We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various re...We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various reaction conditions under microwave irradiation(0-50 W).These conditions included reaction temperatures(300-600℃),oxygen concentrations(0-6%),and varying K^(+)doping levels on the catalysts'activity.The crystalline phase,microstructure,and the catalytic activity of the catalyst were analyzed by XRD,TEM,H_2-TPR,and O_(2)-TPD.The experimental results reveal that La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts consistently form homogeneous perovskite nanoparticles across different doping levels.The NO decomposition efficiency on these catalysts initially increases and then decreases with variations in doping amount,temperature,and microwave power.Additionally,an increase in oxygen concentration positively influences NO conversion rates.The optimal performance is observed with La_(0.7)K_(0.3)CoO_(3)catalyst under conditions of x=0.3,400℃,10 W microwave power,and 4%oxygen concentration,achieving a peak NO conversion rate of La_(0.7)K_(0.3)CoO_(3)catalyst is 93.1%.展开更多
Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AAC...Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AACH) and their mixture were obtained, and then, different kinds of alumina were obtained after calcination. Three catalysts supported on the different alumina were obtained via impregnating cobalt and ruthenium by incipient wetness. The effects of different precipitants on composition of precursors were?studied by XRD, FTIR, and TGA. The property and structure of alumina were studied by XRD and BET. The supported catalysts were studied by characterizations of XRD and H2-TPR, and the catalytic performance for Fischer-Tropsch synthesis (FTS) were evaluated at a fix-bed reactor. The relations among the composition of precursors, the property of alumina and the catalytic performance of supported catalysts were researched thoroughly.展开更多
To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprisi...To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprising Co,Co_(3)O_(4)and CoN,as well as numerous N heteroatoms,on graphene nanosheets(Co/Co_(3)O_(4)/CoN/NG).The Co/Co_(3)O_(4)/CoN nanoparticles with the size of less than 50 nm are homogeneously dispersed on N-doped graphene(NG)substrate,which greatly improve the catalytic behaviors for ORR.The results show that the half-wave potential is as high as 0.80 V vs.RHE and the limiting current density is 4.60 mA·cm^(−2),which are close to those of commercially available platinum/carbon(Pt/C)catalysts.Applying as cathodic catalyst for ZABs,the battery shows large specific capacity and open circuit voltage of 843.0 mAh∙g^(−1) and 1.41 V,respectively.The excellent performance is attributed to the efficient two-dimensional structure with high accessible surface area and the numerous multiple active sites provided by highly scattered Co/Co_(3)O_(4)/CoN particles and doped nitrogen on the carbon matrix.展开更多
The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(wate...The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.展开更多
Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor ...Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor materials have been intensively explored,some severe issues,such as rapid charge recombination and sluggish redox reaction kinetics,remain.In this regard,cocatalyst modifi cation by trapping charges and boosting surface reactions is one of the most effi cient strategies to improve the effi ciency of semiconductor photocatalysts.This review focuses on recent advances in CO_(2)photoreduction over costeff ective and earth-abundant cobalt(Co)-based cocatalysts,which are competitive candidates of noble metals for practical applications.First,the functions of Co-based cocatalysts for promoting photocatalytic CO_(2)reduction are briefl y discussed.Then,diff erent kinds of Co-based cocatalysts,including cobalt oxides and hydroxides,cobalt nitrides and phosphides,cobalt sulfi des and selenides,Co single-atom,and Co-based metal–organic frameworks(MOFs),are summarized.The underlying mechanisms of these Co-based cocatalysts for facilitating CO_(2)adsorption–activation,boosting charge separation,and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations.In addition,the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO_(2)reduction is highlighted in some selected examples.Finally,the challenges and future perspectives on constructing more effi cient Co-based cocatalysts for practical applications are proposed.展开更多
The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A...The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A major challenge to their performance is the corrosion occurring at phase boundaries under harsh operating conditions.This study investigates the effects of pulsed magnetic field treatment(PMT)on improving corrosion resistance at phase boundaries,specifically at the carbide/matrix Co interface,and seeks to clarify the underlying mechanisms.Advanced characterization techniques,including scanning electron microscopy(SEM),in situ transmission electron microscopy(TEM),in situ scanning kelvin probe force microscopy(SKPFM),and density functional theory(DFT)calculations,were employed.PMT samples exhibited no interface corrosion cracking or carbide spalling and showed a significant reduction in corrosion depth.TEM analysis revealed reduced lattice distortion at phase boundaries and a partial transformation of face-centered cubic(FCC)Co to hexagonal closepacked(HCP)Co.The enhanced corrosion resistance at phase boundaries is attributed to changes in the electronic work function(EWF),as determined by SKPFM measurements and DFT calculations.展开更多
