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
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
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
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
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
The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means ...The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means of XRD and SEM. The results revealed that the rich cerium rare earth carbonate could be changed into the rare earth oxide which was a kind of sandwich made of globose granule whose diameter was between 0.5～3.0 μm after being roasted in 900 ℃ for 2 h. This kind of crystal lattice in rare earth oxide belonged to face-centered cubic lattice and its space between crystal surface {111} and {200} (viz. L111 and L200) would enlarge as the roasting temperature increasing. With increasing roasting temperature, L111 would rise straightly upward, and L200 would rise straightly upward when roasting time was 2～4 h but changed little when roasting time was 4～6 h. The glass-polishing experiments found that the polishing ability of the ceria-based rare earth oxide was the best as L111 was 43～53 nm and the L200 was 43～56 nm.展开更多
Developments in ceria-based soot oxidation catalysts, especially during the last decade, are reviewed. Based on the com- parisons of the activity, durability and cost-efficiency of different soot oxidation catalysts, ...Developments in ceria-based soot oxidation catalysts, especially during the last decade, are reviewed. Based on the com- parisons of the activity, durability and cost-efficiency of different soot oxidation catalysts, four kinds of applicable ceria-based cata- lysts have been screened out, which are： （1） CexZrl-xO2 catalyst with high cerium content （x〉0.76）, （2） rare-earth metals （especially Pr） modified ceria, （3） transition metals （especially Mn and Cu） modified ceria, and （4） Ag/CeO2. Moreover, a general review of recent developments on the morphology-controlled ceria-based catalysts, as well as that on the soot oxidation mechanisms over different ceria-based catalysts, is also presented.展开更多
With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysi...With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.展开更多
In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic ac...In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic acid)ligand.Mg_(2)Ti-ABTC exhibited permanent porosity for N_(2),CO_(2),CH_(4),C_(2)H_(2),C_(2)H_(4),and C_(2)H_(6)gas adsorption.Further-more,Mg_(2)Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corre-sponding sulfoxides under ambient air conditions.Mechanism studies reveal that photoinduced holes(h^(+)),the super-oxide radical(·O_(2)^(-)),and singlet oxygen(^(1)O_(2))are pivotal species involved in the photocatalytic oxidation reaction.展开更多
Noble metal(M:Pt,Pd,PtPd) supported on ceria system catalysts were investigated.The oxidized and reduced forms of the active component were examined in CO oxidation.All catalysts become more active after a reduction p...Noble metal(M:Pt,Pd,PtPd) supported on ceria system catalysts were investigated.The oxidized and reduced forms of the active component were examined in CO oxidation.All catalysts become more active after a reduction pretreatment,which shifts the temperature of CO oxidation.Analysis of the data obtained from characterization techniques indicates that the strong interaction of metal ions with the support prevent the reduction of the initial MO_(x)to metallic M.The formation of M-ceria interfaces efficiently boosts the oxygen activation during CO oxidation,leading to the formation of chemisorbed O on M and the regeneration of the ceria lattice oxygen,thus greatly improving the catalytic performance.展开更多
Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-bas...Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-based layered oxide cathodes-a leading candidate for PIB systems-has been fundamentally constrained by irreversible phase transitions(PT)during the cycling process,manifesting as severe structural degradation and capacity fading.This review presents a transformative paradigm integrating machine learning(ML)with multiscale characterization to analyse the complex phase transition mechanisms in Mn-based cathodes.Through systematic ML-driven interrogation of structure-property relationships,we establish quantitative descriptors for phase stability and develop predictive models for transition dynamics.Furthermore,we highlight recent breakthroughs in cross-disciplinary approaches,enabling the rational design of PT-mitigated cathode architectures.By consolidating these insights into a unified knowledge framework,this work provides strategic guidelines for developing structurally robust Mn-based cathodes and outlines future research directions for next-generation PIB systems.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
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
Cation segregation on cathode surfaces plays a key role in determining the activity and operational stability of solid oxide fuel cells(SOFCs).The double perovskite oxide PrBa_(0.8)Ca_(0.2)Co_(2)O_(5+δ)(PBCC)has been...Cation segregation on cathode surfaces plays a key role in determining the activity and operational stability of solid oxide fuel cells(SOFCs).The double perovskite oxide PrBa_(0.8)Ca_(0.2)Co_(2)O_(5+δ)(PBCC)has been widely studied as an active cathode but still suffer from serious detrimental segregations.To enhance the cathode stability,a PBCC derived A-site medium-entropy Pr_(0.6)La_(0.1)Nd_(0.1)Sm_(0.1)Gd_(0.1)Ba_(0.8)Ca_(0.2)Co_(2)O_(5+δ)(ME-PBCC)oxide was prepared and its segregation behaviors were investigated under different conditions.Compared with initial PBCC oxide,the segregations of BaO and Co_(3)O_(4)on the surface of ME-PBCC material are significantly suppressed,especially for Co_(3)O_(4),which is attributed to its higher configuration entropy.Our results also confirm the improved electrochemical performance and structural stability of ME-PBCC material,enabling it as a promising cathode for SOFCs.展开更多
