It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,...It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,and FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbents were prepared by coupling fly ash-based Si-Al carriers.The active components Fe-Ce-La oxides and Si-Al carriers were characterized by TPD,TG,XRF,BET and XPS,respectively.The effects of temperature,Si/Al ratio and FeCeLaO loading rate on the sulfur resistance were investigated.Results show that the SO_(2) promotes the arsenic removal of Fe_(2)O_(3),CeLaO and FeCeLaO.At 400℃,the arsenic removal efficiencies of the three oxides increase from 45.3%,72.5% and 81.3% without SO_(2) to 62.6%,80.5%and 91.0%,respectively.The SO_(2) inhibits the arsenic removal of La_(2)O_(2)CO_(3) and FeLaO,and the inhibition effect is pronounced at high temperatures.The sulfur poisoning resistance of Si-Al carriers increases with the increase of Si/Al ratio.When the Si/Al ratio is increased to 9.74,the arsenic removal efficiency in the SO_(2) environment is 13.9% higher than that in the absence of SO_(2).Introducing FeCeLaO active components is beneficial for enhancing the SO_(2) poisoning resistance of Si-Al carriers.The strong sulfur resistance of the FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbent results from multiple factors:protective effects of Ce on Fe,La and Al;sulfation-induced generation of Ce^(3+)and surface-adsorbed oxygen;and strong surface acidity of SiO_(2).展开更多
Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic b...Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic behavior of these vacancies as main mass transport mediums to exchange chemical species with surroundings under operating conditions is central to oxide redox reactions running with the Mars-van Krevelen(MvK)mechanism;yet in-situ atomic-scale monitoring of the vacancy dynamics and vacancy-induced secondary defects within oxides remains challenging due to both their rapid transport kinetics at buried subsurface/interface and characterization difficulties,arising from the insulating nature of bulk oxides and the spatial-resolution requirement in reaction conditions.These challenges hinder precise defect engineering for the performance optimization of functional oxides.In this review,recent advancements in tracking oxygen vacancy and vacancyinduced secondary defects dynamics in oxides,including surface steps,cation vacancies,interfacial dislocations,ledges,and interfaces,have been summarized.The dynamic interconversion of defects and their synergistic effects on surface/subsurface/interface evolution are mainly discussed.The aim of this review is to enhance understanding of defect dynamics and their pivotal role in modulating structural dynamics and surface reaction reactivity,which is highly relevant to the catalyst activity/selectivity/stability evaluation of functional oxide catalysts for electroreduction and catalytic oxidation reactions.Finally,strategies to control buried subsurface and interfacial defects(interface engineering)through tailored surface reactions are proposed,offering new pathways to customize the performance of advanced oxide-based materials.展开更多
This study explored the impact of sintering time and temperature on the synthesis and formation of high-entropy rare earth oxides(HEOs).By systematically varying the sintering conditions,a series of Lu_(2)Yb_(2)Tm_(2)...This study explored the impact of sintering time and temperature on the synthesis and formation of high-entropy rare earth oxides(HEOs).By systematically varying the sintering conditions,a series of Lu_(2)Yb_(2)Tm_(2)Er_(2)O_(12) samples was synthesized and their structural and chemical properties were analyzed using scanning electron microscopy(SEM)with energy-dispersive X-ray spectroscopy(EDS)elemental mapping,X-ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM),and X-ray photoelectron spectroscopy(XPS).According to XRD patterns,a single-phase cubic C-type structure is easier to form at higher sintering temperatures(1400-1500℃),with sharper peaks signifying better crystallinity.With longer sintering times improving grain development and homogeneity,SEM research reveals a change in morphology from spherical grains at lower temperatures(1100-1200℃)to blocky grains at higher temperatures(1300-1500℃).HRTEM pictures verified the nanoparticles'strong crystallinity,and at higher temperatures,the lattice fringes widen and become more distinct,indicating better atomic ordering and diffusion.Stable and uniform high-entropy oxide production is indicated by the XPS spectra,which shows uniform elemental distribution and consistent chemical states of the constituent elements with very slight variations in the oxygen peaks.The findings highlight how important the sintering temperature is for reaching the intended high-entropy phase,with higher temperatures promoting improved atomic diffusion and compositional homogeneity.The results open the door for the use of high-entropy rare earth oxides in sophisticated functional materials by offering insightful information on how to best synthesize them.展开更多
Transition metal oxides(TMOs)are widely explored as electrode materials for electrochemical energy storage owing to their rich redox activity,tunable oxidation states,and high theoretical capacitance.However,conventio...Transition metal oxides(TMOs)are widely explored as electrode materials for electrochemical energy storage owing to their rich redox activity,tunable oxidation states,and high theoretical capacitance.However,conventional synthesis routes often rely on toxic chemicals,high-temperature processing,and energy-intensive steps,limiting their sustainability and large-scale applicability.This review highlights recent progress in green synthesis approaches,particularly plant-mediated,microbial,and agro-waste-derived methods that use environmentally benign reducing and stabilizing agents to produce nanostructured TMOs.These green routes enable controlled morphology,enhanced porosity,and defect-rich architectures,resulting in improved charge storage,rate capability,and cycling stability.A comparative assessment of green-synthesized and conventionally prepared TMOs is provided,along with insights into synthesis mechanisms,advantages,limitations,and performance trends.Green chemistry-based strategies show strong potential for developing high-performance,scalable,and eco-friendly electrode materials for next-generation supercapacitors and batteries.展开更多