A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based cataly...A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based catalysts were characterized by XRD, TEM and BET techniques. Their catalytic performances were tested in a slurry-bed reactor under FTS reaction conditions. The drying and crystallization were carried out simultaneously during SCFD, therefore, the catalysts prepared by SCFD method have ideal structure and show the FTS performance superior to the others prepared by CD method. The FTS activity and selectivity were improved via adding Zn, Mn and K promoters, and less CH4 and CO2 as well as higher yield of C5＋ products were achieved. The optimal performance of a 92% CO conversion and a 65% C5＋ product yield was obtained over a catalyst with the component of Co/Zn/Mn/K = 100/50/10/7. Furthermore, the catalytic performance was studied under the conditions of liquid-phase and supercritical phase slurry-bed, and C5＋ product yield were 57.4% and 65.4%, respectively. In summary, better catalytic performance was obtained using the nanosized catalyst prepared by SCFD method under supercritical reaction conditions, resulting in higher conversion of CO, less CO2 byproduct, and higher yield of C5＋ products.展开更多
The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the mo...The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after-treatment tech-nology,which requires the catalyst to have superior low temperature activity.Compared with cerium oxide which is widely used,cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology.This paper elaborates on the influence of modification techniques such as doping,loading,and solid solution on the catalytic performance of cobalt-based catalysts in soot oxidation.Along the same lines,it further reviews the research progress on cobalt-based oxide catalysts with specific dimensional structures and morphologies in soot oxidation.Finally,it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt-based catalysts in soot oxidation.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt...Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.展开更多
To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content ...To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.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
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked ne...Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.展开更多
Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transf...Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.展开更多
Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for...Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.展开更多
High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environm...High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.展开更多
文摘We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various reaction conditions under microwave irradiation(0-50 W).These conditions included reaction temperatures(300-600℃),oxygen concentrations(0-6%),and varying K^(+)doping levels on the catalysts'activity.The crystalline phase,microstructure,and the catalytic activity of the catalyst were analyzed by XRD,TEM,H_2-TPR,and O_(2)-TPD.The experimental results reveal that La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts consistently form homogeneous perovskite nanoparticles across different doping levels.The NO decomposition efficiency on these catalysts initially increases and then decreases with variations in doping amount,temperature,and microwave power.Additionally,an increase in oxygen concentration positively influences NO conversion rates.The optimal performance is observed with La_(0.7)K_(0.3)CoO_(3)catalyst under conditions of x=0.3,400℃,10 W microwave power,and 4%oxygen concentration,achieving a peak NO conversion rate of La_(0.7)K_(0.3)CoO_(3)catalyst is 93.1%.
文摘Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AACH) and their mixture were obtained, and then, different kinds of alumina were obtained after calcination. Three catalysts supported on the different alumina were obtained via impregnating cobalt and ruthenium by incipient wetness. The effects of different precipitants on composition of precursors were?studied by XRD, FTIR, and TGA. The property and structure of alumina were studied by XRD and BET. The supported catalysts were studied by characterizations of XRD and H2-TPR, and the catalytic performance for Fischer-Tropsch synthesis (FTS) were evaluated at a fix-bed reactor. The relations among the composition of precursors, the property of alumina and the catalytic performance of supported catalysts were researched thoroughly.
基金financially supported by the National Natural Science Foundation of China (No. 52102100)the Industry-University-Research Cooperation Project of Jiangsu Province, China (No. BY2021525)the Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (No. SJCX22_1944)
文摘To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprising Co,Co_(3)O_(4)and CoN,as well as numerous N heteroatoms,on graphene nanosheets(Co/Co_(3)O_(4)/CoN/NG).The Co/Co_(3)O_(4)/CoN nanoparticles with the size of less than 50 nm are homogeneously dispersed on N-doped graphene(NG)substrate,which greatly improve the catalytic behaviors for ORR.The results show that the half-wave potential is as high as 0.80 V vs.RHE and the limiting current density is 4.60 mA·cm^(−2),which are close to those of commercially available platinum/carbon(Pt/C)catalysts.Applying as cathodic catalyst for ZABs,the battery shows large specific capacity and open circuit voltage of 843.0 mAh∙g^(−1) and 1.41 V,respectively.The excellent performance is attributed to the efficient two-dimensional structure with high accessible surface area and the numerous multiple active sites provided by highly scattered Co/Co_(3)O_(4)/CoN particles and doped nitrogen on the carbon matrix.