The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the ...The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.展开更多
The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping...The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.展开更多
Bisphenol A(BPA)is a pervasive endocrine disruptor that enters the environment through anthropogenic activities,posing significant risks to ecosystems and human health.Advanced oxidation processes(AOPs)are promising m...Bisphenol A(BPA)is a pervasive endocrine disruptor that enters the environment through anthropogenic activities,posing significant risks to ecosystems and human health.Advanced oxidation processes(AOPs)are promising methods for the removal of organic microcontaminants in the environment.Biogenic manganese oxides(BMO)are reported as catalysts due to their transitionmetal nature,and are also readily generated bymanganeseoxidizing microorganisms in the natural environment,and therefore their roles and effects in AOPs-based environmental remediation should be investigated.However,biogenic ironmanganese oxides(BFMO)are actually generated rather than BMO due to the coexistence of ferrous ionswhich can be oxidized to iron oxides.Therefore,this study produced BFMO originating from a highly efficientmanganese-oxidizing fungus Cladosporium sp.XM01 and chose peroxymonosulfate(PMS)as a typical oxidant for the degradation of bisphenol A(BPA),a model organic micropollutant.Characterization results indicate that the formed BFMO was amorphouswith a lowcrystallinity.The BFMO/PMS system achieved a high degradation performance that 85%BPA was rapidly degraded within 60min,and therefore the contribution of BFMO cannot be ignored during PMS-based environmental remediation.Different from the findings of previous studies(mostly radicals and singlet oxygen),the degradationmechanism was first proven as a 100%electron-transfer pathway mediated by high-valence Mn under acidic conditions provided by PMS.The findings of this study provide new insights into the degradation mechanisms of pollutants using biogenic metal oxides in PMS activation and the contribution of their coexistence in AOPs-based environmental remediation.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
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.
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.
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.
文摘The granule shape and crystal structure of the the ceria-based rare earth oxide which were roasted at 600～1050 ℃ for 2～6 h and then cooled in furnace, cooled out of furnace or cooled in water were studied by means of XRD and SEM. The results revealed that the rich cerium rare earth carbonate could be changed into the rare earth oxide which was a kind of sandwich made of globose granule whose diameter was between 0.5～3.0 μm after being roasted in 900 ℃ for 2 h. This kind of crystal lattice in rare earth oxide belonged to face-centered cubic lattice and its space between crystal surface {111} and {200} (viz. L111 and L200) would enlarge as the roasting temperature increasing. With increasing roasting temperature, L111 would rise straightly upward, and L200 would rise straightly upward when roasting time was 2～4 h but changed little when roasting time was 4～6 h. The glass-polishing experiments found that the polishing ability of the ceria-based rare earth oxide was the best as L111 was 43～53 nm and the L200 was 43～56 nm.
基金supported by Ministry of Science and Technology of China(2013AA061902)the National Development and Reform Commission of China(2013012402)
文摘Developments in ceria-based soot oxidation catalysts, especially during the last decade, are reviewed. Based on the com- parisons of the activity, durability and cost-efficiency of different soot oxidation catalysts, four kinds of applicable ceria-based cata- lysts have been screened out, which are： （1） CexZrl-xO2 catalyst with high cerium content （x〉0.76）, （2） rare-earth metals （especially Pr） modified ceria, （3） transition metals （especially Mn and Cu） modified ceria, and （4） Ag/CeO2. Moreover, a general review of recent developments on the morphology-controlled ceria-based catalysts, as well as that on the soot oxidation mechanisms over different ceria-based catalysts, is also presented.
文摘With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.
文摘In the paper,we report a highly robust and porous bimetallic Ti-MOF(designated Mg_(2)Ti-ABTC)by utiliz-ing a trinuclear[Mg_(2)TiO(COO)_(6)]cluster and a tetradentate H_(4)ABTC(3,3′,5,5′-azobenzene tetracarboxylic acid)ligand.Mg_(2)Ti-ABTC exhibited permanent porosity for N_(2),CO_(2),CH_(4),C_(2)H_(2),C_(2)H_(4),and C_(2)H_(6)gas adsorption.Further-more,Mg_(2)Ti-ABTC exhibited outstanding photocatalytic activity in the oxidation of aromatic sulfides to the corre-sponding sulfoxides under ambient air conditions.Mechanism studies reveal that photoinduced holes(h^(+)),the super-oxide radical(·O_(2)^(-)),and singlet oxygen(^(1)O_(2))are pivotal species involved in the photocatalytic oxidation reaction.
