cholesterol oxides to cGMP. Cholesterol and cholesterol oxide structures fit to a cGMP structural template in several ways, some of which are replicated by corticosteroids and gonadal steroid hormones. The results of this study support the concept that cholesterol oxides modulate cell apoptosis and autophagy via the NO/cGMP pathway and in conjunction with steroid hormones participate in modulating regulation of cell function by cGMP.展开更多
Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still fac...Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.展开更多
Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over...Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over NiV-layered double hydroxides(LDHs) thin films.Mechanistic studies confirmed the hydroxyl active intermediate(-OH*) generated on the surface of NiV-LDHs films by employing electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy.By using advanced techniques,e.g.,extended X-ray absorption fine structure and high-angle annular dark-field scanning transmission electron microscopy,NiV-LDHs films with 2.6 nm could expose larger specific surface area.Taking benzaldehyde as a model,high current density of 200 mA cm^(-2)at 1.8 V vs.RHE,81.1% conversion,77.6% yield of benzoic acid and 90.8% Faradaic efficiency were reached,which was superior to most of previous studies.Theoretical DFT analysis was well matched with experimental findings and documented that NiV-LDHs had high adsorption capacity for the aldehydes to suppress the side reaction,and the aldehydes were oxidized by the electrophilic hydroxyl radicals formed on NiV-LDHs.Our findings offer a universal strategy for the robust upgrading of diverse biomass-derived platform chemicals.展开更多
The direct tandem oxidation synthesis of benzenediol from benzene could simplify or even avoid the separation and purification of reaction intermediates, which is promising but challenged because of the further requir...The direct tandem oxidation synthesis of benzenediol from benzene could simplify or even avoid the separation and purification of reaction intermediates, which is promising but challenged because of the further required immediate consecutive activation of intermediate phenol. In this work, a synergistic benzene tandem-oxidation catalyst that V-Cu bimetallic oxides modified nanoporous silica(VCu-NS)was constructed via a facile assembly strategy which involves addictive negative anion citric acid mediating the intercalation of metal-citric acid chelate in mesopore of silica and subsequent thermal calcination inducing dual-metal active site formation. Such a tactic could make amorphous VOxspecies well covered on the surface of mesopore, and ultrafine copper oxide particles surrounded and neighbored by highly dispersed VOxwith strong interplay in mesopore, which was comprehensively confirmed by various characterizations. Benefiting from the unique V-Cu neighboring effect, the desorption of formed phenol over the catalytic site might be restricted therefore easily further activated by the formed reactive oxidative species, 3VCu-NS shows synergetic tandem-oxidation catalytic activities for benzene towards benzenediol with a selectivity of 57%. The result allows optimal 3VCu-NS to be a promising catalyst for benzenediol synthesis from benzene.展开更多
Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.Ho...Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.However,the irreversible phase transition often brings rapid capacity decay,which seriously hinders the practical application in large-scale energy storage.Herein,we design a nickel-doped Na_(0.70)Fe_(0.10)Cu_(0.20)Ni_(0.05)Mn_(0.65)O_(2)(NFCNM-0.05)cathode material of SIBs with activated anionic redox reaction,and then inhibit the harmful phase transition.The ex-situ X-ray diffraction patterns demonstrate the NFCNM-0.05 always keeps the P2 phase during the sodiation/desodiation process,indicating a high structure stability.The ex-situ X-ray photoelectron spectroscopy implies the redox reactions between O2-and O-occur in the charging process,which offers extra specific capacity.Thus,the NFCNM-0.05 electrode delivers a high initial discharge capacity of 148 mA h g-1and remains a prominent cycling stability with an excellent capacity retention of 95.9%after 200 cycles at 1 C.In addition,the electrochemical impedance spectroscopy and galvanostatic intermittent titration technique show the NFCNM-0.05 electrode possesses fast ion diffusion ability,which is beneficial for the enhancement of rate performance.Even at 10 C,the NFCNM-0.05 can offer a reversible discharge capacity of 81 mA h g-1.DFT calculation demonstrates the doping of appropriate amount of Ni ions is benefit for the enhancement of the electrochemical performance of the layer oxides.This work provides an effective strategy to enhance the electrochemical performance of Fe-Mn based cathode materials of SIBs.展开更多
基金financially supported by the National Key Research and Development Program of China (No.2021YFA0718900)the National Natural Science Foundation of China (No.62074014)the Xiaomi Scholar project。
文摘Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.
