Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The p...Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEAM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and mille TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test. Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.展开更多
In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of...In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of ZK60 Mg alloy after single MPO and HCPEB＋MPO compounded treatment were investigated by SEM. The results showed that the density of the ceramic layer of HCPEB＋MPO-treated ZK60 Mg alloy was improved and defects were reduced compared to that under MPO treatment alone. Surface modified layer of ZK60 Mg alloys treated by HCPEB＋MPO was divided into three zones, namely the top loose ceramic zone, middle compact zone and inside HCPEB-induced melted zone. Corrosion resistance of ZK60 Mg alloy before and after the compounded surface modification was measured in a solution of 3.5% NaCl by potentiodynamic polarization curves. It was found that the corrosion current density of ZK60 Mg alloys could be reduced by about three orders of magnitude, from 311μA/cm^2 of the original sample to 0.2μA/cm^2 of the HCPEB＋MPO-treated sample. This indicates the great application potential of the HCPEB＋MPO compounded surface modification technology in improving the corrosion resistance of ZK60 Mg alloys in the future.展开更多
Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffr...Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction （XRD） and the scanning electron microscopy （SEM）, respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing： after 20 min, the ceramics coatings are composed of α-Al2O3, 7-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount ofAl2O3.展开更多
Composite coatings were obtained on A3 steel by hot dipping aluminum(HDA) at 720 ℃ for 6 min and micro-plasma oxidation(MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure...Composite coatings were obtained on A3 steel by hot dipping aluminum(HDA) at 720 ℃ for 6 min and micro-plasma oxidation(MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure of composite coatings were studied by means of XRD, SEM and EDS. The results show that the composite coatings obtained through HDA/MPO on A3 steel consist of four layers. From the surface to the substrate, the layer is loose Al2O3 ceramic, compact Al2O3 ceramic, Al and FeAl intermetallic compound layer in turn. The adhesions among all the layers are strengthened because the ceramic layer formed at the Al surface originally, FeAl intermetallic compound layer and substrate are combined in metallurgical form through mutual diffusion during HDA process.Initial experiment results disclose that the anti-corrosion performance and wear resistance of composite coating are obviously improved through HDA/MPO treatment.展开更多
Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO2 solution. The phase composition was studied by XRD. And the electrochemical imped...Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO2 solution. The phase composition was studied by XRD. And the electrochemical impedance spectra (EIS) of the coatings were measured to study the structure of the coatings, combined with the surface morphology. Using the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and meanwhile fitting values of equivalent element were obtained. The results show that the coating is composed of Al2 TiO5, α-Al2O3 and rutile TiO2, of which Al2 TiO5 is the main crystalline. Increasing the MPO time, the contents of Al2TiO5, rutile TiO2 and α-Al2O3 in the surface of the coating increase. And the EIS analysis and the surface morphology of the coatings illustrates the double-layer structure of the coatings, and the outer layer is loosen and the inner layer is compact. With the increase of the oxidizing time, the surface coarse degree of the coatings and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coating is improved.展开更多
Microporous titanium dioxide thin films have been fabricated on titanium plates by the micro-plasma oxidation method with the electrolyte of Na3PO4+Na2B4O7.The influence of V5+ions addition in the electrolyte on the p...Microporous titanium dioxide thin films have been fabricated on titanium plates by the micro-plasma oxidation method with the electrolyte of Na3PO4+Na2B4O7.The influence of V5+ions addition in the electrolyte on the photocatalytic activities was investigated.A kind of typical textile industry pollutant(methylene blue)was used to evaluate the photo-catalytic activity of the films.The results showed that this activity of the films had been improved by adding V5+ions into the electrolyte solution.The removal of methylene blue reaches 90%for 60 min when V5+ions addition concentrate is 0.3 g/L.X-ray diffraction,scanning electron microscopy and atomic force microscopy techniques were applied to characterize the modified films.Experimental results show that the improvement in activity was related to the forming of titanium dioxide lattice distortion,which could accept more photoexcitated holes and produce more strong surface free radicals to oxidate adsorptive molecules.展开更多
Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on Al, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared fo...Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on Al, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar MPO in NaAlO2 solution. The phase composition, morphology and the element distribution of the coatings were studied by XRD, SEM and JEOL SUPERPROBE 733 electric probe, respectively. Electrochemical Impedance Spectra (EIS) of the coatings were measured to study the structure character of the coatings. Through the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and the fitting values of equivalent element were calculated. The coating is mainly composed of Al2TiO5, a-A12O3 and rutile TiO2. The content of Ti element in the coating is less than that of substrate; its distribution is relatively uniform, and Ti in the outer layer is less than that in the inner layer. The content of Al in the coating is more than that of substrate, and its distribution is not even: Al in the middle part is more than that on both sides of the coating; And the EIS analysis has illustrated the double-layer structure of the coatings, and the outside layer is loosen and the inner layer compact; with the increase of the oxidizing time, the surface roughness of the coatings, and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coatings are improved.展开更多
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
Carbon fiber-reinforced carbon aerogel(C/CA)composites are one of the most promising candidates for applications requiring both thermal insulation and load bearing capabilities.The preparation of anti-oxidation coatin...Carbon fiber-reinforced carbon aerogel(C/CA)composites are one of the most promising candidates for applications requiring both thermal insulation and load bearing capabilities.The preparation of anti-oxidation coatings on C/CA to address its susceptibility to oxidation is a feasible approach to promote its application in oxidative environments.However,the currently reported coatings on C/CA mainly focus on improving the ablation performance and coating preparation process typically necessitating high-temperature heat treatment.This procedure can increase its thermal conductivity and reduce its thermal insulation ability.In this study,a series of ceramic-resin coatings were fabricated on C/CA through a simple slurry brushing-drying approach at room temperature.The effects of phenolic resin content on the coating structure,residual stress,thermal shock,and oxidation behaviors were investigated.Due to the adhesive properties and curing-induced shrinkage,the PR-7.5 coating(containing 7.5%(in mass)phenolic resin in the slurry)exhibits bonding strength close to fracture strength of the substrate and residual compressive stress of 0.853 GPa,which is beneficial for resisting thermal shock cracking.However,excessive resin content(PR-10.0 containing 10.0%(in mass)phenolic resin in the slurry)induces tensile stress due to uneven curing shrinkage,thereby leading to thermal shock cracking.Meanwhile,oxidation tests reveal significantly reduced weight losses for PR-7.5(17.46%at 800℃/100 min,8.15%at 1000℃/120 min,3.15%at 1200℃/120 min)versus uncoated C/CA’s 44.60%loss at 800℃/20 min.This work provides a brand-new and simple approach to improving the anti-oxidation performance of C/CA and expands its application in mild oxidative environments.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
To elucidate the accelerated degradation mechanisms of metallic interconnects in operational solid oxide fuel cells,the oxidation behavior of FSS430 ferritic stainless steel under the coupling of simultaneous electric...To elucidate the accelerated degradation mechanisms of metallic interconnects in operational solid oxide fuel cells,the oxidation behavior of FSS430 ferritic stainless steel under the coupling of simultaneous electrical current and high-temperature exposure is investigated.Isothermal thermogravimetric analysis was employed to quantify oxidation kinetics,complemented by microstructural characterization using X-ray diffraction,scanning electron microscopy with energy-dispersive spectroscopy and transmission electron microscopy.Experimental results demonstrate that the applied current dramatically enhances oxidation rates,increasing specific mass gain from 0.25 mg/cm^(2)(0 A/cm^(2))to 5.20 mg/cm^(2)(0.2 A/cm^(2))and oxide scale thickness from 1.87 to 15.62μm after 200 h.This acceleration originates from current-induced electromigration forces that promote cationic transport through the oxide layer.The quantitative relationships between current density and oxidation parameters are established,enabling predictive modeling of interconnector degradation in solid oxide fuel cell(SOFC)systems.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
