To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical pr...The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.展开更多
Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materi...Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.展开更多
Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,...Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.展开更多
Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert...Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.展开更多
Electrocatalytic oxidation of glycerol for value-added chemicals is a superior strategy to utilize the excess glycerol produced in the biodiesel industry.Pd is one of the few active catalysts for alkaline glycerol oxi...Electrocatalytic oxidation of glycerol for value-added chemicals is a superior strategy to utilize the excess glycerol produced in the biodiesel industry.Pd is one of the few active catalysts for alkaline glycerol oxidation reaction(GOR);however,glycerol inevitably dissociates and converts to carbon dioxide on the Pd surface,which results in its low total Faradaic efficiency(FE)for high-value-added products.Herein,a series of Pd/C and Pd10Bix/C catalysts were synthesized to investigate the GOR pathway.The Pd10Bi3/C catalyst with optimal Bi content achieved an excellent GOR mass activity of 7.5±0.2 A mgPd−1 and an outstanding total FE of 90%±3%,which are much higher than those values on Pd/C(1.2±0.2 A mgPd−1 for mass activity and 63%±4%for total FE).Combined results of in-situ attenuated total reflection surface enhanced infrared absorption spectroscopy and density functional theory calculations show that Bi suppresses the dissociation of glycerol through the“shielding effect”of Bi to the adjacent Pd sites,which weakens the adsorption strength of GOR intermediates on those sites.This work provides a new insight into the GOR mechanism and puts forward a valid strategy for the rational design of catalysts to enable the transformation of glycerol into high-value-added products.展开更多
The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as ano...The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as anode materials for fuel cells.However,the exploration of trimetallic nanoflowers with porous architectures remains limited.In this study,we present a straightforward one-step solvothermal method for the synthesis of trimetallic Pd Cu Ni porous nanoflowers(PNFs).Leveraging several unique advantages,such as an open superstructure,high porosity,and enhanced electronic interactions among the trimetals,the resulting Pd Cu Ni PNFs demonstrate significantly improved electrochemical performance,with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction(EOR)and the ethylene glycol oxidation reaction(EGOR),respectively.Furthermore,the Pd Cu Ni PNFs exhibit optimized d-band centers and the most negative onset oxidation potential,indicating enhanced antitoxicity and stability.This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.展开更多
The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts rem...The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.展开更多
TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing Ti...TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Alzheimer’s disease(AD)is a complex neurodegenerative disorder associated with changes in inflammation,oxidative stress,and gut microbiota composition.Butyrolactone Ⅰ(BTL-Ⅰ),a fungal metabolite,has shown anti-infla...Alzheimer’s disease(AD)is a complex neurodegenerative disorder associated with changes in inflammation,oxidative stress,and gut microbiota composition.Butyrolactone Ⅰ(BTL-Ⅰ),a fungal metabolite,has shown anti-inflammatory,microbiota regulating,and memory-improving potentials in previous in vitro and AlCl3-induced zebrafish studies.However,its effects of memory-improving and gutbrain axis regulating on Aβ-induced mammalian AD models have not been explored.In this study,intragastric administrated BTL-Ⅰ ameliorated cognitive deficits related to recognition and spatial memory impaired by Aβ_(1-42)intracerebroventricular injection in mice.BTL-Ⅰ maintained gut microbiota balance by increasing the abundance of Blautia,Muribaculaceae,Bacteroides,Akkermansia,etc.,and decreasing CAG-352,Clostridia UCG-014,different Lachnospiraceae groups,etc.,and Firmicutes/Bacteroidota ratio and elevated the levels of short-chain fatty acids.Additionally,it alleviated intestinal oxidative stress,inflammatory responses,and pathological damage.Furthermore,BTL-I reversed Aβ_(1-42)-induced activation of microglia and astrocytes in the hippocampus and inhibited the elevated oxidative stress and proinflammatory cytokines in both plasma and brain.The correlation analysis between the regulated taxa and biomarkers supports the role of gut microbiota in adjusting inflammation,oxidative stress,and memory.In conclusion,BTL-I may serve as a valuable drug lead for treating Alzheimer’s disease by systematically inhibiting microbiota imbalance,inflammation,and oxidative stress along the gut-brain axis.展开更多