基金This study was supported by the National Research Foundation of Korea(NRF-2021R1C1C1010233)funded by the Korean government(MSIT)+1 种基金This research was also supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant(No.G032542411)funded by the Korea Ministry of Trade,Industry,and Energy(MOTIE).
文摘Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications,including fuel cells,chemical conversion,and batteries.Nanocatalysts demonstrate high activity by expanding the number of active sites,but they also intensify deactivation issues,such as agglomeration and poisoning,simultaneously.Exsolution for bottomup synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials.Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process.Their uniformity and stability,resulting from the socketed structure,play a crucial role in the development of novel nanocatalysts.Recently,tremendous research efforts have been dedicated to further controlling exsolution particles.To effectively address exsolution at a more precise level,understanding the underlying mechanism is essential.This review presents a comprehensive overview of the exsolution mechanism,with a focus on its driving force,processes,properties,and synergetic strategies,as well as new pathways for optimizing nanocatalysts in diverse applications.
基金supported by Key Science and Technology Innovation Team of Shaanxi Province(No.2022TD-33)National Natural Science Foundation of China(Grant Nos.21373161,21504067)。
文摘Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.
基金The authors acknowledge the support of the Shenyang University of Technology(QNPY202209-4)the National Natural Science Foundation of China(21571132)+1 种基金Jiangsu University Advanced Talent Fund(5501710002)the Education Department of Liaoning Province(JYTQN2023285).
文摘Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金co-supported by the China Geological Survey(Grant Nos.DD20230229,DD20190011,DD20221643)the National Key Research and Development Project of China(Grant No.2018YFC0603701)。
文摘The Panzhihua mafic intrusion,which hosts a world-class Fe-Ti-V ore deposit,is in the western Emeishan region,SW China.The formation age(~260 Ma),and Sr and Nd isotopes indicate that the Panzhihua intrusion is part of the Emeishan large igneous province and has little crustal contamination.To assess ore genesis of the Panzhihua Fe-Ti-V ore deposit,two different models have been provided to explain the formation,namely silicate immiscibility and normal fractional crystallization.Silicate immiscibility occurring around 1,000℃at the late stage of basaltic magma evolution argues against the silicate immiscibility model.Apatite-hosted melt inclusion research indicates that silicate immiscibility occurred at the late stage of Panzhihua magma evolution,which may not have offered potential to form such large ore deposits as Panzhihua.Alternatively,continuous compositional variations of the Panzhihua intrusion and calculations using thermodynamic modelling software support the hypothesis that the Panzhihua deposit was formed by normal fractional crystallization.Reciprocal trace element patterns of the Panzhihua intrusion and nearby felsic rocks also coincide with the fractional crystallization model.Normal fractional crystallization of high-Ti basaltic magma played a key role in the formation of the Panzhihua Fe-Ti-V ore deposit.
基金the Shenyang University of Technology(QNPY202209-4)the Key R&D project of Liaoning Province of China(2020JH2/10300079)+2 种基金the“Liaoning BaiQianWan Talents Program”(2018921006)the Liaoning Revitalization Talents Program(XLYC1908034)the National Natural Science Foundation of China(21571132).
