The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile...The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.展开更多
Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covale...Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.展开更多
Light cycle oil(LCO) with high content of poly-aromatics was difficult to upgrade and convert,which had hindered upgrading fuel quality to meet with the standard of automotive diesel for the purpose of sustainable dev...Light cycle oil(LCO) with high content of poly-aromatics was difficult to upgrade and convert,which had hindered upgrading fuel quality to meet with the standard of automotive diesel for the purpose of sustainable development.The hydrocracking behaviors of typical aromatics in LCO of naphthalene and tetralin were investigated over NiMo and CoMo catalysts.Several characterization methods including N2-adsoprtion and desorption,ammonia temperature-programmed desorption(NH3-TPD),Pyridine infrared spectroscopy(Py-IR),CO infrared spectroscopy(CO-IR),Raman and X-ray photoelectron spectroscopy(XPS) were applied to determine the properties of different catalysts.The results showed that CoMo catalyst with high concentration of S-edges could hydrosaturate more naphthalene to tetralin but exhibit lower yield of high-value light aromatics(carbon numbers less than 10) than NiMo catalyst.NiMo catalyst with high concentration of Mo-edges also presented a higher selectivity of converting naphthalene into cyclanes than CoMo catalyst.Subsequently,the naphthalene and LCO hydrocracking performances were also investigated over different catalysts systems.The activity evaluation and kinetic analysis results showed that the naphthalene hydrocracking conversion and the yield of light aromatics for CoMo-AY/NiMo-AY grading catalysts were higher than NiMo-AY/CoMo-AY grading catalysts at same condition.A stepwise reaction principle was proposed to explain the high efficiency of CoMo-AY/NiMoAY grading catalysts.Finally,the LCO hydrocracking evaluation results confirmed that CoMo-AY/NiMoAY catalysts grading system with low carbon deposition and high stability could remain high percentage of active phases,which was more efficient to convert LCO to high-octane gasoline.展开更多
Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is st...Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is still a great challenge to design the heterogeneous selective electrochemical catalyst for inhibiting the“shuttle effect”.Herein,nickel cobalt phosphide and cobalt phosphide as the heterogeneous catalyst active sites embedded in the nitrogen-doped hollow carbon nanocages(NiCoP@CoP/NC)are reported,used for multi-step and multi-phase sulfur electrode reaction,and it is found that metal-sulfur d-p hybridization can effectively indicate the intrinsic catalytic activity of metal site.Division of labor and cooperation of the bi-active NiCoP@CoP as heterogeneous catalysts propel the stepwise polysulfide conversion.NiCoP and CoP sites preferentially accelerate the long-chain polysulfide conversion reaction(S_(8)■LiPSs)and the short-chain polysulfide conversion reactions(LiPSs■Li_(2)S),respectively.Moreover,the hollow and porous N-doped carbon structure can successfully suppress the volume effect and improve the conductivity of the sulfur cathode.The unique design can obtain an effective inhibition of the shuttle effect and rapid electrode reaction.As a result,Li-S batteries demonstrate a high initial capacity of 1063 mAh g^(-1) and a low-capacity decay of 0.04% per cycle within 1000 cycles.Our work provides a feasible idea for the design of host materials in Li-S batteries.展开更多
The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system...The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.展开更多
A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related ...A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.展开更多
In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification...In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.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
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
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
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
Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organ...Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.展开更多
基金supported by the National Natural Science Foundation of China (51901083)the Fundamental Research Funds for the Central Universities。
文摘The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.
基金the financially supported from the National Nat-ural Science Foundation of China(Nos.21978178,22008157,and 21776187)the Distinguished Young Scholars for the Natural Science Foundation of Sichuan Province(No.2023NSFSC1915)。
文摘Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.