Valence state engineering has emerged as a powerful strategy to optimize catalytic performance by modulating the electronic structure of metal active sites.However,the valence state regulation in high-entropy compound...Valence state engineering has emerged as a powerful strategy to optimize catalytic performance by modulating the electronic structure of metal active sites.However,the valence state regulation in high-entropy compounds(HECs)remains elusive due to their complex multi-element components and electronic interactions.Here,the valence states of different metals in twodimensional(2D)high entropy oxide(HEO)(FeNiMoRuV)O_(2-x)are precisely modulated through controlled pyrolysis of corresponding 2D high entropy hydroxide(HEHO)(FeNiMoRuV)(OH)_(2)under varying temperatures.Temperature-controlled pyrolysis selectively reduces the oxidation state of Ru,while simultaneously increasing the valence state of other constituent metals(Fe,Ni,Mo,and V),suggesting a competitive redox equilibrium.Notably,these low-valence Ru sites with oxygen vacancy in 2D HEO significantly reduce Ru-O bond energy and promote the generation of O-^(O)intermediates,thereby enabling oxygen evolution with a lattice oxygen mediated-oxygen vacancy site mechanism.2D HEO with low-valence Ru exhibits superior electrolytic water performance(HER/OER)compared to HEHO and other HEO with high-valence Ru,achieving a current density of 1000 mA cm^(-2)at 1.923 V,which exceeds the commercial Pt/C‖RuO_(2)system.Therefore,this study reveals the valence state regulatory mechanism of HECs and provides a solid hammer for the catalytic mechanism of valence state engineering.展开更多
Tetrahydrofuran-2,5-dicarboxylic acid(THFDCA)is a bio-based cyclic dicarboxylic acid with greater flexibility and biosafety than the renowned 2,5-furandicarboxylic acid(FDCA),but its synthesis is limited to thermochem...Tetrahydrofuran-2,5-dicarboxylic acid(THFDCA)is a bio-based cyclic dicarboxylic acid with greater flexibility and biosafety than the renowned 2,5-furandicarboxylic acid(FDCA),but its synthesis is limited to thermochemical methods with only several reports.This study pioneers an electrocatalytic strategy for the efficient synthesis of THFDCA via the oxidation of tetrahydrofuran dimethanol(THFDM).By constructing NiCo bimetallic oxides micron sheets on nickel foam(NiCoMS/NF)through controlled pyrolysis of a metal-organic framework(MOF)-like precursor,we achieved a remarkable THFDM conversion of 99.0%and THFDCA yield up to 98.2%,surpassing all reports on thermocatalytic oxidation as we know.In-depth analysis revealed that the synergistic effect between NiO and Co_(3)O_(4) contributes to the high catalytic performance.In-situ Raman and rotating ring-disk electrode(RRDE)techniques were employed to discuss the reaction mechanism and the inhibitory effect on oxygen evolution reaction(OER).This study not only provides a paradigm-shifting,groundbreaking strategy for the synthesis of the flexible cyclic dicarboxylic acid derived from furanic biomass but also offers deep insights into the synergistic effects of electrocatalysts.展开更多
Fenton technology has garnered significant attention for the deep removal of low-concentration emerging contaminants due to its remarkable oxidation performance.However,the traditional mineralization process for emerg...Fenton technology has garnered significant attention for the deep removal of low-concentration emerging contaminants due to its remarkable oxidation performance.However,the traditional mineralization process for emerging contaminants requires a substantial amount of hydroxyl radicals(HO˙),leading to excessive consumption of H_(2)O_(2).Through interfacial engineering of Fe-Zr bimetallic catalysts(FeZrO_(x)),this study demonstrates synergistic enhancement of phenolic pollutant removal at heterojunction interfaces while achieving an 80%reduction in H_(2)O_(2)dosage compared to traditional Fe_(2)O_(3)systems.The chemical states of Fe and Zr at the(104)/(111)heterojunction interface in FeZrO_(x)exhibit marked modifications relative to their monometallic Fe_(2)O_(3)and ZrO_(2)counterparts.The elevated charge density at interfacial Fe sites in FeZrO_(x)promotes HO˙generation,while optimized antibonding orbital composition below the Fermi level in bisphenol A adsorbed on Zr sites enhances hydrogen abstraction and subsequent polymerization.This Fe-Zr synergy at the(104)/(111)heterojunction concurrently suppresses HO˙diffusion losses and directs phenolic pollutant(e.g.,phenol and bisphenol A)polymerization within the reactive interface,thereby reducing H_(2)O_(2)consumption compared to monometallic systems.展开更多
The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most s...The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most significant applications of metal oxides is heterogeneous catalysis,which represents a pivotal technology in industrial production on a global scale.Catalysts serve as the primary enabling agents for chemical reactions,and among the plethora of catalysts,metal oxides including magnesium oxide(MgO),ceria(CeO_(2))and titania(TiO_(2)),have been identified to be particularly effective in catalyzing a variety of reactions[1].Theoretical calculations based on density functional theory(DFT)and a multitude of other quantum chemistry methods have proven invaluable in elucidating the mechanisms of metal-oxide-catalyzed reactions,thereby facilitating the design of high-performance catalysts[2].展开更多
Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as lumi...Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials,magnetic materials,catalytic materials,electronic devices,they have an important strategic position.In the field of electrocatalysis,rare earth metal elements have great potential for development due to their unique 4f electron layer structure,spin orbit coupling,high reactivity,controllable coordination number,and rich optical properties.However,there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis.Therefore,in order to stimulate the enthusiasm of researchers,this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment,hydrogen peroxide synthesis,hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and machine learning assisted research.In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance.This review is of great significance for further developing high-performance and multifunctional electrocatalysts,and is expected to provide strong support for the development of energy,environment,and chemical industries.展开更多
