Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consum...Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.展开更多
The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close atten...The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.展开更多
Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitat...Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.展开更多
Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
Metallurgical dust(MD)was used as raw material to prepare rare earth Ce-doped Fe-based catalysts.The results show that the Ce_(0.1)/AMD-300℃catalyst prepared from acid-modified diatomite(AMD)with mCe/mMD=0.1(m_(Ce)an...Metallurgical dust(MD)was used as raw material to prepare rare earth Ce-doped Fe-based catalysts.The results show that the Ce_(0.1)/AMD-300℃catalyst prepared from acid-modified diatomite(AMD)with mCe/mMD=0.1(m_(Ce)and m_(MD)are the mass of Ce and MD,respectively)after being roasted at 300℃can reach 99%NO_(x)removal rate in the wide temperature range of 230–430℃and exhibits excellent So_(2)and H_(2)o resistance.The MD effectively removes alkali metal elements by the modification process,increases the specific surface area and optimizes the pore structure of MD.The doping of Ce element makes Fe-based catalysts have more surface adsorbed oxygen O_(α)and a higher Ce^(3+)/Ce^(4+)ratio.Through ammonia temperature-programmed desorption and hydrogen temperature-programmed reduction,it was found that the strong interaction between cerium and iron promotes the formation of more oxygen cavities in the catalyst,thereby generating more active and easily reducible oxygen species and promoting the transformation of Brønsted acid site to Lewis acid site.The research results provide a theoretical basis for the preparation of efficient and inexpensive Fe-based catalysts from MD.展开更多
As one of the most important chemicals and carbon-free energy carriers,ammonia(NH3)has significant energy-related applications in industry and agriculture.Ninety percent of NH_(3) is produced by the Haber-Bosch proces...As one of the most important chemicals and carbon-free energy carriers,ammonia(NH3)has significant energy-related applications in industry and agriculture.Ninety percent of NH_(3) is produced by the Haber-Bosch process using high-purity N_(2) and H_(2) at high temperatures and pressures,which consumes about 1%of the total energy production and causes 1.4% of global CO_(2) emissions.The environmentally friendly electrochemical nitrogen reduction reaction(NRR)with low energy consumption is a promising alternative to the conventional Haber-Bosch process.However,the main issue is the low Faradaic efficiency and NH3 selectivity of electrochemical NRR,caused by inert nitrogen molecules and competitive hydrogen evolution reaction.As one of the cheapest and most abundant transition metals widely utilized in the Haber-Bosch process,the Fe element has presented the potential high performance for the electrochemical NRR.This article summarizes recent advances and research progress in non-noble Fe-based catalysts used for NH_(3) electrosynthesis.Various synthetic protocols,structure/morphology modification,performance improvement,and reaction mechanisms are comprehensively presented.Based on recent experimental and theoretical studies,we aim to illuminate the structure-property relationship and offer an excellent opportunity for engineering advanced Fe-based catalysts for nitrogen fixation.The most critical challenges and opportunities for Fe-based catalysts are also provided.This review would open up a promising avenue toward developing platinum-group-metal-free catalysts for electrochemical NRR applications in the future.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.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
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.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
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
The development of catalysts with highly efficient oxygen evolution performance and low-Ir loading is key to scaling up the application of proton exchange membrane(PEM)water electrolysis technology.Here,an Ir-skin cat...The development of catalysts with highly efficient oxygen evolution performance and low-Ir loading is key to scaling up the application of proton exchange membrane(PEM)water electrolysis technology.Here,an Ir-skin catalyst(Ir@KM)is realized on a potassium-manganese oxide(K_(0.25)MnO_(x)(KM))using an ion-exchange method.The Ir-skin over the prepared Ir@KM has a low Ir-Ir atomic distance,endowing an energetically favorable oxide path mechanism to allow a low theoretical overpotential of 0.13 V.Ir@KM offers a low overpotential of~280 mV at a current density of 10 mA cm^(-2)and provides a high mass activity of up to 18,500 A at a cell voltage of 1.8 V in PEM,which is 17.6 times higher than that of IrO_(2),demonstrating a significant advantage in reducing the cost of the membrane electrode.The presented Ir-skin concept represents a promising strategy to fabricate low-Ir catalyst with high activity and durability for practical applications of PEM.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
Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tai...Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.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
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
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
The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from ...The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.展开更多
基金the Haihe Laboratory of Sus-tainable Chemical Transformations for financial support(No.24HHWCSS00009).