文摘Potassium-ion batteries(PIBs)have been considered as promising candidates in the post-lithium-ion battery era.Till now,a large number of materials have been used as electrode materials for PIBs,among which vanadium oxides exhibit great potentiality.Vanadium oxides can provide multiple electron transfers during electrochemical reactions because vanadium possesses a variety of oxidation states.Meanwhile,their relatively low cost and superior material,structural,and physicochemical properties endow them with strong competitiveness.Although some inspiring research results have been achieved,many issues and challenges remain to be further addressed.Herein,we systematically summarize the research progress of vanadium oxides for PIBs.Then,feasible improvement strategies for the material properties and electrochemical performance are introduced.Finally,the existing challenges and perspectives are discussed with a view to promoting the development of vanadium oxides and accelerating their practical applications.
基金supported by the National Natural Science Foundation of China (51877173)the Key R&D Project of Shaanxi Province (2023-YBGY-057)+1 种基金the State Key Laboratory of Electrical Insulation and Power Equipment (EIPE22314, EIPE22306)the Natural Science Basic Research Program of Shaanxi (2023-JC-QN-0483)。
文摘Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC.
基金The authors are thankful for the financial support from the Beijing Natural Science Foundation(No.3222050)the National Natural Science Foundation of China(Nos.22075304 and 52202324).
文摘High-entropy oxides(HEOs)are gaining prominence in the field of electrochemistry due to their distinctive structural characteristics,which give rise to their advanced stable and modifiable functional properties.This review presents fundamental preparations,incidental characterizations,and typical structures of HEOs.The prospective applications of HEOs in various electrochemical aspects of electrocatalysis and energy conversion-storage are also summarized,including recent developments and the general trend of HEO structure design in the catalysis containing oxygen evolution reaction(OER)and oxygen reduction reaction(ORR),supercapacitors(SC),lithium-ion batteries(LIBs),solid oxide fuel cells(SOFCs),and so forth.Moreover,this review notes some apparent challenges and multiple opportunities for the use of HEOs in the wide field of energy to further guide the development of practical applications.The influence of entropy is significant,and high-entropy oxides are expected to drive the improvement of energy science and technology in the near future.
基金the financial support from the National Natural Science Foundation of China(21908010)Jilin Provincial Department of Science and Technology(20220101089JC)the Education Department of Jilin Province(JJKH20220694KJ)。
文摘Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.
基金supported by the Natural Science Foundation of China(5207123251871165)。
文摘Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anode of the Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies(Ov-BMO-Cu)are in-situ generated by phase separation and hydrogen etching using nanoporous Cu-Mn alloy as selfsacrificial templates.On this basis,we have elucidated the relationship between the phase evolution,oxygen vacancies and sodium-ion storage mechanisms,further demonstrating the evolution of oxygen vacancies and the inhibition effect of manganese oxides as an“anchor”on grain aggregation of copper oxides.The kinetic analyses confirm that the expanded lattice space and increased oxygen vacancies of cycled Ov-BMO-Cu synergistically guarantee effective sodium-ion diffusion and storage mechanisms.Therefore,the Ov-BMO-Cu electrode exhibits higher reversible capacities of 4.04 mA h cm^(-2)at 0.2 mA cm^(-2)after 100 cycles and 2.20 m A h cm^(-2)at 1.0 mA cm^(-2)after 500 cycles.Besides,the presodiated Ov-BMO-Cu anode delivers a considerable reversible capacity of 0.79 m A h cm^(-2)at 1.0 mA cm^(-2)after 60 cycles in full cells with Na_(3)V_(2)(PO_(4))_(3)cathode,confirming its outstanding practicality.Thus,this work is expected to provide enlightenment for designing high-capacity bimetallic oxide anodes.
基金financially supported by the National Key R&D Program of China (No.2021YFB3700400)the National Natural Science Foundation of China (Nos.52074030,51904021,and 52174294)。
文摘A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.
基金supported by the National Natural Science Foundation of China(52272253)the"Lingyan"Research and Development Plan of Zhejiang Province(2022C01071)+2 种基金the S&T Innovation 2025 Major Special Programme of Ningbo(2018B10081)the Natural Science Foundation of Ningbo(202003N4030)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022299)。
文摘Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.