The influence of the certain specific vacuum pre-oxidation process on the phase transformation of thermally-grown oxides（TGO） was studied.The CoCrAlY high temperature corrosion resistance coatings were produced onto...The influence of the certain specific vacuum pre-oxidation process on the phase transformation of thermally-grown oxides（TGO） was studied.The CoCrAlY high temperature corrosion resistance coatings were produced onto the nickel-based superalloy substrate by high velocity oxygen fuel（HVOF）.It suggests that the TGO usually consists of a great number of chromium oxides,cobalt oxides and spinel oxides besides alumina during the initial period of the high temperature oxidation if the specimens are not subjected to the appropriate vacuum pre-oxidation process.Furthermore,the amount of alumina is strongly dependent on the partial pressure of oxygen;while the CoCr2O4 spinel oxides are usually formed under the conditions of higher partial pressure of oxygen during the initial period and the lower partial pressure of oxygen during the subsequent period of the isothermal oxidation.After the appropriate vacuum pre-oxidation process,the TGO is mainly composed of alumina that contains lower Y element,while alumina that contains higher Y element sporadically distributes,and the spinel oxides cannot be found.After a longer period of the isothermal oxidation,a small amount of porous CoCr2O4 and the chrome oxide sporadically distribute near the continuous alumina.Additionally,after the appropriate vacuum pre-oxidation process,the TGO growth rate is relatively slow.展开更多
Engineering the morphology of spinel mixed metal oxides is a critical strategy for developing highperformance hybrid supercapacitors as they enhance both energy storage performance and cyclic stability.Herein,we prese...Engineering the morphology of spinel mixed metal oxides is a critical strategy for developing highperformance hybrid supercapacitors as they enhance both energy storage performance and cyclic stability.Herein,we present a simple,binder-free method to fabricate hierarchical,pineapple-like CuCo_(2)O_(4)nanostructures on carbon fibers via low-temperature wet-chemical method.By utilizing a combination of hexamine and urea,we tailored the morphology and crystallinity of CuCo_(2)O_(4),improving ion accessibility and interconnectivity,which led to superior electrochemical performance compared to individual components.Particularly,the pineapple-like CuCo_(2)O_(4)demonstrated diffusion-dominated behavior,achieving a higher specific capacitance of 745 F g^(-1)at 1 A g^(-1)and excellent cycling stability.Moreover,a hybrid supercapacitor was fabricated using diffusion-type CuCo_(2)O_(4)electrode and activated carbon as the capacitive electrode,which exhibited good synergy in delivering excellent energy storage performance.The device achieved a specific capacity of 140.5 C g^(-1)at 0.5 A g^(-1)and an energy density of 45.5 Wh kg^(-1)with a high-power density of5950 W kg^(-1).Even at a high current density of 10 A g^(-1),the hybrid supercapacitor maintained excellent rate capability and remarkable cycling stability(89.6%retention after 10,000 cycles),demonstrating efficient charge storage and transfer.Benefiting from high voltage and energy density,the fabricated hybrid supercapacitors successfully powered various LEDs,illustrating their potential for real-world applications.Our work demonstrates the importance of spinal-type nanostructure engineering to achieve enhanced electrochemical performance,providing a straightforward pathway for developing next-generation supercapacitors and battery materials.展开更多
A chain of GdCe oxides boosted biochars derived from maize straw and sewage sludge(GdyCe1-y/MPBs)were fabricated for formaldehyde(HCHO)catalytic decomposition.The ingenerate relationship between the abatement performa...A chain of GdCe oxides boosted biochars derived from maize straw and sewage sludge(GdyCe1-y/MPBs)were fabricated for formaldehyde(HCHO)catalytic decomposition.The ingenerate relationship between the abatement performance and corresponding structural feature was comprehensively evaluated by XPS,in situ DRIFTS,BET,XRD,SEM and H_(2)-TPR.Meanwhile,10%Gd0.25Ce0.75/MPB exhibited excellent performance,favorable SO_(2) and moisture toleration over a broad temperature range from 160 to 320℃,where it achieved 96.8%removal efficiency with 90.5%selectivity at 200℃.The single or united effects of O_(2),SO_(2),H_(2)O on HCHO abatement over 10%Gd_(0.25)Ce_(0.75)/MPB were tested,and the findings demonstrated that the suppressive effects of SO_(2) and H_(2)O outweighed the promoting influence of O_(2) within a specific range.Gd and Ce co-modified MPB revealed superior HCHO removal capability in contrast to that of Gd or Ce severally modified MPB,ascribing to the synergistic effect of GdO_(x) and CeO_(x) and benefitting from the augmentation of surface area and total pore volume,the aggrandizement of surface active oxygen species,the promotion of redox ability and the inhibition crystallization of CeO_(x).According to in situ DRIFTS,a series of intermediates including formate species and dioxymethylene(DOM)were produced,which would eventually decompose into H_(2)O and CO_(2).In addition,the mass transfer and diffusion of the reactants along with the accessibility of the catalytic sites were enlarged by the hierarchical porous structure of the support,which were also answerable for its distinguished catalytic performance.Furthermore,10%Gd0.25Ce0.75/MPB possessed remarkable potential for industrial applications.展开更多
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and re...Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.展开更多
Recently,the strategy of tuning the dielectric parameters of absorbers for their excellent electromag-netic wave absorption(EMA)performance has attracted much attention.Among those candidates used for EMA application,...Recently,the strategy of tuning the dielectric parameters of absorbers for their excellent electromag-netic wave absorption(EMA)performance has attracted much attention.Among those candidates used for EMA application,high-entropy oxides(HEOs)can be implemented with this strategy due to their rich composition modulability.In this work,a series of implementation approaches varying from elemental design to structural modulation are employed to modulate the dielectric parameters of HEOs,resulting in their excellent EMA performance.The addition of Ti element optimizes the dipole distribution at the microscopic scales,improving the dielectric polarization of the materials.Moreover,a composite mate-rial is constructed by physically blending HEO with acetylene black(ACET),which significantly improves the macroscopic conduction loss of the material.The optimization of the dielectric genes of HEO/ACET is achieved with the blending effect and excellent EMA performance could be obtained.Among them,HEO with 17.5%ACET addition exhibits dual-band absorption,while Ti-HEO containing Ti element exhibits not only low-frequency absorption with reflection loss(RL)up to-29.81 dB at C-band but broadband absorption over 6 GHz as well as an optimal RL value up to-52.31 dB.In addition to the development of innovative EMA materials,this study offers a new perspective on how the EMA characteristics can be effectively regulated.展开更多
Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,...Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,and XRD raw data were kept and can be offered.The correct Fig.2 has been provided in this Correction.展开更多
In this study,a string of Cr-Mnco-modified activated coke catalysts(XCryMn1-y/AC)were prepared to investigate toluene and Hg^(0) removal performance.Multifarious characterizations including XRD,TEM,SEM,in situ DRIFTS,...In this study,a string of Cr-Mnco-modified activated coke catalysts(XCryMn1-y/AC)were prepared to investigate toluene and Hg^(0) removal performance.Multifarious characterizations including XRD,TEM,SEM,in situ DRIFTS,BET,XPS and H_(2)-TPR showed that 4%Cr0.5Mn0.5/AC had excellent physicochemical properties and exhibited the best toluene and Hg^(0) removal efficiency at 200℃.By varying the experimental gas components and conditions,it was found that too large weight hourly space velocity would reduce the removal efficiency of toluene and Hg^(0).Although O_(2) promoted the abatement of toluene and Hg^(0),the inhibitory role of H_(2)O and SO_(2) offset the promoting effect of O_(2) to some extent.Toluene significantly inhibited Hg^(0) removal,resulting from that toluene was present at concentrations orders of magnitude greater than mercury’s or the catalyst was more prone to adsorb toluene,while Hg^(0) almost exerted non-existent influence on toluene elimination.The mechanistic analysis showed that the forms of toluene and Hg^(0) removal included both adsorption and oxidation,where the high-valent metal cations and oxygen vacancy clusters promoted the redox cycle of Cr^(3+)+Mn^(3+)/Mn^(4+)+Cr^(6+)+Mn^(2+),which facilitated the conversion and replenishment of reactive oxygen species in the oxidation process,and even the CrMn_(1.5)O_(4) spinel structure could provide a larger catalytic interface,thus enhancing the adsorption/oxidation of toluene and Hg^(0).Therefore,its excellent physicochemical properties make it a costeffective potential industrial catalyst with outstanding synergistic toluene and Hg^(0) removal performance and preeminent resistance to H_(2)O and SO_(2).展开更多
In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatu...In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatures and hydrocarbon concentrations in the FCC riser reactor to convert SOxinto H_(2)S.Subsequently,H_(2)S,along with the cracked gas,is processed downstream to produce sulfur.Thermodynamic analysis of the key reduction reactions in the FCC-DeSOxprocess revealed that complete conversion of SOxto H_(2)S is feasible in the dry gas(hydrogen-rich) prelift zone,as well as the upper and lower zones of the riser,upon achieving thermodynamic equilibrium.Experimental studies were conducted to replicate the conditions of these reaction zones using a low concentration of hydrogen gas as the reducing agent.Through process optimization,investigation of the minimum reaction time,and kinetic studies,the potential of this method for the complete reduction of SOxwas further confirmed.展开更多
The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthen...The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthenium/iridium oxides(RuO_(2)/IrO_(2)).In this work,we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO_(2)with Pt.Pt dopants in ruthenium oxides(Pt-RuO_(2))create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates,evidenced by downshifted d band center and increment in e_(g)orbital filling of Ru atom;thereby,the acidic OER performance of Pt-RuO_(2)is enhanced by 3.5-fold than commercial RuO_(2)by mean of turnover frequency at 1.6 V vs.RHE.Moreover,Pt-RuO_(2)exhibits a similar HER performance to commercial Pt/C.The potential for overall water splitting is decreased by 0.18 V at100 mA/cm^(2);besides,an excellent stability is also recorded after the incorporation of Pt dopants.TheΔ_(ε_(d-p))value of Pt-RuO_(2)was 1.76 e V,which is lower than the counterpart of RuO_(2),suggesting easy electron transition between d and p orbitals,suppressing the over-oxidation of RuO_(2);thereby,a higher stability is achieved for Pt-RuO_(2).The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO_(2).展开更多
The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based...The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.展开更多
Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(F...Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(FNP)were investigated on the fresh leachate AD process.Firstly,a simple hydrothermal method was used to prepare FNP,then introduced into the UASB reactor to evaluate its AD efficiency.Results showed that the inclusion of FNP could shorten the lag phase by 10 days compared to the control group.Furthermore,cumulative methane production in the FNP group was enhanced by 20.11%.Mechanistic studies suggested that hydrogenotrophic methanogenesis in the FNP group was more pronounced due to the influence of key enzymes(i.e.,dehydrogenase and coenzyme F420).Microbial community analysis demonstrated that FNP could enhance the abundance of Methanosarcina,Proteobacteria,Sytrophomonas,and Limnobacter,which might elevate enzyme activity involved in methane production.These findings suggest that FNP might mediate interspecies electron transfer among these microorganisms,which is essential for efficient leachate treatment.展开更多
文摘It is crucial to develop arsenic removal adsorbents with strong sulfur resistance under middle-low-temperature flue gas conditions(<400℃).In this work,five Fe-Ce-La oxides were prepared by co-precipitation method,and FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbents were prepared by coupling fly ash-based Si-Al carriers.The active components Fe-Ce-La oxides and Si-Al carriers were characterized by TPD,TG,XRF,BET and XPS,respectively.The effects of temperature,Si/Al ratio and FeCeLaO loading rate on the sulfur resistance were investigated.Results show that the SO_(2) promotes the arsenic removal of Fe_(2)O_(3),CeLaO and FeCeLaO.At 400℃,the arsenic removal efficiencies of the three oxides increase from 45.3%,72.5% and 81.3% without SO_(2) to 62.6%,80.5%and 91.0%,respectively.The SO_(2) inhibits the arsenic removal of La_(2)O_(2)CO_(3) and FeLaO,and the inhibition effect is pronounced at high temperatures.The sulfur poisoning resistance of Si-Al carriers increases with the increase of Si/Al ratio.When the Si/Al ratio is increased to 9.74,the arsenic removal efficiency in the SO_(2) environment is 13.9% higher than that in the absence of SO_(2).Introducing FeCeLaO active components is beneficial for enhancing the SO_(2) poisoning resistance of Si-Al carriers.The strong sulfur resistance of the FeCeLaO/SiO_(2)-Al_(2)O_(3) composite adsorbent results from multiple factors:protective effects of Ce on Fe,La and Al;sulfation-induced generation of Ce^(3+)and surface-adsorbed oxygen;and strong surface acidity of SiO_(2).
