In recent years, immune genetic algorithm (IGA) is gaining popularity for finding the optimal solution for non-linear optimization problems in many engineering applications. However, IGA with deterministic mutation fa...In recent years, immune genetic algorithm (IGA) is gaining popularity for finding the optimal solution for non-linear optimization problems in many engineering applications. However, IGA with deterministic mutation factor suffers from the problem of premature convergence. In this study, a modified self-adaptive immune genetic algorithm (MSIGA) with two memory bases, in which immune concepts are applied to determine the mutation parameters, is proposed to improve the searching ability of the algorithm and maintain population diversity. Performance comparisons with other well-known population-based iterative algorithms show that the proposed method converges quickly to the global optimum and overcomes premature problem. This algorithm is applied to optimize a feed forward neural network to measure the content of products in the combustion side reaction of p-xylene oxidation, and satisfactory results are obtained.展开更多
The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemi...The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemical process in industry [ 1 ]. PX oxidation reaction involves many complex side reactions, among which acetic acid combustion and PX combustion are the most important. As the target product of this oxidation process, the quality and yield of TPA are of great concern. However, the improvement of the qualified product yield can bring about the high energy consumption, which means that the economic objectives of this process cannot be achieved simulta- neously because the two objectives are in conflict with each other. In this paper, an improved self-adaptive multi-objective differential evolution algorithm was proposed to handle the multi-objective optimization prob- lems. The immune concept is introduced to the self-adaptive multi-objective differential evolution algorithm （SADE） to strengthen the local search ability and optimization accuracy. The proposed algorithm is successfully tested on several benchmark test problems, and the performance measures such as convergence and divergence metrics are calculated. Subsequently, the multi-objective optimization of an industrial PX oxidation process is carried out using the proposed immune self-adaptive multi-objective differential evolution algorithm （ISADE）. Optimization results indicate that application oflSADE can greatly improve the yield of TPA with low combustion loss without degenerating TA quality.展开更多
Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a co...Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a complex process involving three-phase reaction of gas, liquid and solid. To monitor the process and to improve the product quality, as well as to visualize the fault type clearly, a fault diagnosis method based on selforganizing map(SOM) and high dimensional feature extraction method, local tangent space alignment(LTSA),is proposed. In this method, LTSA can reduce the dimension and keep the topology information simultaneously,and SOM distinguishes various states on the output map. Monitoring results of PX oxidation reaction process indicate that the LTSA–SOM can well detect and visualize the fault type.展开更多
The p-xylene(PX) oxidation process is of great industrial importance because of the strong demand of the global polyester fiber.A steady-state model of the PX oxidation has been studied by many researchers.In our prev...The p-xylene(PX) oxidation process is of great industrial importance because of the strong demand of the global polyester fiber.A steady-state model of the PX oxidation has been studied by many researchers.In our previous work,a novel industrial p-xylene oxidation reactor model using the free radical mechanism based kinetics has been developed.However,the disturbances such as production rate change,feed composition variability and reactor temperature changes widely exist in the industry process.In this paper,dynamic simulation of the PX oxidation reactor was designed by Aspen Dynamics and used to develop an effective plantwide control structure,which was capable of effectively handling the disturbances in the load and the temperature of the reactor.Step responses of the control structure to the disturbances were shown and served as the foundation of the smooth operation and advanced control strategy of this process in our future work.展开更多
During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experi...During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.展开更多
An attempt has been made to prepare terephthalic acid（TPA） by solvent-free oxidation of p-xylene（PX） with air over tetra（pchlorophenylporphinato） manganese chloride（T（p-Cl）PPMnCl） and cobalt acetate.The co-c...An attempt has been made to prepare terephthalic acid（TPA） by solvent-free oxidation of p-xylene（PX） with air over tetra（pchlorophenylporphinato） manganese chloride（T（p-Cl）PPMnCl） and cobalt acetate.The co-catalysis between T（p-Cl）PPMnCl and Co（OAc）_2 has been discovered under solvent-free conditions.TPA yield could be increased significantly when T（p-Cl）PPMnCl and Co（OAc）_2 were used together.The addition of T（p-Cl）PPMnCl into the reaction mixture over Co（OAc）_2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.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
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
An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achievin...An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achieving a critical load of 87.8 N.Silicon doping induced nanocrystallization and amorphization,increasing the hardness to 26 GPa.At high temperatures,a nanoscale Cr-rich(Cr,Al)_(2)O_(3) layer was formed,effectively inhibiting oxygen diffusion.The coating underwent unique phase transformations,during which Cr_(2)N and amorphous Si3N4 were converted into dispersed SiCr_(3) nanoparticles,which stabilized Cr atoms and suppressed their outward diffusion.Ab initio molecular dynamics simulations revealed that Cr atoms exhibited higher chemical activity and oxygen-capture capability than Al atoms and Si atoms served as diffusion barriers by pinning onto the oxidized surface,considerably improving the oxidation resistance of the coating.展开更多
Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the effica...Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.展开更多
基金Supported by the Major State Basic Research Development Program of China (2012CB720500)the National Natural Science Foundation of China (Key Program: U1162202)+1 种基金the National Natural Science Foundation of China (General Program:61174118)Shanghai Leading Academic Discipline Project (B504)
文摘In recent years, immune genetic algorithm (IGA) is gaining popularity for finding the optimal solution for non-linear optimization problems in many engineering applications. However, IGA with deterministic mutation factor suffers from the problem of premature convergence. In this study, a modified self-adaptive immune genetic algorithm (MSIGA) with two memory bases, in which immune concepts are applied to determine the mutation parameters, is proposed to improve the searching ability of the algorithm and maintain population diversity. Performance comparisons with other well-known population-based iterative algorithms show that the proposed method converges quickly to the global optimum and overcomes premature problem. This algorithm is applied to optimize a feed forward neural network to measure the content of products in the combustion side reaction of p-xylene oxidation, and satisfactory results are obtained.