Oxidation resistance is a critical metric for assessing the high-temperature property of superalloys.Tra-ditional models are often constrained by the parabolic rate law,limiting their ability to simulate com-plex oxid...Oxidation resistance is a critical metric for assessing the high-temperature property of superalloys.Tra-ditional models are often constrained by the parabolic rate law,limiting their ability to simulate com-plex oxidation behavior.This study introduces a hybrid machine learning model that combines a one-dimensional convolutional neural network with a long short-term memory network to predict oxidation behavior with high accuracy(R^(2)=0.981)and smoothness.The model demonstrates improved predictive performance across various stages of oxidation,successfully fitting a wide range of oxidation kinetics and accurately estimating the activation energy for the Co-9W-9Al-0.12B alloy.It also identifies the critical Cr content range for the transition from internal to external oxidation in Co-based superalloys,which aligns well with experimental results and theoretical calculations.Although this study focuses on Co-based su-peralloys,the versatility extends its applicability to other superalloy systems,paving the way for future research in materials science.展开更多
This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by t...This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.展开更多
The abiotic oxidation of divalentmanganese(Mn(Ⅱ))and the formation of Mn oxides are important geochemical processes,which control the mobility and availability of Mn as well as element cycling and pollutant behavior ...The abiotic oxidation of divalentmanganese(Mn(Ⅱ))and the formation of Mn oxides are important geochemical processes,which control the mobility and availability of Mn as well as element cycling and pollutant behavior in soils.It was found that iron(oxyhydr)oxides can catalyze Mn(Ⅱ)oxidation,but the effects of the coexisting dissolved organic matter(DOM)molecules on the catalysis of different iron(oxyhydr)oxides for Mn(Ⅱ)oxidation are poorly understood.Herein,we investigated Mn(Ⅱ)oxidation under the impacts of the interactions between iron(oxyhydr)oxides(i.e.,ferrihydrite,goethite and hematite)and DOM molecules.Simultaneously,we elucidated the variations of DOM composition and properties.Our results indicated that the catalysis of iron(oxyhydr)oxides for Mn(Ⅱ)oxidation was significantly inhibited by DOM.Moreover,DOM had less inhibiting effect on the catalysis of ferrihydrite for Mn(Ⅱ)oxidation and the formation of Mn oxides(e.g.,hausmannite and buserite)relative to goethite and hematite,whichwas partially because of the higher electron transfer capacities of ferrihydrite.Meanwhile,DOM molecules with high nominal oxidation state of carbon(NOSC),molecular weight,unsaturation and aromaticity were selectively adsorbed and oxidized by Mn oxides,including the oxygenated phenols and polyphenols.The newly formed molecules mainly belonged to phenols depleted of oxygen and aliphatics.Furthermore,NOSC was a key molecular characteristic for controlling DOM composition during DOM adsorption and oxidation by Mn oxides when iron minerals were present.Overall,our research contributes to understanding Mn(Ⅱ)oxidation mechanisms under heterogeneous systems and behaviors of DOM molecules in the environment.展开更多
Nitrification,the process by which ammonia is oxidized to nitrite(ammonia oxidation,AO)and subsequently to nitrate(nitrite oxidation,NO),plays a critical role in the nitrogen cycle by linking the oxidized and reduced ...Nitrification,the process by which ammonia is oxidized to nitrite(ammonia oxidation,AO)and subsequently to nitrate(nitrite oxidation,NO),plays a critical role in the nitrogen cycle by linking the oxidized and reduced forms of nitrogen.This process consumes dissolved oxygen,releases protons,and produces the potent greenhouse gas nitrous oxide(N2O),rendering it highly relevant to various environmental challenges,especially in coastal seas with high anthropogenic nitrogen input.Despite its importance,research has predominantly focused on AO,with fewer studies simultaneously investigating ammonia oxidation rates(AOR)and nitrite oxidation rates(NOR).This study measured AOR and NOR using the 15N tracer technique in the Changjiang(Yangtze)River Estuary(CRE)during the summer of 2022,a season when bottom-water hypoxia occurred frequently.Overall,our findings showed