基金supported by the funding support from the National Key R&D Program of China(2024YFA1509400)the Beijing Natural Science Foundation(F251001)+2 种基金the National Natural Science Foundation of China(No.22479148)the Institute of Weiqiao UCAS Science and Technology(GYY-GDHX-2024-ZY-007)supported by the U.S.National Science Foundation Under Grant No.DMR 2303712。
文摘Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic behavior of these vacancies as main mass transport mediums to exchange chemical species with surroundings under operating conditions is central to oxide redox reactions running with the Mars-van Krevelen(MvK)mechanism;yet in-situ atomic-scale monitoring of the vacancy dynamics and vacancy-induced secondary defects within oxides remains challenging due to both their rapid transport kinetics at buried subsurface/interface and characterization difficulties,arising from the insulating nature of bulk oxides and the spatial-resolution requirement in reaction conditions.These challenges hinder precise defect engineering for the performance optimization of functional oxides.In this review,recent advancements in tracking oxygen vacancy and vacancyinduced secondary defects dynamics in oxides,including surface steps,cation vacancies,interfacial dislocations,ledges,and interfaces,have been summarized.The dynamic interconversion of defects and their synergistic effects on surface/subsurface/interface evolution are mainly discussed.The aim of this review is to enhance understanding of defect dynamics and their pivotal role in modulating structural dynamics and surface reaction reactivity,which is highly relevant to the catalyst activity/selectivity/stability evaluation of functional oxide catalysts for electroreduction and catalytic oxidation reactions.Finally,strategies to control buried subsurface and interfacial defects(interface engineering)through tailored surface reactions are proposed,offering new pathways to customize the performance of advanced oxide-based materials.
基金Project supported by Natural Science Foundation of Zhejiang Province(LD21E080001)Zhejiang Provincial Ten Thousand Talent Program(ZJWR0302055)。
文摘This study explored the impact of sintering time and temperature on the synthesis and formation of high-entropy rare earth oxides(HEOs).By systematically varying the sintering conditions,a series of Lu_(2)Yb_(2)Tm_(2)Er_(2)O_(12) samples was synthesized and their structural and chemical properties were analyzed using scanning electron microscopy(SEM)with energy-dispersive X-ray spectroscopy(EDS)elemental mapping,X-ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM),and X-ray photoelectron spectroscopy(XPS).According to XRD patterns,a single-phase cubic C-type structure is easier to form at higher sintering temperatures(1400-1500℃),with sharper peaks signifying better crystallinity.With longer sintering times improving grain development and homogeneity,SEM research reveals a change in morphology from spherical grains at lower temperatures(1100-1200℃)to blocky grains at higher temperatures(1300-1500℃).HRTEM pictures verified the nanoparticles'strong crystallinity,and at higher temperatures,the lattice fringes widen and become more distinct,indicating better atomic ordering and diffusion.Stable and uniform high-entropy oxide production is indicated by the XPS spectra,which shows uniform elemental distribution and consistent chemical states of the constituent elements with very slight variations in the oxygen peaks.The findings highlight how important the sintering temperature is for reaching the intended high-entropy phase,with higher temperatures promoting improved atomic diffusion and compositional homogeneity.The results open the door for the use of high-entropy rare earth oxides in sophisticated functional materials by offering insightful information on how to best synthesize them.
文摘Transition metal oxides(TMOs)are widely explored as electrode materials for electrochemical energy storage owing to their rich redox activity,tunable oxidation states,and high theoretical capacitance.However,conventional synthesis routes often rely on toxic chemicals,high-temperature processing,and energy-intensive steps,limiting their sustainability and large-scale applicability.This review highlights recent progress in green synthesis approaches,particularly plant-mediated,microbial,and agro-waste-derived methods that use environmentally benign reducing and stabilizing agents to produce nanostructured TMOs.These green routes enable controlled morphology,enhanced porosity,and defect-rich architectures,resulting in improved charge storage,rate capability,and cycling stability.A comparative assessment of green-synthesized and conventionally prepared TMOs is provided,along with insights into synthesis mechanisms,advantages,limitations,and performance trends.Green chemistry-based strategies show strong potential for developing high-performance,scalable,and eco-friendly electrode materials for next-generation supercapacitors and batteries.
基金supported by the National Natural Science Foundation of China(22205209)China Postdoctoral Science Foundation(2024T170837 and2022M722867)+2 种基金Joint Fund for Provincial Scientific Research and Development Plan of Henan Province(242301420039)the Key Research Projects of Higher Education Institutions of Henan Province(24A530009)Special Fund for Young Teachers from the Zhengzhou University(JC23257011)。
文摘Valence state engineering has emerged as a powerful strategy to optimize catalytic performance by modulating the electronic structure of metal active sites.However,the valence state regulation in high-entropy compounds(HECs)remains elusive due to their complex multi-element components and electronic interactions.Here,the valence states of different metals in twodimensional(2D)high entropy oxide(HEO)(FeNiMoRuV)O_(2-x)are precisely modulated through controlled pyrolysis of corresponding 2D high entropy hydroxide(HEHO)(FeNiMoRuV)(OH)_(2)under varying temperatures.Temperature-controlled pyrolysis selectively reduces the oxidation state of Ru,while simultaneously increasing the valence state of other constituent metals(Fe,Ni,Mo,and V),suggesting a competitive redox equilibrium.Notably,these low-valence Ru sites with oxygen vacancy in 2D HEO significantly reduce Ru-O bond energy and promote the generation of O-^(O)intermediates,thereby enabling oxygen evolution with a lattice oxygen mediated-oxygen vacancy site mechanism.2D HEO with low-valence Ru exhibits superior electrolytic water performance(HER/OER)compared to HEHO and other HEO with high-valence Ru,achieving a current density of 1000 mA cm^(-2)at 1.923 V,which exceeds the commercial Pt/C‖RuO_(2)system.Therefore,this study reveals the valence state regulatory mechanism of HECs and provides a solid hammer for the catalytic mechanism of valence state engineering.