基金financial support from the National Natural Science Foundation of China(21528302)Zhejiang Province Natural Science Foundation(LQ15B060004)
文摘The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.
基金supported by the National Natural Science Foundation of China(Nos.21905049,22178057)the Natural Science Foundation of Fujian Province(Nos.2020J01201,2021J01197)+1 种基金the Research Foundation of the Academy of Carbon Neutrality of Fujian Normal University(TZH2022-07)the Award Program for Minjiang Scholar Professorship。
文摘Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor materials have been intensively explored,some severe issues,such as rapid charge recombination and sluggish redox reaction kinetics,remain.In this regard,cocatalyst modifi cation by trapping charges and boosting surface reactions is one of the most effi cient strategies to improve the effi ciency of semiconductor photocatalysts.This review focuses on recent advances in CO_(2)photoreduction over costeff ective and earth-abundant cobalt(Co)-based cocatalysts,which are competitive candidates of noble metals for practical applications.First,the functions of Co-based cocatalysts for promoting photocatalytic CO_(2)reduction are briefl y discussed.Then,diff erent kinds of Co-based cocatalysts,including cobalt oxides and hydroxides,cobalt nitrides and phosphides,cobalt sulfi des and selenides,Co single-atom,and Co-based metal–organic frameworks(MOFs),are summarized.The underlying mechanisms of these Co-based cocatalysts for facilitating CO_(2)adsorption–activation,boosting charge separation,and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations.In addition,the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO_(2)reduction is highlighted in some selected examples.Finally,the challenges and future perspectives on constructing more effi cient Co-based cocatalysts for practical applications are proposed.
基金financially supported by the National Key Research and Development Program of China(No.2020YFA0714900)the Joint Fund of the Ministry of Education(No.8091B012201)
文摘The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A major challenge to their performance is the corrosion occurring at phase boundaries under harsh operating conditions.This study investigates the effects of pulsed magnetic field treatment(PMT)on improving corrosion resistance at phase boundaries,specifically at the carbide/matrix Co interface,and seeks to clarify the underlying mechanisms.Advanced characterization techniques,including scanning electron microscopy(SEM),in situ transmission electron microscopy(TEM),in situ scanning kelvin probe force microscopy(SKPFM),and density functional theory(DFT)calculations,were employed.PMT samples exhibited no interface corrosion cracking or carbide spalling and showed a significant reduction in corrosion depth.TEM analysis revealed reduced lattice distortion at phase boundaries and a partial transformation of face-centered cubic(FCC)Co to hexagonal closepacked(HCP)Co.The enhanced corrosion resistance at phase boundaries is attributed to changes in the electronic work function(EWF),as determined by SKPFM measurements and DFT calculations.
基金supported by Research Fund for the Doctoral Program of Higher Education (China,No.20050010014)
文摘A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based catalysts were characterized by XRD, TEM and BET techniques. Their catalytic performances were tested in a slurry-bed reactor under FTS reaction conditions. The drying and crystallization were carried out simultaneously during SCFD, therefore, the catalysts prepared by SCFD method have ideal structure and show the FTS performance superior to the others prepared by CD method. The FTS activity and selectivity were improved via adding Zn, Mn and K promoters, and less CH4 and CO2 as well as higher yield of C5＋ products were achieved. The optimal performance of a 92% CO conversion and a 65% C5＋ product yield was obtained over a catalyst with the component of Co/Zn/Mn/K = 100/50/10/7. Furthermore, the catalytic performance was studied under the conditions of liquid-phase and supercritical phase slurry-bed, and C5＋ product yield were 57.4% and 65.4%, respectively. In summary, better catalytic performance was obtained using the nanosized catalyst prepared by SCFD method under supercritical reaction conditions, resulting in higher conversion of CO, less CO2 byproduct, and higher yield of C5＋ products.