that AOR exceeded NOR across different estuarine conditions.Specifically,higher ammonium and total suspended matter(TSM)concentrations significantly boosted AOR.Notably,despite lower TSM levels compared to previous studies,AOR remained high,suggesting that smaller particles may offer more surface area for ammonia-oxidizing microorganisms.In addition,surface productivity,indicated by the concentration of chlorophyll a(Chl a),was positively correlated with bottom-water nitrification and oxygen consumption.This suggested that increased surface productivity could enhance deep-water microbial nitrification,intensifying oxygen demand and promoting hypoxia,particularly during summer stratification when vertical oxygen replenishment was limited.These findings underscored the complex coupling between particle dynamics,primary production,and microbial nitrogen transformations,and offered important insights for hypoxia mitigation and estuarine ecosystem management.展开更多
Preferential oxidation of CO(CO-PROX)in H_(2)-rich streams is highly important for purifying the industrial grade H_(2)used in proton-exchange-membrane fuel cells(PEMFC),but it is still limited to a relatively narrow ...Preferential oxidation of CO(CO-PROX)in H_(2)-rich streams is highly important for purifying the industrial grade H_(2)used in proton-exchange-membrane fuel cells(PEMFC),but it is still limited to a relatively narrow operation temperature window.In this study,the trace amounts of Cu are used to modify a Pt/Al_(2)O_(3)catalyst.The introduced Cu_(2+)species are atomically anchored on Pt nanoparticles through strong electrostatic adsorption.展开更多
To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galv...To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galvanic replacement reaction between the initially prepared PdAg NTs and Pt ions.Due to the multilevel porous tree-like structure and the incorporation of low amounts of Pt,the electrocatalytic activity and stability of PtPdAg NTs are markedly enhanced,achieving 1.65 and 1.69 A·mg^(-1)Pt+Pd for the anodic reactions of formic acid oxidation(FAOR)and methanol oxidation(MOR)within DLFCs,surpassing the performance of PdAg NTs,as well as that of commercial Pt and Pd black.Density functional theory(DFT)calculations reveal that the addition of low amounts of Pt leads to an increase in the d-band center of PtPdAg NTs and lower the COads adsorption energy to-1.23 eV,enhancing the anti-CO toxicity properties optimally.This approach offers an effective means for designing low Pt catalysts as exceptional anodic electrocatalysts for direct liquid fuel cells.展开更多
The high-temperature oxidation resistance of AISI 321 stainless steel used in solar thermal power heat exchangers determines its service life.In this study,aluminizing and subsequent laser shock peening(LSP)treatments...The high-temperature oxidation resistance of AISI 321 stainless steel used in solar thermal power heat exchangers determines its service life.In this study,aluminizing and subsequent laser shock peening(LSP)treatments were employed to improve the high-temperature oxidation resistance of AISI 321 stainless steel at 620°C.These two treatments decreased the oxidation rate of AISI 321 steel.Specifically,the optimal oxidation resistance was observed in aluminized steel before oxidation for 144 h owing to the increased entropy of the LSP-treated specimen.After 144 h,LSP-treated steel achieved the best oxidation resistance because of the formation of a protectiveα-Al2O3film.Moreover,the large amount of subgrain boundaries formed on the aluminized layer of the LSP-treated samples could act as short-circuit paths for the outward diffusion of Al,facilitating the rapid nucleation ofα-Al2O3.Meanwhile,the aluminized layer could isolate the contact between the oxidation environment and matrix,thereby decreasing the oxidation rate.Furthermore,the minimum oxidation parabolic constant was calculated for LSP-treated steel(6.45787×10^(-14)),which was 69.18%and 36.36%that of aluminized and 321 steel,respectively,during the entire oxidation process.Therefore,the combination of aluminizing and LSP treatments can improve the high-temperature oxidation resistance of 321 stainless steel,providing a new idea for its surface treatment to achieve a long service life at high temperatures.展开更多
The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synth...The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.展开更多
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
基金supported by the Key R&D Program of Shandong Province,China(No.2025CXGC 010412)the National Key Research and Development Program of China(No.2022YFB3709300)the National Natural Science Foundation of China(No.U21A2048).