基金supported by the National Natural Science Foundation of China(51978436,52000092,22272116)Fundamental Research Program of Shanxi Province(202103021224043)。
文摘In this work,the CuAl-LDO/c-CNTs catalyst was fabricated via in situ oriented assembly of layered-double hydroxides(LDHs)and citric acid-modified carbon nanotubes(c-CNTs)followed by annealing treatment,and evaluated in the selective catalytic oxidation(SCO)of NH_(3)to N_(2).The CuAl-LDO/c-CNTs catalyst presented better catalytic performance(98%NH_(3)conversion with nearly 90%N_(2)selectivity at 513 K)than other catalysts,such as CuAlO_(x)/CNTs,CuAlO_(x)/c-CNTs and CuAl-LDO/CNTs.Multiple characterizations were utilized to analyze the difference of physicochemical properties among four catalysts.XRD,TEM and XPS analyses manifested that CuO and Cu_(2)O nanoparticles dispersed well on the surface of the Cu Al-LDO/c-CNTs catalyst.Compared with other catalysts,larger specific surface area and better dispersion of CuAl-LDO/c-CNTs catalyst were conducive to the exposure of more active sites,thus improving the redox capacity of the active site and NH_(3)adsorption capacity.In-situ DRIFTS results revealed that the internal selective catalytic reduction(iSCR)mechanism was found over CuAl-LDO/c-CNTs catalyst.
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
文摘Cholesterol and cholesterol oxides impact on the functional properties of cells, in respect of the intracellular and extracellular distribution of compounds across cell membranes, carcinogenesis and drug resistance. Abnormal levels of cholesterol oxides and steroids in cancerous tissues promote interest in steroid receptor cross-talk during cell-signalling and the steroid metabolome of cancer patients. The research literature links the cytotoxic properties of oxysterols to interference with the NO/cGMP pathway. cGMP participates in cell-signalling and has a molecular structure that relates to cancer-inducing and cancer-preventing agents. This study uses a molecular modelling approach to compare the structures of cholesterol oxides to cGMP. Cholesterol and cholesterol oxide structures fit to a cGMP structural template in several ways, some of which are replicated by corticosteroids and gonadal steroid hormones. The results of this study support the concept that cholesterol oxides modulate cell apoptosis and autophagy via the NO/cGMP pathway and in conjunction with steroid hormones participate in modulating regulation of cell function by cGMP.
基金the financial support from National Natural Science Foundation of China (No. 21972102)National Key Research and Development Program of China (2021YFA0910400)+3 种基金Natural Science Foundation of Jiangsu Province (BK20200991)Suzhou Science and Technology Planning Project (SS202016)the USTS starting fund (No.332012104)the Natural Science Foundation of Suzhou University of Science and Technology (No.342134401)。
文摘Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.
基金supported by the National Natural Science Foundation of China(22078374,21776324)the Scientific and Technological Planning Project of Guangzhou(202206010145)+2 种基金the National Ten Thousand Talent Plan,Key-Area Research and Development Program of Guangdong Province(2019B110209003)the Guangdong Basic and Applied Basic Research Foundation(2019B1515120058,2020A1515011149)the Start-up Fund for Senior Talents in Jiangsu University(21JDG060)。
文摘Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over NiV-layered double hydroxides(LDHs) thin films.Mechanistic studies confirmed the hydroxyl active intermediate(-OH*) generated on the surface of NiV-LDHs films by employing electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy.By using advanced techniques,e.g.,extended X-ray absorption fine structure and high-angle annular dark-field scanning transmission electron microscopy,NiV-LDHs films with 2.6 nm could expose larger specific surface area.Taking benzaldehyde as a model,high current density of 200 mA cm^(-2)at 1.8 V vs.RHE,81.1% conversion,77.6% yield of benzoic acid and 90.8% Faradaic efficiency were reached,which was superior to most of previous studies.Theoretical DFT analysis was well matched with experimental findings and documented that NiV-LDHs had high adsorption capacity for the aldehydes to suppress the side reaction,and the aldehydes were oxidized by the electrophilic hydroxyl radicals formed on NiV-LDHs.Our findings offer a universal strategy for the robust upgrading of diverse biomass-derived platform chemicals.