基金supported by the National Natural Science Foundation of China(22072170,U23A20125)the President Foundation of Ningbo Institute of Materials Technology and Engineering。
文摘Tetrahydrofuran-2,5-dicarboxylic acid(THFDCA)is a bio-based cyclic dicarboxylic acid with greater flexibility and biosafety than the renowned 2,5-furandicarboxylic acid(FDCA),but its synthesis is limited to thermochemical methods with only several reports.This study pioneers an electrocatalytic strategy for the efficient synthesis of THFDCA via the oxidation of tetrahydrofuran dimethanol(THFDM).By constructing NiCo bimetallic oxides micron sheets on nickel foam(NiCoMS/NF)through controlled pyrolysis of a metal-organic framework(MOF)-like precursor,we achieved a remarkable THFDM conversion of 99.0%and THFDCA yield up to 98.2%,surpassing all reports on thermocatalytic oxidation as we know.In-depth analysis revealed that the synergistic effect between NiO and Co_(3)O_(4) contributes to the high catalytic performance.In-situ Raman and rotating ring-disk electrode(RRDE)techniques were employed to discuss the reaction mechanism and the inhibitory effect on oxygen evolution reaction(OER).This study not only provides a paradigm-shifting,groundbreaking strategy for the synthesis of the flexible cyclic dicarboxylic acid derived from furanic biomass but also offers deep insights into the synergistic effects of electrocatalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.22476187 and 22206173)the Natural Science Foundation of Henan Province(Grant No.252300421179)+1 种基金the Foundation of Henan Educational Committee(Grant No.25A610001)the Science and Technology Innovation Leading Talent Support Program of Henan Province(Grant No.254000510035).
文摘Fenton technology has garnered significant attention for the deep removal of low-concentration emerging contaminants due to its remarkable oxidation performance.However,the traditional mineralization process for emerging contaminants requires a substantial amount of hydroxyl radicals(HO˙),leading to excessive consumption of H_(2)O_(2).Through interfacial engineering of Fe-Zr bimetallic catalysts(FeZrO_(x)),this study demonstrates synergistic enhancement of phenolic pollutant removal at heterojunction interfaces while achieving an 80%reduction in H_(2)O_(2)dosage compared to traditional Fe_(2)O_(3)systems.The chemical states of Fe and Zr at the(104)/(111)heterojunction interface in FeZrO_(x)exhibit marked modifications relative to their monometallic Fe_(2)O_(3)and ZrO_(2)counterparts.The elevated charge density at interfacial Fe sites in FeZrO_(x)promotes HO˙generation,while optimized antibonding orbital composition below the Fermi level in bisphenol A adsorbed on Zr sites enhances hydrogen abstraction and subsequent polymerization.This Fe-Zr synergy at the(104)/(111)heterojunction concurrently suppresses HO˙diffusion losses and directs phenolic pollutant(e.g.,phenol and bisphenol A)polymerization within the reactive interface,thereby reducing H_(2)O_(2)consumption compared to monometallic systems.
基金financial support from the National Key R&D Program of China(2021YFB3500700)the National Natural Science Foundation of China(22473042,22003016,and 92145302).
文摘The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most significant applications of metal oxides is heterogeneous catalysis,which represents a pivotal technology in industrial production on a global scale.Catalysts serve as the primary enabling agents for chemical reactions,and among the plethora of catalysts,metal oxides including magnesium oxide(MgO),ceria(CeO_(2))and titania(TiO_(2)),have been identified to be particularly effective in catalyzing a variety of reactions[1].Theoretical calculations based on density functional theory(DFT)and a multitude of other quantum chemistry methods have proven invaluable in elucidating the mechanisms of metal-oxide-catalyzed reactions,thereby facilitating the design of high-performance catalysts[2].
基金supported by the National Key Research and Development Program of China(No.2023YFC3708005)The Fundamental Research Funds for the Central Universities,Nankai University(No.63241208)supported by the National Natural Science Foundation of China(Nos.21872102 and 22172080)。
文摘Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials,magnetic materials,catalytic materials,electronic devices,they have an important strategic position.In the field of electrocatalysis,rare earth metal elements have great potential for development due to their unique 4f electron layer structure,spin orbit coupling,high reactivity,controllable coordination number,and rich optical properties.However,there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis.Therefore,in order to stimulate the enthusiasm of researchers,this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment,hydrogen peroxide synthesis,hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and machine learning assisted research.In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance.This review is of great significance for further developing high-performance and multifunctional electrocatalysts,and is expected to provide strong support for the development of energy,environment,and chemical industries.
基金Project supported the by State Key Laboratory of Internal Combustion Engines of Tianjin University,ChinaProject(51507077)supported by the National Natural Science Foundation of China+1 种基金Project(15KJB470005)supported by the Natural Science Research of Higher Education Institutions of Jiangsu Province,ChinaProjects(YKJ201308,QKJB201401)supported by Nanjing Institute of Technology,China
文摘The influence of the certain specific vacuum pre-oxidation process on the phase transformation of thermally-grown oxides（TGO） was studied.The CoCrAlY high temperature corrosion resistance coatings were produced onto the nickel-based superalloy substrate by high velocity oxygen fuel（HVOF）.It suggests that the TGO usually consists of a great number of chromium oxides,cobalt oxides and spinel oxides besides alumina during the initial period of the high temperature oxidation if the specimens are not subjected to the appropriate vacuum pre-oxidation process.Furthermore,the amount of alumina is strongly dependent on the partial pressure of oxygen;while the CoCr2O4 spinel oxides are usually formed under the conditions of higher partial pressure of oxygen during the initial period and the lower partial pressure of oxygen during the subsequent period of the isothermal oxidation.After the appropriate vacuum pre-oxidation process,the TGO is mainly composed of alumina that contains lower Y element,while alumina that contains higher Y element sporadically distributes,and the spinel oxides cannot be found.After a longer period of the isothermal oxidation,a small amount of porous CoCr2O4 and the chrome oxide sporadically distribute near the continuous alumina.Additionally,after the appropriate vacuum pre-oxidation process,the TGO growth rate is relatively slow.