文摘The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.
文摘Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.
基金supported by the National Key Research and Development Program of China(2024YFA1612900)the National Natural Science Foundation of China(Grant No.52103365 and No.12375270)the Guangdong Innovative and Entrepreneurial Research Team Program,China(Grant No.2021ZT09L227).
文摘Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.
基金financially supported by the National Natural Science Foundation of China(22472199)Chinese Universities Scientific Fund(15055009)and Central University Guided Funds for Building World-Class Universities(Disciplines)and Advancing Characteristic Development.The authors extend their gratitude to Theoretical and Computational Chemistry Team(from Scientific Compass www.shiyanjia.com)for providing invaluable assistance.
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金support from the Australian Research Council(ARC)Linkage Project(No.LP230100166).
文摘Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.
基金supported by the National Natural Science Foundation of China(Grant number 22172112)and the Fundamental Research Funds for the Central Universities.
文摘Electrocatalytic oxidation of glycerol for value-added chemicals is a superior strategy to utilize the excess glycerol produced in the biodiesel industry.Pd is one of the few active catalysts for alkaline glycerol oxidation reaction(GOR);however,glycerol inevitably dissociates and converts to carbon dioxide on the Pd surface,which results in its low total Faradaic efficiency(FE)for high-value-added products.Herein,a series of Pd/C and Pd10Bix/C catalysts were synthesized to investigate the GOR pathway.The Pd10Bi3/C catalyst with optimal Bi content achieved an excellent GOR mass activity of 7.5±0.2 A mgPd−1 and an outstanding total FE of 90%±3%,which are much higher than those values on Pd/C(1.2±0.2 A mgPd−1 for mass activity and 63%±4%for total FE).Combined results of in-situ attenuated total reflection surface enhanced infrared absorption spectroscopy and density functional theory calculations show that Bi suppresses the dissociation of glycerol through the“shielding effect”of Bi to the adjacent Pd sites,which weakens the adsorption strength of GOR intermediates on those sites.This work provides a new insight into the GOR mechanism and puts forward a valid strategy for the rational design of catalysts to enable the transformation of glycerol into high-value-added products.
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as anode materials for fuel cells.However,the exploration of trimetallic nanoflowers with porous architectures remains limited.In this study,we present a straightforward one-step solvothermal method for the synthesis of trimetallic Pd Cu Ni porous nanoflowers(PNFs).Leveraging several unique advantages,such as an open superstructure,high porosity,and enhanced electronic interactions among the trimetals,the resulting Pd Cu Ni PNFs demonstrate significantly improved electrochemical performance,with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction(EOR)and the ethylene glycol oxidation reaction(EGOR),respectively.Furthermore,the Pd Cu Ni PNFs exhibit optimized d-band centers and the most negative onset oxidation potential,indicating enhanced antitoxicity and stability.This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
基金financially supported by the Sichuan Science and Technology Program(Grant No.2025NSFSC0139)the China Postdoctoral Science Foundation(Grant No.2023MD734228)+5 种基金The authors extend their gratitude to Ms.Zhou Yuke(from Scientific Compass www.shiyanjia.com)for providing invaluable assistance with the XPS analysis.ICN2 acknowledges funding from Generalitat de Catalunya 2021SGR00457This study is part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU(PRTR-C17.I1)by Generalitat de Catalunya(In-CAEM Project)The authors thank the support from the project AMaDE(PID2023-149158OB-C43)funded by MCIN/AEI/10.13039/501100011033/and by“ERDF A way of making Europe”,by the“European Union”.ICN2 is supported by the Severo Ochoa program from Spanish MCIN/AEI(Grant No.:CEX2021-001214-S)is funded by the CERCA Programme/Generalitat de Catalunya.Part of the present work has been performed in the framework of Universitat Autònoma de Barcelona Materials Science PhD program.JY has received funding from the CSC-UAB PhD scholarship program.ICN2 is founding member of e-DREAM[87].