基金financially supported by the National Natural Science Foundation of China (21908085)Natural Science Foundation of Jiangsu Province, China (BK20190961)+1 种基金Postdoctoral Research Foundation of Jiangsu Province (2020Z291)the Jiangsu Provincial Key Laboratory of Environmental Science and Engineering (JSHJZDSYS-202103)。
文摘The direct tandem oxidation synthesis of benzenediol from benzene could simplify or even avoid the separation and purification of reaction intermediates, which is promising but challenged because of the further required immediate consecutive activation of intermediate phenol. In this work, a synergistic benzene tandem-oxidation catalyst that V-Cu bimetallic oxides modified nanoporous silica(VCu-NS)was constructed via a facile assembly strategy which involves addictive negative anion citric acid mediating the intercalation of metal-citric acid chelate in mesopore of silica and subsequent thermal calcination inducing dual-metal active site formation. Such a tactic could make amorphous VOxspecies well covered on the surface of mesopore, and ultrafine copper oxide particles surrounded and neighbored by highly dispersed VOxwith strong interplay in mesopore, which was comprehensively confirmed by various characterizations. Benefiting from the unique V-Cu neighboring effect, the desorption of formed phenol over the catalytic site might be restricted therefore easily further activated by the formed reactive oxidative species, 3VCu-NS shows synergetic tandem-oxidation catalytic activities for benzene towards benzenediol with a selectivity of 57%. The result allows optimal 3VCu-NS to be a promising catalyst for benzenediol synthesis from benzene.
基金supported by the National Natural Science Foundation of China(U1960107)the Natural Science Foundation of Hebei Province(E2022501014)+3 种基金the “333”Talent Project of Hebei Province(A202005018)the Fundamental Research Funds for the Central Universities(N2123034)the Science and Technology Research Youth Fund Project of Higher Education Institutions of Hebei Province(QN2022196)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(22567627H)。
文摘Fe-Mn based layer oxides cathode materials have attracted widespread attention as a potential candidate for sodium-ion batteries(SIBs)owing to the earth abundance,cost-effectiveness and acceptable specific capacity.However,the irreversible phase transition often brings rapid capacity decay,which seriously hinders the practical application in large-scale energy storage.Herein,we design a nickel-doped Na_(0.70)Fe_(0.10)Cu_(0.20)Ni_(0.05)Mn_(0.65)O_(2)(NFCNM-0.05)cathode material of SIBs with activated anionic redox reaction,and then inhibit the harmful phase transition.The ex-situ X-ray diffraction patterns demonstrate the NFCNM-0.05 always keeps the P2 phase during the sodiation/desodiation process,indicating a high structure stability.The ex-situ X-ray photoelectron spectroscopy implies the redox reactions between O2-and O-occur in the charging process,which offers extra specific capacity.Thus,the NFCNM-0.05 electrode delivers a high initial discharge capacity of 148 mA h g-1and remains a prominent cycling stability with an excellent capacity retention of 95.9%after 200 cycles at 1 C.In addition,the electrochemical impedance spectroscopy and galvanostatic intermittent titration technique show the NFCNM-0.05 electrode possesses fast ion diffusion ability,which is beneficial for the enhancement of rate performance.Even at 10 C,the NFCNM-0.05 can offer a reversible discharge capacity of 81 mA h g-1.DFT calculation demonstrates the doping of appropriate amount of Ni ions is benefit for the enhancement of the electrochemical performance of the layer oxides.This work provides an effective strategy to enhance the electrochemical performance of Fe-Mn based cathode materials of SIBs.