Ethylene(C_(2)H_(4))in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a...Ethylene(C_(2)H_(4))in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a key precursor of PM_(2.5).In this study,a novel MgO-supported Ag-Cu bimetallic catalyst was designed and investigated using density functional theory(DFT).The effects of Ag and Cu loading on the geometric structure,stability,and reactant adsorption characteristics of the catalyst were analyzed,and the catalytic oxidation pathways of C_(2)H_(4)over AgCu-MgO was elucidated.The results indicate that loading Ag significantly enhances the adsorption of C_(2)H_(4).The incorporation of Cu into Ag-MgO to form a AgCu-MgO bimetallic catalyst(dual atom catalyst,DACS)further improves the oxidative activity toward C_(2)H_(4).Based on the binding energies of the Ag and Cu bimetallic sites and the adsorption energies of C_(2)H_(4)and O_(2),three representative configurations were selected for detailed reaction pathway analysis.Among them,Configuration 6 of AgCu-MgO exhibited the highest catalytic oxidation performance.This study provides new atomic-scale insights for the rational design of efficient catalysts targeting olefinic pollutants in automotive emissions and offers valuable guidance for advancing exhaust after-treatment technologies.展开更多
Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents ...Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents a novel perovskite oxide that exhibits enhanced catalytic activity and superior durability for toluene combustion at reduced temperatures.This improvement is achieved by phosphorus doping at the B-site of LaCoO_(3-δ)(LC)perovskite oxide,followed by post-synthesis acid etching for a proper time.The resulting catalyst demonstrates increased specific surface area,higher total pore volume,and enhanced oxygen vacancy concentration both in the bulk and on the surface.Additionally,the activity of surface lattice oxygen species is significantly improved,leading to enhanced catalytic performance in toluene combustion.Notably,the optimized catalyst shows an exceptionally low activation energy(E_(a))of 49.3 kJ mol^(-1),with a T90 reduction of over 214℃compared to the phosphorus doped LC and 190℃compared to pristine LC.Phosphorus doping plays a main role in significantly improving the long-term durability,particularly in the presence of CO_(2)and H_(2)O,while acid etching boosts the catalytic activity.This work introduces a rational and innovative strategy for optimizing VOC oxidation by improving the structure and surface chemical states of perovskite catalysts.展开更多
Severe internal oxidation formed in advanced high-strength steels(AHSSs)during the hot-rolled coiling process compromises subsequent cold rolling and galvanizing processes.Herein,we report how Sn microalloying governs...Severe internal oxidation formed in advanced high-strength steels(AHSSs)during the hot-rolled coiling process compromises subsequent cold rolling and galvanizing processes.Herein,we report how Sn microalloying governs internal oxidation behavior and modulates iron oxide phase transition process.Sn addition significantly reduces the depth of grain boundaries oxidation and the area of internal oxidation,as well as retards the process of oxide scale transformation.Sn preferentially segregates at the iron oxide/substrate interface,forming a diffusion barrier that suppresses outward diffusion of alloying elements and inward oxygen transport.Concurrently,Sn enrichment at grain boundaries obstructs short-circuit oxygen diffusion pathways,significantly reducing the depth of oxidation at the grain boundaries.Furthermore,Sn segregation decreases the interfacial oxygen chemical potential and oxygen availability for selective oxidation reaction.The strategic incorporation of surface-active elements has emerged as a viable metallurgical approach to reduce internal oxidation in hot-rolled coils for AHSS applications.展开更多