基金funding of the Deanship of Graduate Studies and Scientific Research,Jazan University,Saudi Arabia(No.JU-202503193-DGSSR-RP2025)
文摘Engineering the morphology of spinel mixed metal oxides is a critical strategy for developing highperformance hybrid supercapacitors as they enhance both energy storage performance and cyclic stability.Herein,we present a simple,binder-free method to fabricate hierarchical,pineapple-like CuCo_(2)O_(4)nanostructures on carbon fibers via low-temperature wet-chemical method.By utilizing a combination of hexamine and urea,we tailored the morphology and crystallinity of CuCo_(2)O_(4),improving ion accessibility and interconnectivity,which led to superior electrochemical performance compared to individual components.Particularly,the pineapple-like CuCo_(2)O_(4)demonstrated diffusion-dominated behavior,achieving a higher specific capacitance of 745 F g^(-1)at 1 A g^(-1)and excellent cycling stability.Moreover,a hybrid supercapacitor was fabricated using diffusion-type CuCo_(2)O_(4)electrode and activated carbon as the capacitive electrode,which exhibited good synergy in delivering excellent energy storage performance.The device achieved a specific capacity of 140.5 C g^(-1)at 0.5 A g^(-1)and an energy density of 45.5 Wh kg^(-1)with a high-power density of5950 W kg^(-1).Even at a high current density of 10 A g^(-1),the hybrid supercapacitor maintained excellent rate capability and remarkable cycling stability(89.6%retention after 10,000 cycles),demonstrating efficient charge storage and transfer.Benefiting from high voltage and energy density,the fabricated hybrid supercapacitors successfully powered various LEDs,illustrating their potential for real-world applications.Our work demonstrates the importance of spinal-type nanostructure engineering to achieve enhanced electrochemical performance,providing a straightforward pathway for developing next-generation supercapacitors and battery materials.
基金supported by the Scientific Research Project of Hunan Provincial EducationDepartment(No.22B0458)the National Natural Science Foundation of China(No.52270102).
文摘A chain of GdCe oxides boosted biochars derived from maize straw and sewage sludge(GdyCe1-y/MPBs)were fabricated for formaldehyde(HCHO)catalytic decomposition.The ingenerate relationship between the abatement performance and corresponding structural feature was comprehensively evaluated by XPS,in situ DRIFTS,BET,XRD,SEM and H_(2)-TPR.Meanwhile,10%Gd0.25Ce0.75/MPB exhibited excellent performance,favorable SO_(2) and moisture toleration over a broad temperature range from 160 to 320℃,where it achieved 96.8%removal efficiency with 90.5%selectivity at 200℃.The single or united effects of O_(2),SO_(2),H_(2)O on HCHO abatement over 10%Gd_(0.25)Ce_(0.75)/MPB were tested,and the findings demonstrated that the suppressive effects of SO_(2) and H_(2)O outweighed the promoting influence of O_(2) within a specific range.Gd and Ce co-modified MPB revealed superior HCHO removal capability in contrast to that of Gd or Ce severally modified MPB,ascribing to the synergistic effect of GdO_(x) and CeO_(x) and benefitting from the augmentation of surface area and total pore volume,the aggrandizement of surface active oxygen species,the promotion of redox ability and the inhibition crystallization of CeO_(x).According to in situ DRIFTS,a series of intermediates including formate species and dioxymethylene(DOM)were produced,which would eventually decompose into H_(2)O and CO_(2).In addition,the mass transfer and diffusion of the reactants along with the accessibility of the catalytic sites were enlarged by the hierarchical porous structure of the support,which were also answerable for its distinguished catalytic performance.Furthermore,10%Gd0.25Ce0.75/MPB possessed remarkable potential for industrial applications.
基金supported by National Natural Science Fundation of China(Nos.52170086,22308194,U22A20423)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn202211012)Shandong Provincial Excellent Youth(No.ZR2022YQ47)。
文摘Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.
基金supported by the National Natural Science Foundation of China(Nos.52372289 and 52102368)the Guangdong Special Fund for key Areas(No.20237DZX3042)+1 种基金the State Key Laboratory of New Ceramic Materials Tsinghua University(No.KF202415)the Shenzhen Stable Support Project.
文摘Recently,the strategy of tuning the dielectric parameters of absorbers for their excellent electromag-netic wave absorption(EMA)performance has attracted much attention.Among those candidates used for EMA application,high-entropy oxides(HEOs)can be implemented with this strategy due to their rich composition modulability.In this work,a series of implementation approaches varying from elemental design to structural modulation are employed to modulate the dielectric parameters of HEOs,resulting in their excellent EMA performance.The addition of Ti element optimizes the dipole distribution at the microscopic scales,improving the dielectric polarization of the materials.Moreover,a composite mate-rial is constructed by physically blending HEO with acetylene black(ACET),which significantly improves the macroscopic conduction loss of the material.The optimization of the dielectric genes of HEO/ACET is achieved with the blending effect and excellent EMA performance could be obtained.Among them,HEO with 17.5%ACET addition exhibits dual-band absorption,while Ti-HEO containing Ti element exhibits not only low-frequency absorption with reflection loss(RL)up to-29.81 dB at C-band but broadband absorption over 6 GHz as well as an optimal RL value up to-52.31 dB.In addition to the development of innovative EMA materials,this study offers a new perspective on how the EMA characteristics can be effectively regulated.
文摘Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,and XRD raw data were kept and can be offered.The correct Fig.2 has been provided in this Correction.