文摘The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.
基金supported by the Original Exploratory Program of the National Natural Science Foundation of China(No.52450012)。
文摘TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金Supported by the Guangdong Provincial Natural Science Foundation(No.2022A1515010783)the Sustainable Development Program of Shenzhen Science and Technology Major Program(No.KCXFZ20240903093925033)+4 种基金the Guangdong Provincial Special Project in Science and Technology(No.2021A05240)the Special Project in Key Fields of Guangdong Provincial Higher Education Institutions(No.2021ZDZX2064)the Basic Research Project of Shenzhen Science and Technology Innovation Commission(No.JCYJ20220530162014032)the Zhanjiang Marine Youth Talent Innovation Project(No.2022E05010)the Program for Scientific Research Start-up Funds of Guangdong Ocean University(Nos.R18008,060302042201)。
文摘Alzheimer’s disease(AD)is a complex neurodegenerative disorder associated with changes in inflammation,oxidative stress,and gut microbiota composition.Butyrolactone Ⅰ(BTL-Ⅰ),a fungal metabolite,has shown anti-inflammatory,microbiota regulating,and memory-improving potentials in previous in vitro and AlCl3-induced zebrafish studies.However,its effects of memory-improving and gutbrain axis regulating on Aβ-induced mammalian AD models have not been explored.In this study,intragastric administrated BTL-Ⅰ ameliorated cognitive deficits related to recognition and spatial memory impaired by Aβ_(1-42)intracerebroventricular injection in mice.BTL-Ⅰ maintained gut microbiota balance by increasing the abundance of Blautia,Muribaculaceae,Bacteroides,Akkermansia,etc.,and decreasing CAG-352,Clostridia UCG-014,different Lachnospiraceae groups,etc.,and Firmicutes/Bacteroidota ratio and elevated the levels of short-chain fatty acids.Additionally,it alleviated intestinal oxidative stress,inflammatory responses,and pathological damage.Furthermore,BTL-I reversed Aβ_(1-42)-induced activation of microglia and astrocytes in the hippocampus and inhibited the elevated oxidative stress and proinflammatory cytokines in both plasma and brain.The correlation analysis between the regulated taxa and biomarkers supports the role of gut microbiota in adjusting inflammation,oxidative stress,and memory.In conclusion,BTL-I may serve as a valuable drug lead for treating Alzheimer’s disease by systematically inhibiting microbiota imbalance,inflammation,and oxidative stress along the gut-brain axis.
基金supported by the National Natural Science Foundation of China(Nos.52171107 and 52471004)the Industry-University-Research Cooperation Project of Hebei Based Universities and Shijiazhuang City(No.241791237A)the Funded by Science and Technology Project of Hebei Education De-partment(No.QN2023155).
文摘Oxidation resistance is a critical metric for assessing the high-temperature property of superalloys.Tra-ditional models are often constrained by the parabolic rate law,limiting their ability to simulate com-plex oxidation behavior.This study introduces a hybrid machine learning model that combines a one-dimensional convolutional neural network with a long short-term memory network to predict oxidation behavior with high accuracy(R^(2)=0.981)and smoothness.The model demonstrates improved predictive performance across various stages of oxidation,successfully fitting a wide range of oxidation kinetics and accurately estimating the activation energy for the Co-9W-9Al-0.12B alloy.It also identifies the critical Cr content range for the transition from internal to external oxidation in Co-based superalloys,which aligns well with experimental results and theoretical calculations.Although this study focuses on Co-based su-peralloys,the versatility extends its applicability to other superalloy systems,paving the way for future research in materials science.
基金supported by the Petrochemical Joint Funds of NSFC-CNPC (U1362202)the Postgraduate Innovation Project of China University of Petroleum (East China) (YCXJ2016030)~~
文摘This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.
基金supported by the National Natural Science Foundation of China(Nos.42207309 and 22306087)the Natural Science Foundation of Hunan Province(Nos.2022JJ40369 and 2023JJ40547)the Program for Education Department of Hunan Province,China(No.21B0405).