Peroxymonosulfate(PMS)-based Fenton-like technologies have been increasingly employed in the upgrading of biomass,but they are commonly limited by the trade-off between conversion and selectivity due to the short life...Peroxymonosulfate(PMS)-based Fenton-like technologies have been increasingly employed in the upgrading of biomass,but they are commonly limited by the trade-off between conversion and selectivity due to the short lifetime of reactive oxygen species(ROS)and uncontrollable oxidation pathways.Herein,we show that single-atom Co supported on carbon nitride enables the high-valent-oxo cobalt species(Co(IV)O)mediated oxidation of glucose into value-added products in acetonitrile.This photocatalytic Fenton-like system achieved an overall selectivity of gluconic acid,glucaric acid,arabinose,and formic acid up to 90.3%at glucose conversion of 69.6%,outperforming most of previously reported catalytic systems.The small amount(0.72 wt%)of single-atom Co could not only elevate the optical absorption and the efficiency of photo-generated carriers separation but also induce the efficient generation of Co(IV)O with reduced ROS to enable efficient and selective oxidation.These findings prove the great promise of high-valent metal-oxo species in biomass conversions.展开更多
A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-cat...A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-catalysis plays a central role among others catalysis systems own to its longstanding history. While a chemodivergent reaction based on organo-catalysis, especially photocatalysis, is rather limited as these concepts were only prevalent in the last two decades. With the ever-increasing importance of photocatalysis, a chemodivergent reaction based on such an activation pathway would be a meaningful direction. Herein, an efficient chemodivergent strategy for visible light photocatalysis is developed. By employing commercially available Rose Bengal as a photocatalyst, naturally occurring Viridicatin and its derivatives can be transformed into three different types of products through switchable single electron transfer (SET) or energy transfer (EnT) processes. Mechanistic studies have revealed that the oxygen as a reactive center, rather than carbon, is favored, which accounts for the first example of a C–O homo-dimerization product.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
The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and slugg...The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and sluggish oxygen evolution reaction kinetics.This work overcomes those challenges through a synergistic strategy that co-designs the hematite architecture and the surface reaction pathway.We introduce a textured and hierarchically porous Ti-doped Fe_(2)O_(3)(tp-Fe_(2)O_(3))photoanode,synthesized via multi-cycle growth and flame annealing method.This unique architecture features a high texture(110),enlarged surface area,and hierarchically porous structure,which enable significantly enhanced bulk charge transport and interfacial charge transfer compared to typical nanorod Ti-doped Fe_(2)O_(3)(nr-Fe_(2)O_(3)).As a result,the tp-Fe_(2)O_(3)photoanode achieves a photocurrent density of 3.1 mA cm^(-2)at 1.23 V vs.RHE with exceptional stability over 105 h,notably without any co-catalyst.By replacing the OER with the hydrazine oxidation reaction,the photocurrent further reaches a record-high level of 7.1 mA cm^(-2)at 1.23 V_(RHE).Finally,when we integrate the tp-Fe_(2)O_(3)with a commercial Si solar cell,it achieves a solar-to-hydrogen efficiency of 8.7%-the highest reported value for any Fe_(2)O_(3)-based PVtandem system.This work provides critical insights into rational Fe_(2)O_(3)photoanode design and highlights the potential of hydrazine as an efficient alternative anodic reaction,enabling waste valorization.展开更多
基金the National Natural Science Foundation of China (No. 50171026)the Natu-ral Science Foundation of Heilongjiang Province, China (No. E2007-36).
文摘Ceramic coatings were prepared on Ti-6Al-4V alloy in NaAlO2 solution by micro-plasma oxidation （MPO）. The salt spray tests of the coated samples and the substrates were carded out in a salt spray test machine. The phase composition and surface morphology of the coatings were investigated by XRD and SEAM. Severe corrosion occurred on the substrate surface, while there were no obvious corrosion phenomena on the coated samples. The coatings were composed of Al2TiO5 and a little α-Al2O3 and mille TiO2, and the salt spray test did not change the composition of the coatings. The weight loss rate of the coatings decreased with increasing MPO time because of the increase in density and thickness of the coatings. The surface morphology of the coatings was influenced by salt spray corrosion test. Among the coated samples, the coating prepared for 2 h has the best corrosion resistance under salt spray test.