基金supported by the Scientific Research Project of Hunan Provincial Department of Education (No.22B0458)the National Natural Science Foundation of China (No.52270102).
文摘In this study,a string of Cr-Mnco-modified activated coke catalysts(XCryMn1-y/AC)were prepared to investigate toluene and Hg^(0) removal performance.Multifarious characterizations including XRD,TEM,SEM,in situ DRIFTS,BET,XPS and H_(2)-TPR showed that 4%Cr0.5Mn0.5/AC had excellent physicochemical properties and exhibited the best toluene and Hg^(0) removal efficiency at 200℃.By varying the experimental gas components and conditions,it was found that too large weight hourly space velocity would reduce the removal efficiency of toluene and Hg^(0).Although O_(2) promoted the abatement of toluene and Hg^(0),the inhibitory role of H_(2)O and SO_(2) offset the promoting effect of O_(2) to some extent.Toluene significantly inhibited Hg^(0) removal,resulting from that toluene was present at concentrations orders of magnitude greater than mercury’s or the catalyst was more prone to adsorb toluene,while Hg^(0) almost exerted non-existent influence on toluene elimination.The mechanistic analysis showed that the forms of toluene and Hg^(0) removal included both adsorption and oxidation,where the high-valent metal cations and oxygen vacancy clusters promoted the redox cycle of Cr^(3+)+Mn^(3+)/Mn^(4+)+Cr^(6+)+Mn^(2+),which facilitated the conversion and replenishment of reactive oxygen species in the oxidation process,and even the CrMn_(1.5)O_(4) spinel structure could provide a larger catalytic interface,thus enhancing the adsorption/oxidation of toluene and Hg^(0).Therefore,its excellent physicochemical properties make it a costeffective potential industrial catalyst with outstanding synergistic toluene and Hg^(0) removal performance and preeminent resistance to H_(2)O and SO_(2).
基金supported by General Program of National Natural Science Foundation of China (22178385)。
文摘In this work,a new process for achieving the recovery of elemental sulfur by utilizing a fluidized catalytic cracking(FCC) riser reactor for SOxtreatment(FCC-DeSOx) is proposed.The process leverages the high temperatures and hydrocarbon concentrations in the FCC riser reactor to convert SOxinto H_(2)S.Subsequently,H_(2)S,along with the cracked gas,is processed downstream to produce sulfur.Thermodynamic analysis of the key reduction reactions in the FCC-DeSOxprocess revealed that complete conversion of SOxto H_(2)S is feasible in the dry gas(hydrogen-rich) prelift zone,as well as the upper and lower zones of the riser,upon achieving thermodynamic equilibrium.Experimental studies were conducted to replicate the conditions of these reaction zones using a low concentration of hydrogen gas as the reducing agent.Through process optimization,investigation of the minimum reaction time,and kinetic studies,the potential of this method for the complete reduction of SOxwas further confirmed.
基金supported by the National Natural Science Foundation of China(No.22209126)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(No.JDGD-202314)。
文摘The commercialization of polymer electrolyte membrane water splitting technology significantly depends on the oxygen/hydrogen evolution reaction(OER/HER)electrocatalysts;customarily catalyzed by platinum(Pt)and ruthenium/iridium oxides(RuO_(2)/IrO_(2)).In this work,we have devised a novel strategy to improve the catalytic activities towards OER and HER catalysis via the decoration of RuO_(2)with Pt.Pt dopants in ruthenium oxides(Pt-RuO_(2))create more oxygen vacancies inducing a weaker interaction between active site and oxygen reaction intermediates,evidenced by downshifted d band center and increment in e_(g)orbital filling of Ru atom;thereby,the acidic OER performance of Pt-RuO_(2)is enhanced by 3.5-fold than commercial RuO_(2)by mean of turnover frequency at 1.6 V vs.RHE.Moreover,Pt-RuO_(2)exhibits a similar HER performance to commercial Pt/C.The potential for overall water splitting is decreased by 0.18 V at100 mA/cm^(2);besides,an excellent stability is also recorded after the incorporation of Pt dopants.TheΔ_(ε_(d-p))value of Pt-RuO_(2)was 1.76 e V,which is lower than the counterpart of RuO_(2),suggesting easy electron transition between d and p orbitals,suppressing the over-oxidation of RuO_(2);thereby,a higher stability is achieved for Pt-RuO_(2).The invitation of Pt dopants to boost catalytic activity and stability has also been extended to IrO_(2).
基金National Natural Science Foundation of China,Grant/Award Numbers:22179008,21875022Yibin“Jie Bang Gua Shuai”,Grant/Award Number:2022JB004+2 种基金Beijing Nova Program,Grant/Award Number:20230484241Postdoctoral Fellowship Program of CPSF,Grant/Award Number:GZB20230931Special Support of Chongqing Postdoctoral Research Project,Grant/Award Number:2023CQBSHTB2041。
文摘The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.
基金supported by the National Key Research and Development Program of China(No.2019YFC0408500)the Scientific Research Project of China State Construction Engineering Corporation Limited(CSCEC-2022-K-(36))the Scientific Research Project of CSCEC AECOM Consultants Corporation Limited(XBSZKY2216).
文摘Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(FNP)were investigated on the fresh leachate AD process.Firstly,a simple hydrothermal method was used to prepare FNP,then introduced into the UASB reactor to evaluate its AD efficiency.Results showed that the inclusion of FNP could shorten the lag phase by 10 days compared to the control group.Furthermore,cumulative methane production in the FNP group was enhanced by 20.11%.Mechanistic studies suggested that hydrogenotrophic methanogenesis in the FNP group was more pronounced due to the influence of key enzymes(i.e.,dehydrogenase and coenzyme F420).Microbial community analysis demonstrated that FNP could enhance the abundance of Methanosarcina,Proteobacteria,Sytrophomonas,and Limnobacter,which might elevate enzyme activity involved in methane production.These findings suggest that FNP might mediate interspecies electron transfer among these microorganisms,which is essential for efficient leachate treatment.