文摘The abiotic oxidation of divalentmanganese(Mn(Ⅱ))and the formation of Mn oxides are important geochemical processes,which control the mobility and availability of Mn as well as element cycling and pollutant behavior in soils.It was found that iron(oxyhydr)oxides can catalyze Mn(Ⅱ)oxidation,but the effects of the coexisting dissolved organic matter(DOM)molecules on the catalysis of different iron(oxyhydr)oxides for Mn(Ⅱ)oxidation are poorly understood.Herein,we investigated Mn(Ⅱ)oxidation under the impacts of the interactions between iron(oxyhydr)oxides(i.e.,ferrihydrite,goethite and hematite)and DOM molecules.Simultaneously,we elucidated the variations of DOM composition and properties.Our results indicated that the catalysis of iron(oxyhydr)oxides for Mn(Ⅱ)oxidation was significantly inhibited by DOM.Moreover,DOM had less inhibiting effect on the catalysis of ferrihydrite for Mn(Ⅱ)oxidation and the formation of Mn oxides(e.g.,hausmannite and buserite)relative to goethite and hematite,whichwas partially because of the higher electron transfer capacities of ferrihydrite.Meanwhile,DOM molecules with high nominal oxidation state of carbon(NOSC),molecular weight,unsaturation and aromaticity were selectively adsorbed and oxidized by Mn oxides,including the oxygenated phenols and polyphenols.The newly formed molecules mainly belonged to phenols depleted of oxygen and aliphatics.Furthermore,NOSC was a key molecular characteristic for controlling DOM composition during DOM adsorption and oxidation by Mn oxides when iron minerals were present.Overall,our research contributes to understanding Mn(Ⅱ)oxidation mechanisms under heterogeneous systems and behaviors of DOM molecules in the environment.
基金The Hainan Provincial Natural Science Foundation of China under contract No.423RC438the Major Science and Technology Plan of Hainan Province under contract No.ZDKJ2021008+1 种基金the National Natural Science Foundation of China under contract Nos 42406041,92251306,42266002,41806062,and 42476032the Open Research Fund of Guangdong Provincial Key Laboratory of Marine Disaster Prediction and Prevention under contract No.GPKLMD2023004.
文摘Nitrification,the process by which ammonia is oxidized to nitrite(ammonia oxidation,AO)and subsequently to nitrate(nitrite oxidation,NO),plays a critical role in the nitrogen cycle by linking the oxidized and reduced forms of nitrogen.This process consumes dissolved oxygen,releases protons,and produces the potent greenhouse gas nitrous oxide(N2O),rendering it highly relevant to various environmental challenges,especially in coastal seas with high anthropogenic nitrogen input.Despite its importance,research has predominantly focused on AO,with fewer studies simultaneously investigating ammonia oxidation rates(AOR)and nitrite oxidation rates(NOR).This study measured AOR and NOR using the 15N tracer technique in the Changjiang(Yangtze)River Estuary(CRE)during the summer of 2022,a season when bottom-water hypoxia occurred frequently.Overall,our findings showed that AOR exceeded NOR across different estuarine conditions.Specifically,higher ammonium and total suspended matter(TSM)concentrations significantly boosted AOR.Notably,despite lower TSM levels compared to previous studies,AOR remained high,suggesting that smaller particles may offer more surface area for ammonia-oxidizing microorganisms.In addition,surface productivity,indicated by the concentration of chlorophyll a(Chl a),was positively correlated with bottom-water nitrification and oxygen consumption.This suggested that increased surface productivity could enhance deep-water microbial nitrification,intensifying oxygen demand and promoting hypoxia,particularly during summer stratification when vertical oxygen replenishment was limited.These findings underscored the complex coupling between particle dynamics,primary production,and microbial nitrogen transformations,and offered important insights for hypoxia mitigation and estuarine ecosystem management.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3504200)the National Natural Science Foundation of China(Nos.U21A20326 and 22376063)+4 种基金the fund of the National Engineering Laboratory for Mobile Source Emission Control Technology(No.NELMS2020A05)the Fundamental Research Funds for the Central Universitiesthe funding received from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 897197.Y.L.(CSC No.202006740085)is grateful for thegrant from the China Scholarship Councilthe ICREA Academia program and grants MICINN/FEDER PID2021124572OB-C31 and GC 2021 SGR 01061part of Maria de Maeztu Units of Excellence Programme CEX2023-001300-M/funded by MCIN/AEI/https://doi.org/10.13039/501100011033
文摘Preferential oxidation of CO(CO-PROX)in H_(2)-rich streams is highly important for purifying the industrial grade H_(2)used in proton-exchange-membrane fuel cells(PEMFC),but it is still limited to a relatively narrow operation temperature window.In this study,the trace amounts of Cu are used to modify a Pt/Al_(2)O_(3)catalyst.The introduced Cu_(2+)species are atomically anchored on Pt nanoparticles through strong electrostatic adsorption.