基金supported by Liaoning BaiQianWan Talents Program of China (No. 2008921028)Doctoral Fund of Ministry of Education of China (No. 200801451082)
文摘In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of ZK60 Mg alloy after single MPO and HCPEB＋MPO compounded treatment were investigated by SEM. The results showed that the density of the ceramic layer of HCPEB＋MPO-treated ZK60 Mg alloy was improved and defects were reduced compared to that under MPO treatment alone. Surface modified layer of ZK60 Mg alloys treated by HCPEB＋MPO was divided into three zones, namely the top loose ceramic zone, middle compact zone and inside HCPEB-induced melted zone. Corrosion resistance of ZK60 Mg alloy before and after the compounded surface modification was measured in a solution of 3.5% NaCl by potentiodynamic polarization curves. It was found that the corrosion current density of ZK60 Mg alloys could be reduced by about three orders of magnitude, from 311μA/cm^2 of the original sample to 0.2μA/cm^2 of the HCPEB＋MPO-treated sample. This indicates the great application potential of the HCPEB＋MPO compounded surface modification technology in improving the corrosion resistance of ZK60 Mg alloys in the future.
基金National Natural Science Foundation of China (50171026)
文摘Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction （XRD） and the scanning electron microscopy （SEM）, respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing： after 20 min, the ceramics coatings are composed of α-Al2O3, 7-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount ofAl2O3.
基金Project(50071066) supported by the National Natural Science Foundation of China Project(B41) supported by the Doctoral Foundation of Yanshan University, China Project(YDJJ: 0169) supported by the Science & Technology Foundation of Yanshan University, China
文摘Composite coatings were obtained on A3 steel by hot dipping aluminum(HDA) at 720 ℃ for 6 min and micro-plasma oxidation(MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure of composite coatings were studied by means of XRD, SEM and EDS. The results show that the composite coatings obtained through HDA/MPO on A3 steel consist of four layers. From the surface to the substrate, the layer is loose Al2O3 ceramic, compact Al2O3 ceramic, Al and FeAl intermetallic compound layer in turn. The adhesions among all the layers are strengthened because the ceramic layer formed at the Al surface originally, FeAl intermetallic compound layer and substrate are combined in metallurgical form through mutual diffusion during HDA process.Initial experiment results disclose that the anti-corrosion performance and wear resistance of composite coating are obviously improved through HDA/MPO treatment.
基金Project (50171026) supported by the National Natural Science Foundation of China
文摘Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO2 solution. The phase composition was studied by XRD. And the electrochemical impedance spectra (EIS) of the coatings were measured to study the structure of the coatings, combined with the surface morphology. Using the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and meanwhile fitting values of equivalent element were obtained. The results show that the coating is composed of Al2 TiO5, α-Al2O3 and rutile TiO2, of which Al2 TiO5 is the main crystalline. Increasing the MPO time, the contents of Al2TiO5, rutile TiO2 and α-Al2O3 in the surface of the coating increase. And the EIS analysis and the surface morphology of the coatings illustrates the double-layer structure of the coatings, and the outer layer is loosen and the inner layer is compact. With the increase of the oxidizing time, the surface coarse degree of the coatings and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coating is improved.
基金Education Department of Liaoning Province National Science Foundation(2008615)
文摘Microporous titanium dioxide thin films have been fabricated on titanium plates by the micro-plasma oxidation method with the electrolyte of Na3PO4+Na2B4O7.The influence of V5+ions addition in the electrolyte on the photocatalytic activities was investigated.A kind of typical textile industry pollutant(methylene blue)was used to evaluate the photo-catalytic activity of the films.The results showed that this activity of the films had been improved by adding V5+ions into the electrolyte solution.The removal of methylene blue reaches 90%for 60 min when V5+ions addition concentrate is 0.3 g/L.X-ray diffraction,scanning electron microscopy and atomic force microscopy techniques were applied to characterize the modified films.Experimental results show that the improvement in activity was related to the forming of titanium dioxide lattice distortion,which could accept more photoexcitated holes and produce more strong surface free radicals to oxidate adsorptive molecules.