基金National Natural Science Foundation of China,Grant/Award Number:22406050Top-Notch Personnel Fund of Henan Agricultural University,Grant/Award Number:30501029+2 种基金Natural Science Foundation of Henan Province,Grant/Award Number:232300420293Science and Technology Project of China Tobacco Shaanxi Industrial Co.,Ltd,Grant/Award Number:2024610000340104Postgraduate Education Reform and Quality Improvement Project of Henan Province,Grant/Award Number:YJS2024JD17。
文摘The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after-treatment tech-nology,which requires the catalyst to have superior low temperature activity.Compared with cerium oxide which is widely used,cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology.This paper elaborates on the influence of modification techniques such as doping,loading,and solid solution on the catalytic performance of cobalt-based catalysts in soot oxidation.Along the same lines,it further reviews the research progress on cobalt-based oxide catalysts with specific dimensional structures and morphologies in soot oxidation.Finally,it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt-based catalysts in soot oxidation.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金supported by the National Natural Science Foundation of China(Grant Nos.:21825201,52401244 and 52201227)Henan Province Key Research and Development and Promotion Program(Scientific and Technological Breakthrough Project:232102240088 and 252102230078)+3 种基金the Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(252102230078)Doctoral Research Startup Fund Project of Henan Open University(BSJH-2025-04)Zhejiang Provincial Natural Science Foundation of China(LQ24B020005,LQ23B030001)China Postdoctoral Science Foundation(2024M762442).
文摘Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.
基金Supported by the Science and Technology Cooperation and Exchange special project of Cooperation of Shanxi Province(202404041101014)the Fundamental Research Program of Shanxi Province(202403021212333)+3 种基金the Joint Funds of the National Natural Science Foundation of China(U24A20555)the Lvliang Key R&D of University-Local Cooperation(2023XDHZ10)the Initiation Fund for Doctoral Research of Taiyuan University of Science and Technology(20242026)the Outstanding Doctor Funding Award of Shanxi Province(20242080).
文摘To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
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.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金support from the National Natural Science Foundation of China(Nos.22293011,T2341001)the Major Science and Technology Project of Anhui Province(202203a06020010).
文摘Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.
基金supported by the National Natural Science Foundation of China(No.52064035)the Key Research and Development Program of Gansu Province,China(No.25YFGA024)the Natural Science Foundation of Zhejiang Province,China(No.LGG22E020003).
文摘Lithium-sulfur(Li-S)batteries boast a theoretical energy density as high as 2600 Wh·kg^(−1),positioning them as a highly attractive option for future advanced energy storage systems.Challenges such as slow transformation kinetics and shuttle effects associated with lithium polysulfides(LiPSs)have seriously hindered their practical applications.In this paper,we present a new method for the synthesis of hollow carbon-sphere-supported Co monatomic catalysts(Co-N-C).This new synthesis method achieves pyrolytic coordination using a precursor rich in imide(-RC=N-)polymers.This synthesis method not only improves the adsorbability and catalytic activity of LiPS but also significantly weakens the shuttle effect and generates Co-N-C with superior conductivity,abundant hollow structures,and a high specific surface area,thus efficiently capturing and restricting the movement of LiPS intermediates.The dispersed Co monoatomic catalysts(Co SACs)were anchored to a highly conductive nitrogen-doped carbon framework and exhibited symmetric N-coordination active sites(Co-N_(4))to ensure fast redox kinetics of LiPS and Li_(2)S_(2)/Li_(2)S solid-state products.The lithium-sulfur battery with Co-N-C as the sulfur carrier showed excellent discharging capacity of 1146.6 mAh·g^(−1) at a discharge rate of 0.5 C and maintained excellent performance at a high discharge rate of 2 C.The capacity decay rate in 500 cycles was only 0.086%per cycle,reflecting excellent long-term cycle stability.This study highlights the key role of the synergistic effect between single-atom cobalt catalysts and hollow carbon spheres in enhancing the efficiency of lithium-sulfur(Li-S)batteries.It also provides valuable insights into the construction and fabrication of highly active monatomic catalysts.The catalytic conversion efficiency of lithium polysulfides is significantly enhanced when embedded in hollow carbon architectures,which serves as a critical strategy for optimizing the electrochemical behavior of next-generation Li-S batteries.
基金supported by the National Natural Science Foundation of China(No.22208374)the Excellent Youth Scientist Award Foundation of Shandong Province(No.ZR2024YQ009)+2 种基金the Distinguished Young Scholars of the National Natural Science Foundation of China(No.22322814)CNPC Innovation Found(2022DQ02-0607)the Fundamental Research Funds for the Central Universities(No.24CX07006A).
文摘Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.
基金supported by the Australian Research Council(ARC)Projects(DP220101139,DP220101142,and LP240100542).
文摘High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.