基金supported by the National Natural Science Foundation of China(Nos.22202104,22279062,22232004 and 22072067)the Natural Science Foundation of Jiangsu Province(No.BK20220933)Shuangchuang Doctor Plan of Jiangsu Province(No.JSSCBS20220273).
文摘To efficiently diminish the Pt consumption while concurrently enhancing the anodic reaction kinetics,a straightforward synthesis for PtPdAg nanotrees(NTs)with exceedingly low Pt content is presented,utilizing the galvanic replacement reaction between the initially prepared PdAg NTs and Pt ions.Due to the multilevel porous tree-like structure and the incorporation of low amounts of Pt,the electrocatalytic activity and stability of PtPdAg NTs are markedly enhanced,achieving 1.65 and 1.69 A·mg^(-1)Pt+Pd for the anodic reactions of formic acid oxidation(FAOR)and methanol oxidation(MOR)within DLFCs,surpassing the performance of PdAg NTs,as well as that of commercial Pt and Pd black.Density functional theory(DFT)calculations reveal that the addition of low amounts of Pt leads to an increase in the d-band center of PtPdAg NTs and lower the COads adsorption energy to-1.23 eV,enhancing the anti-CO toxicity properties optimally.This approach offers an effective means for designing low Pt catalysts as exceptional anodic electrocatalysts for direct liquid fuel cells.
基金Supported by National Natural Science Foundation of China(Grant Nos.52075048,51675058,12232004)Hunan Provincial Excellent Youth Project of the Education Department(Grant No.21B0304)+2 种基金Natural Science Foundation of Hunan Province(Grant No.2023JJ30025)Science and Technology Innovation Program of Hunan Province(Grant No.2023RC1058)Scientific Research Innovation Project for Graduate Student of Changsha University of Science and Technology(Grant No.CLSJCX22096)。
文摘The high-temperature oxidation resistance of AISI 321 stainless steel used in solar thermal power heat exchangers determines its service life.In this study,aluminizing and subsequent laser shock peening(LSP)treatments were employed to improve the high-temperature oxidation resistance of AISI 321 stainless steel at 620°C.These two treatments decreased the oxidation rate of AISI 321 steel.Specifically,the optimal oxidation resistance was observed in aluminized steel before oxidation for 144 h owing to the increased entropy of the LSP-treated specimen.After 144 h,LSP-treated steel achieved the best oxidation resistance because of the formation of a protectiveα-Al2O3film.Moreover,the large amount of subgrain boundaries formed on the aluminized layer of the LSP-treated samples could act as short-circuit paths for the outward diffusion of Al,facilitating the rapid nucleation ofα-Al2O3.Meanwhile,the aluminized layer could isolate the contact between the oxidation environment and matrix,thereby decreasing the oxidation rate.Furthermore,the minimum oxidation parabolic constant was calculated for LSP-treated steel(6.45787×10^(-14)),which was 69.18%and 36.36%that of aluminized and 321 steel,respectively,during the entire oxidation process.Therefore,the combination of aluminizing and LSP treatments can improve the high-temperature oxidation resistance of 321 stainless steel,providing a new idea for its surface treatment to achieve a long service life at high temperatures.
文摘The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.