文摘Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on Al, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar MPO in NaAlO2 solution. The phase composition, morphology and the element distribution of the coatings were studied by XRD, SEM and JEOL SUPERPROBE 733 electric probe, respectively. Electrochemical Impedance Spectra (EIS) of the coatings were measured to study the structure character of the coatings. Through the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and the fitting values of equivalent element were calculated. The coating is mainly composed of Al2TiO5, a-A12O3 and rutile TiO2. The content of Ti element in the coating is less than that of substrate; its distribution is relatively uniform, and Ti in the outer layer is less than that in the inner layer. The content of Al in the coating is more than that of substrate, and its distribution is not even: Al in the middle part is more than that on both sides of the coating; And the EIS analysis has illustrated the double-layer structure of the coatings, and the outside layer is loosen and the inner layer compact; with the increase of the oxidizing time, the surface roughness of the coatings, and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coatings are improved.
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National Natural Science Foundation of China(52272075,52472053)Research Fund of Youth Innovation Promotion Association of CAS,China(2021190)Defense Industrial Technology Development Program(JCKY2021130B007)。
文摘Carbon fiber-reinforced carbon aerogel(C/CA)composites are one of the most promising candidates for applications requiring both thermal insulation and load bearing capabilities.The preparation of anti-oxidation coatings on C/CA to address its susceptibility to oxidation is a feasible approach to promote its application in oxidative environments.However,the currently reported coatings on C/CA mainly focus on improving the ablation performance and coating preparation process typically necessitating high-temperature heat treatment.This procedure can increase its thermal conductivity and reduce its thermal insulation ability.In this study,a series of ceramic-resin coatings were fabricated on C/CA through a simple slurry brushing-drying approach at room temperature.The effects of phenolic resin content on the coating structure,residual stress,thermal shock,and oxidation behaviors were investigated.Due to the adhesive properties and curing-induced shrinkage,the PR-7.5 coating(containing 7.5%(in mass)phenolic resin in the slurry)exhibits bonding strength close to fracture strength of the substrate and residual compressive stress of 0.853 GPa,which is beneficial for resisting thermal shock cracking.However,excessive resin content(PR-10.0 containing 10.0%(in mass)phenolic resin in the slurry)induces tensile stress due to uneven curing shrinkage,thereby leading to thermal shock cracking.Meanwhile,oxidation tests reveal significantly reduced weight losses for PR-7.5(17.46%at 800℃/100 min,8.15%at 1000℃/120 min,3.15%at 1200℃/120 min)versus uncoated C/CA’s 44.60%loss at 800℃/20 min.This work provides a brand-new and simple approach to improving the anti-oxidation performance of C/CA and expands its application in mild oxidative environments.
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.
基金supported by Natural Science Foundation of Wuhan(2024040701010051)Natural Science Foundation of Hubei(2023AFB111)and National Natural Science Foundation of China(52401108).
文摘To elucidate the accelerated degradation mechanisms of metallic interconnects in operational solid oxide fuel cells,the oxidation behavior of FSS430 ferritic stainless steel under the coupling of simultaneous electrical current and high-temperature exposure is investigated.Isothermal thermogravimetric analysis was employed to quantify oxidation kinetics,complemented by microstructural characterization using X-ray diffraction,scanning electron microscopy with energy-dispersive spectroscopy and transmission electron microscopy.Experimental results demonstrate that the applied current dramatically enhances oxidation rates,increasing specific mass gain from 0.25 mg/cm^(2)(0 A/cm^(2))to 5.20 mg/cm^(2)(0.2 A/cm^(2))and oxide scale thickness from 1.87 to 15.62μm after 200 h.This acceleration originates from current-induced electromigration forces that promote cationic transport through the oxide layer.The quantitative relationships between current density and oxidation parameters are established,enabling predictive modeling of interconnector degradation in solid oxide fuel cell(SOFC)systems.