基金Supported by the Shanghai Second Polytechnic University Key Discipline Construction-Control Theory & Control Engineering(No.XXKPY1609)the National Natural Science Foundation of China(61422303)+1 种基金Shanghai Talent Development Funding(H200-2R-15111)2017 Shanghai Second Polytechnic University Cultivation Research Program of Young Teachers(02)
文摘The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemical process in industry [ 1 ]. PX oxidation reaction involves many complex side reactions, among which acetic acid combustion and PX combustion are the most important. As the target product of this oxidation process, the quality and yield of TPA are of great concern. However, the improvement of the qualified product yield can bring about the high energy consumption, which means that the economic objectives of this process cannot be achieved simulta- neously because the two objectives are in conflict with each other. In this paper, an improved self-adaptive multi-objective differential evolution algorithm was proposed to handle the multi-objective optimization prob- lems. The immune concept is introduced to the self-adaptive multi-objective differential evolution algorithm （SADE） to strengthen the local search ability and optimization accuracy. The proposed algorithm is successfully tested on several benchmark test problems, and the performance measures such as convergence and divergence metrics are calculated. Subsequently, the multi-objective optimization of an industrial PX oxidation process is carried out using the proposed immune self-adaptive multi-objective differential evolution algorithm （ISADE）. Optimization results indicate that application oflSADE can greatly improve the yield of TPA with low combustion loss without degenerating TA quality.
基金Supported by the Major State Basic Research Development Program of China(2012CB720500)the National Natural Science Foundation of China(6133301021276078)+3 种基金the National Science Fund for Outstanding Young Scholars(61222303)the Fundamental Research Funds for the Central Universities,Shanghai Rising-Star Program(13QH1401200)the Program for New Century Excellent Talents in University(NCET-10-0885)Shanghai R&D Platform Construction Program(13DZ2295300)
文摘Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a complex process involving three-phase reaction of gas, liquid and solid. To monitor the process and to improve the product quality, as well as to visualize the fault type clearly, a fault diagnosis method based on selforganizing map(SOM) and high dimensional feature extraction method, local tangent space alignment(LTSA),is proposed. In this method, LTSA can reduce the dimension and keep the topology information simultaneously,and SOM distinguishes various states on the output map. Monitoring results of PX oxidation reaction process indicate that the LTSA–SOM can well detect and visualize the fault type.
基金Supported by the Major State Basic Research Development Program of China(2012CB720500)the National Natural Science Foundation of China(U1162202)+2 种基金the Shanghai Second Polytechnic University Key Discipline Construction(4th term)-Control Theory&Control Engineering(XXKPY1308)the Cultivation Program of Young Teachers in Colleges and Universities of Shanghai(ZZegdl4013)the School Foundation of Shanghai Second Polytechnic University(EGD14XQD02)
文摘The p-xylene(PX) oxidation process is of great industrial importance because of the strong demand of the global polyester fiber.A steady-state model of the PX oxidation has been studied by many researchers.In our previous work,a novel industrial p-xylene oxidation reactor model using the free radical mechanism based kinetics has been developed.However,the disturbances such as production rate change,feed composition variability and reactor temperature changes widely exist in the industry process.In this paper,dynamic simulation of the PX oxidation reactor was designed by Aspen Dynamics and used to develop an effective plantwide control structure,which was capable of effectively handling the disturbances in the load and the temperature of the reactor.Step responses of the control structure to the disturbances were shown and served as the foundation of the smooth operation and advanced control strategy of this process in our future work.
基金Supported by the Natural National Science Foundation of China （20080672） and the Research Fund for the Doctoral Program of Higher Education of China （200803351111）.
文摘During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.
文摘An attempt has been made to prepare terephthalic acid（TPA） by solvent-free oxidation of p-xylene（PX） with air over tetra（pchlorophenylporphinato） manganese chloride（T（p-Cl）PPMnCl） and cobalt acetate.The co-catalysis between T（p-Cl）PPMnCl and Co（OAc）_2 has been discovered under solvent-free conditions.TPA yield could be increased significantly when T（p-Cl）PPMnCl and Co（OAc）_2 were used together.The addition of T（p-Cl）PPMnCl into the reaction mixture over Co（OAc）_2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA.The effect of temperature on reaction was also investigated.
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.
基金financially supported by the National Science and Technology Major Project(No.2024ZD1404705)。
文摘An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achieving a critical load of 87.8 N.Silicon doping induced nanocrystallization and amorphization,increasing the hardness to 26 GPa.At high temperatures,a nanoscale Cr-rich(Cr,Al)_(2)O_(3) layer was formed,effectively inhibiting oxygen diffusion.The coating underwent unique phase transformations,during which Cr_(2)N and amorphous Si3N4 were converted into dispersed SiCr_(3) nanoparticles,which stabilized Cr atoms and suppressed their outward diffusion.Ab initio molecular dynamics simulations revealed that Cr atoms exhibited higher chemical activity and oxygen-capture capability than Al atoms and Si atoms served as diffusion barriers by pinning onto the oxidized surface,considerably improving the oxidation resistance of the coating.
基金supported by the National Key R&D Program of China (2021YFA1502802)the National Natural Science Foundation of China (U21B2092, 22202213, 22402210, 22502215, 22502214, 22572200, and 22579171)+3 种基金the International Partnership Program of Chinese Academy of Sciences (172GJHZ2022028MI)the Shenyang Bureau of Science and Technology (24-213-3-25)the Natural Science Foundation of Liaoning Province (2025BS0153)Zhongke Technology Achievement Transfer and Transformation Center of Henan Province 2025119
文摘Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.