基金supported by the National Natural Science Foundation of China (Nos. 21878330, 21676298)the National Science and Technology Major Project, the CNPC Key Research Project (2016E-0707)the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award (No. OSR-2019-CPF-4103.2)。
文摘Light cycle oil(LCO) with high content of poly-aromatics was difficult to upgrade and convert,which had hindered upgrading fuel quality to meet with the standard of automotive diesel for the purpose of sustainable development.The hydrocracking behaviors of typical aromatics in LCO of naphthalene and tetralin were investigated over NiMo and CoMo catalysts.Several characterization methods including N2-adsoprtion and desorption,ammonia temperature-programmed desorption(NH3-TPD),Pyridine infrared spectroscopy(Py-IR),CO infrared spectroscopy(CO-IR),Raman and X-ray photoelectron spectroscopy(XPS) were applied to determine the properties of different catalysts.The results showed that CoMo catalyst with high concentration of S-edges could hydrosaturate more naphthalene to tetralin but exhibit lower yield of high-value light aromatics(carbon numbers less than 10) than NiMo catalyst.NiMo catalyst with high concentration of Mo-edges also presented a higher selectivity of converting naphthalene into cyclanes than CoMo catalyst.Subsequently,the naphthalene and LCO hydrocracking performances were also investigated over different catalysts systems.The activity evaluation and kinetic analysis results showed that the naphthalene hydrocracking conversion and the yield of light aromatics for CoMo-AY/NiMo-AY grading catalysts were higher than NiMo-AY/CoMo-AY grading catalysts at same condition.A stepwise reaction principle was proposed to explain the high efficiency of CoMo-AY/NiMoAY grading catalysts.Finally,the LCO hydrocracking evaluation results confirmed that CoMo-AY/NiMoAY catalysts grading system with low carbon deposition and high stability could remain high percentage of active phases,which was more efficient to convert LCO to high-octane gasoline.
基金supported by the National Natural Science Foundation of China(Nos.NSFC 51772060,51672059,and 51621091)the Heilongjiang Touyan Team Program,and the Fundamental Research Funds for the Central Universities(Grant No.HIT.OCEF.2021003)。
文摘Designing electrochemical catalysts has become a research hotspot due to their accelerating the polysulfide conversion of the sulfur cathode to inhibit the“shuttle effect”in lithium-sulfur batteries.However,it is still a great challenge to design the heterogeneous selective electrochemical catalyst for inhibiting the“shuttle effect”.Herein,nickel cobalt phosphide and cobalt phosphide as the heterogeneous catalyst active sites embedded in the nitrogen-doped hollow carbon nanocages(NiCoP@CoP/NC)are reported,used for multi-step and multi-phase sulfur electrode reaction,and it is found that metal-sulfur d-p hybridization can effectively indicate the intrinsic catalytic activity of metal site.Division of labor and cooperation of the bi-active NiCoP@CoP as heterogeneous catalysts propel the stepwise polysulfide conversion.NiCoP and CoP sites preferentially accelerate the long-chain polysulfide conversion reaction(S_(8)■LiPSs)and the short-chain polysulfide conversion reactions(LiPSs■Li_(2)S),respectively.Moreover,the hollow and porous N-doped carbon structure can successfully suppress the volume effect and improve the conductivity of the sulfur cathode.The unique design can obtain an effective inhibition of the shuttle effect and rapid electrode reaction.As a result,Li-S batteries demonstrate a high initial capacity of 1063 mAh g^(-1) and a low-capacity decay of 0.04% per cycle within 1000 cycles.Our work provides a feasible idea for the design of host materials in Li-S batteries.
基金Project supported by the National Key R&D Program of China(2023YFC3707201)National Natural Science Foundation of China(52200136,52270112,22106172)National Energy-Saving and Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)。
文摘The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21908225)the National Key Research and Development Program of China(Grant No.2016YFB0600505)Youth Innovation Promotion Association,CAS(2014037).
文摘A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.
基金Supported by the National Natural Science Foundation of China(52506188,52476215)Natural Science Foundation of Liaoning Province(2024-MS-139,2024JH3/10200047)Scientific Research Program of Department of Education of Liaoning Province(310125042,LJ212410143033。
文摘In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.
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 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.
基金financially supported by the National Natural Science Foundation of China(U22A20421)the Qinglan Project of Jiangsu Province,the 533 Talent Program of Huaian City,and the College Students’Innovative Entrepreneurial Training Plan Program of Jiangsu Province(X202510323027).
文摘Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.