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 Natural Science Foundation of China Project(22362018)the Yunnan Fundamental Research Projects(202401AS070102)。
文摘Ethylene(C_(2)H_(4))in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a key precursor of PM_(2.5).In this study,a novel MgO-supported Ag-Cu bimetallic catalyst was designed and investigated using density functional theory(DFT).The effects of Ag and Cu loading on the geometric structure,stability,and reactant adsorption characteristics of the catalyst were analyzed,and the catalytic oxidation pathways of C_(2)H_(4)over AgCu-MgO was elucidated.The results indicate that loading Ag significantly enhances the adsorption of C_(2)H_(4).The incorporation of Cu into Ag-MgO to form a AgCu-MgO bimetallic catalyst(dual atom catalyst,DACS)further improves the oxidative activity toward C_(2)H_(4).Based on the binding energies of the Ag and Cu bimetallic sites and the adsorption energies of C_(2)H_(4)and O_(2),three representative configurations were selected for detailed reaction pathway analysis.Among them,Configuration 6 of AgCu-MgO exhibited the highest catalytic oxidation performance.This study provides new atomic-scale insights for the rational design of efficient catalysts targeting olefinic pollutants in automotive emissions and offers valuable guidance for advancing exhaust after-treatment technologies.
基金support from the National Key Research and Development Program of China(Project No.2018YFB1502903).
文摘Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents a novel perovskite oxide that exhibits enhanced catalytic activity and superior durability for toluene combustion at reduced temperatures.This improvement is achieved by phosphorus doping at the B-site of LaCoO_(3-δ)(LC)perovskite oxide,followed by post-synthesis acid etching for a proper time.The resulting catalyst demonstrates increased specific surface area,higher total pore volume,and enhanced oxygen vacancy concentration both in the bulk and on the surface.Additionally,the activity of surface lattice oxygen species is significantly improved,leading to enhanced catalytic performance in toluene combustion.Notably,the optimized catalyst shows an exceptionally low activation energy(E_(a))of 49.3 kJ mol^(-1),with a T90 reduction of over 214℃compared to the phosphorus doped LC and 190℃compared to pristine LC.Phosphorus doping plays a main role in significantly improving the long-term durability,particularly in the presence of CO_(2)and H_(2)O,while acid etching boosts the catalytic activity.This work introduces a rational and innovative strategy for optimizing VOC oxidation by improving the structure and surface chemical states of perovskite catalysts.
基金National Key Research and Development Program of China(No.2023YFB3712400)Science and Technology Committee of Shanghai(Grant No.21ZR1423600)+2 种基金Central Government Guides the Development of Local Science and Technology Special Fund of China(Grant No.216Z1004G)and Baosteelsupport from Ningbo Yongjiang Talent Introduction Programme(2022A-023-C)Zhejiang Phenomenological Materials Technology Co.,Ltd.,China.Finally,the author Jin thanks Baosteel for permission to publish this work.
文摘Severe internal oxidation formed in advanced high-strength steels(AHSSs)during the hot-rolled coiling process compromises subsequent cold rolling and galvanizing processes.Herein,we report how Sn microalloying governs internal oxidation behavior and modulates iron oxide phase transition process.Sn addition significantly reduces the depth of grain boundaries oxidation and the area of internal oxidation,as well as retards the process of oxide scale transformation.Sn preferentially segregates at the iron oxide/substrate interface,forming a diffusion barrier that suppresses outward diffusion of alloying elements and inward oxygen transport.Concurrently,Sn enrichment at grain boundaries obstructs short-circuit oxygen diffusion pathways,significantly reducing the depth of oxidation at the grain boundaries.Furthermore,Sn segregation decreases the interfacial oxygen chemical potential and oxygen availability for selective oxidation reaction.The strategic incorporation of surface-active elements has emerged as a viable metallurgical approach to reduce internal oxidation in hot-rolled coils for AHSS applications.