基金Project partially supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental orders and the state funding。
文摘Noble metal(M:Pt,Pd,PtPd) supported on ceria system catalysts were investigated.The oxidized and reduced forms of the active component were examined in CO oxidation.All catalysts become more active after a reduction pretreatment,which shifts the temperature of CO oxidation.Analysis of the data obtained from characterization techniques indicates that the strong interaction of metal ions with the support prevent the reduction of the initial MO_(x)to metallic M.The formation of M-ceria interfaces efficiently boosts the oxygen activation during CO oxidation,leading to the formation of chemisorbed O on M and the regeneration of the ceria lattice oxygen,thus greatly improving the catalytic performance.
基金financially supported by the National Natural Science Foundation of China(U20A20247)the National Key Research and Development Program of the Ministry of Science and Technology(2022YFA1402504)+1 种基金Guangdong Provincial Key Laboratory of Materials and Technologies for Energy Conversion(MATEC2023KF002)Guangdong Science and Technology Department(STKJ2021016)。
文摘Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-based layered oxide cathodes-a leading candidate for PIB systems-has been fundamentally constrained by irreversible phase transitions(PT)during the cycling process,manifesting as severe structural degradation and capacity fading.This review presents a transformative paradigm integrating machine learning(ML)with multiscale characterization to analyse the complex phase transition mechanisms in Mn-based cathodes.Through systematic ML-driven interrogation of structure-property relationships,we establish quantitative descriptors for phase stability and develop predictive models for transition dynamics.Furthermore,we highlight recent breakthroughs in cross-disciplinary approaches,enabling the rational design of PT-mitigated cathode architectures.By consolidating these insights into a unified knowledge framework,this work provides strategic guidelines for developing structurally robust Mn-based cathodes and outlines future research directions for next-generation PIB systems.
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supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
基金Project supported by the National Natural Science Foundation of China(22279025,21773048,52302119)the Fundamental Research Funds for the Central Universities(2023FRFK06005,HIT.NSRIF202204)。
文摘Cation segregation on cathode surfaces plays a key role in determining the activity and operational stability of solid oxide fuel cells(SOFCs).The double perovskite oxide PrBa_(0.8)Ca_(0.2)Co_(2)O_(5+δ)(PBCC)has been widely studied as an active cathode but still suffer from serious detrimental segregations.To enhance the cathode stability,a PBCC derived A-site medium-entropy Pr_(0.6)La_(0.1)Nd_(0.1)Sm_(0.1)Gd_(0.1)Ba_(0.8)Ca_(0.2)Co_(2)O_(5+δ)(ME-PBCC)oxide was prepared and its segregation behaviors were investigated under different conditions.Compared with initial PBCC oxide,the segregations of BaO and Co_(3)O_(4)on the surface of ME-PBCC material are significantly suppressed,especially for Co_(3)O_(4),which is attributed to its higher configuration entropy.Our results also confirm the improved electrochemical performance and structural stability of ME-PBCC material,enabling it as a promising cathode for SOFCs.
基金supported by the National Key R&D Program of China(No.2022YFB2404400)the National Natural Science Foundation of China(Nos.U23A20577,52372168,92263206 and 21975006)+1 种基金the“The Youth Beijing Scholars program”(No.PXM2021_014204_000023)the Beijing Natural Science Foundation(Nos.2222001 and KM202110005009).
文摘The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.
基金supported by the National Natural Science Foundation of China(52276204 and U22A20435)。
文摘The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.
基金supported by the National Key Research and Development Program of China(No.2021YFC3200700)the National Natural Science Foundation of China(No.52400010)+1 种基金the Science and Technology Commission of Shanghai Municipality(No.24ZR1472300)the Fundamental Research Funds for the Central Universities.
文摘Bisphenol A(BPA)is a pervasive endocrine disruptor that enters the environment through anthropogenic activities,posing significant risks to ecosystems and human health.Advanced oxidation processes(AOPs)are promising methods for the removal of organic microcontaminants in the environment.Biogenic manganese oxides(BMO)are reported as catalysts due to their transitionmetal nature,and are also readily generated bymanganeseoxidizing microorganisms in the natural environment,and therefore their roles and effects in AOPs-based environmental remediation should be investigated.However,biogenic ironmanganese oxides(BFMO)are actually generated rather than BMO due to the coexistence of ferrous ionswhich can be oxidized to iron oxides.Therefore,this study produced BFMO originating from a highly efficientmanganese-oxidizing fungus Cladosporium sp.XM01 and chose peroxymonosulfate(PMS)as a typical oxidant for the degradation of bisphenol A(BPA),a model organic micropollutant.Characterization results indicate that the formed BFMO was amorphouswith a lowcrystallinity.The BFMO/PMS system achieved a high degradation performance that 85%BPA was rapidly degraded within 60min,and therefore the contribution of BFMO cannot be ignored during PMS-based environmental remediation.Different from the findings of previous studies(mostly radicals and singlet oxygen),the degradationmechanism was first proven as a 100%electron-transfer pathway mediated by high-valence Mn under acidic conditions provided by PMS.The findings of this study provide new insights into the degradation mechanisms of pollutants using biogenic metal oxides in PMS activation and the contribution of their coexistence in AOPs-based environmental remediation.
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.