基金supported by the National Natural Science Foundation of China(22478202,22208169,U23A20125,22478203)China Postdoctoral Science Foundation(2022M721703).
文摘Peroxymonosulfate(PMS)-based Fenton-like technologies have been increasingly employed in the upgrading of biomass,but they are commonly limited by the trade-off between conversion and selectivity due to the short lifetime of reactive oxygen species(ROS)and uncontrollable oxidation pathways.Herein,we show that single-atom Co supported on carbon nitride enables the high-valent-oxo cobalt species(Co(IV)O)mediated oxidation of glucose into value-added products in acetonitrile.This photocatalytic Fenton-like system achieved an overall selectivity of gluconic acid,glucaric acid,arabinose,and formic acid up to 90.3%at glucose conversion of 69.6%,outperforming most of previously reported catalytic systems.The small amount(0.72 wt%)of single-atom Co could not only elevate the optical absorption and the efficiency of photo-generated carriers separation but also induce the efficient generation of Co(IV)O with reduced ROS to enable efficient and selective oxidation.These findings prove the great promise of high-valent metal-oxo species in biomass conversions.
基金the National Natural Science Foundation of China(No.22061012)the Excellent Young Talents Plan of Guizhou Medical University(No.[2023]105)+1 种基金the GMU Training Program of the National Natural Science Foundation of China(No.22NSFCP13)the support from National-Local Joint Engineering Research Center for Innovative&Generic Chemical Drug&Guizhou Province Innovation Base of Common Major Chronic Disease Pathogenesis and Drug Development and Application(No.[2021]4029).
文摘A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-catalysis plays a central role among others catalysis systems own to its longstanding history. While a chemodivergent reaction based on organo-catalysis, especially photocatalysis, is rather limited as these concepts were only prevalent in the last two decades. With the ever-increasing importance of photocatalysis, a chemodivergent reaction based on such an activation pathway would be a meaningful direction. Herein, an efficient chemodivergent strategy for visible light photocatalysis is developed. By employing commercially available Rose Bengal as a photocatalyst, naturally occurring Viridicatin and its derivatives can be transformed into three different types of products through switchable single electron transfer (SET) or energy transfer (EnT) processes. Mechanistic studies have revealed that the oxygen as a reactive center, rather than carbon, is favored, which accounts for the first example of a C–O homo-dimerization product.
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)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
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supported by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.RS-2024-00335976)。
文摘The performance of hematite(α-Fe_(2)O_(3))photoanodes for photoelectrochemical(PEC)water splitting has been limited to around 2-5 mA cm^(-2)under standard conditions due to their short hole diffusion length and sluggish oxygen evolution reaction kinetics.This work overcomes those challenges through a synergistic strategy that co-designs the hematite architecture and the surface reaction pathway.We introduce a textured and hierarchically porous Ti-doped Fe_(2)O_(3)(tp-Fe_(2)O_(3))photoanode,synthesized via multi-cycle growth and flame annealing method.This unique architecture features a high texture(110),enlarged surface area,and hierarchically porous structure,which enable significantly enhanced bulk charge transport and interfacial charge transfer compared to typical nanorod Ti-doped Fe_(2)O_(3)(nr-Fe_(2)O_(3)).As a result,the tp-Fe_(2)O_(3)photoanode achieves a photocurrent density of 3.1 mA cm^(-2)at 1.23 V vs.RHE with exceptional stability over 105 h,notably without any co-catalyst.By replacing the OER with the hydrazine oxidation reaction,the photocurrent further reaches a record-high level of 7.1 mA cm^(-2)at 1.23 V_(RHE).Finally,when we integrate the tp-Fe_(2)O_(3)with a commercial Si solar cell,it achieves a solar-to-hydrogen efficiency of 8.7%-the highest reported value for any Fe_(2)O_(3)-based PVtandem system.This work provides critical insights into rational Fe_(2)O_(3)photoanode design and highlights the potential of hydrazine as an efficient alternative anodic reaction,enabling waste valorization.