文摘Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.
基金supported by the Ministry of Higher Education,Science and Innovation,and the Slovenian Research Agency(ARIS)throughresearch grants J7-4638 and J2-4441.
文摘The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.
基金financially supported by the National Key R&D Program of China (2023YFB4104501)the National Natural Science Foundation of China (22372165)+2 种基金the Liaoning Binhai Laboratory (LBLA-2024-01)the Grant. YLU-DNL Fund (2023001)DICP (Grant: DICP I202457)
文摘Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
基金The research was financially sponsored by the Major Scientific Research Planning Project of Colleges and Universities in Anhui Province(Grant No.2023AH040147)the National Natural Science Foundation of China(Grant No.52074093)the Outstanding Youth Scientific Research Project of Colleges and Universities in Anhui Province(Grant No.2022AH030044).
文摘Metallurgical dust(MD)was used as raw material to prepare rare earth Ce-doped Fe-based catalysts.The results show that the Ce_(0.1)/AMD-300℃catalyst prepared from acid-modified diatomite(AMD)with mCe/mMD=0.1(m_(Ce)and m_(MD)are the mass of Ce and MD,respectively)after being roasted at 300℃can reach 99%NO_(x)removal rate in the wide temperature range of 230–430℃and exhibits excellent So_(2)and H_(2)o resistance.The MD effectively removes alkali metal elements by the modification process,increases the specific surface area and optimizes the pore structure of MD.The doping of Ce element makes Fe-based catalysts have more surface adsorbed oxygen O_(α)and a higher Ce^(3+)/Ce^(4+)ratio.Through ammonia temperature-programmed desorption and hydrogen temperature-programmed reduction,it was found that the strong interaction between cerium and iron promotes the formation of more oxygen cavities in the catalyst,thereby generating more active and easily reducible oxygen species and promoting the transformation of Brønsted acid site to Lewis acid site.The research results provide a theoretical basis for the preparation of efficient and inexpensive Fe-based catalysts from MD.
基金National Natural Science Foundation of China,Grant/Award Numbers:21902021,21908017Fundamental Research Funds for the Central Universities,Grant/Award Numbers:DUT20RC(4)020,DUT20RC(4)018+1 种基金Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering,Grant/Award Numbers:KLIEEE-20-01,KLIEEE-21-02Supercomputing Center of Dalian University of Technology。
文摘As one of the most important chemicals and carbon-free energy carriers,ammonia(NH3)has significant energy-related applications in industry and agriculture.Ninety percent of NH_(3) is produced by the Haber-Bosch process using high-purity N_(2) and H_(2) at high temperatures and pressures,which consumes about 1%of the total energy production and causes 1.4% of global CO_(2) emissions.The environmentally friendly electrochemical nitrogen reduction reaction(NRR)with low energy consumption is a promising alternative to the conventional Haber-Bosch process.However,the main issue is the low Faradaic efficiency and NH3 selectivity of electrochemical NRR,caused by inert nitrogen molecules and competitive hydrogen evolution reaction.As one of the cheapest and most abundant transition metals widely utilized in the Haber-Bosch process,the Fe element has presented the potential high performance for the electrochemical NRR.This article summarizes recent advances and research progress in non-noble Fe-based catalysts used for NH_(3) electrosynthesis.Various synthetic protocols,structure/morphology modification,performance improvement,and reaction mechanisms are comprehensively presented.Based on recent experimental and theoretical studies,we aim to illuminate the structure-property relationship and offer an excellent opportunity for engineering advanced Fe-based catalysts for nitrogen fixation.The most critical challenges and opportunities for Fe-based catalysts are also provided.This review would open up a promising avenue toward developing platinum-group-metal-free catalysts for electrochemical NRR applications in the future.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
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 Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
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)+4 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 2025119The XAS experiments were conducted in Beijing Synchrotron Radiation Facility(BSRF)and Shanghai Synchrotron Radiation Facility(SSRF).
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supported by the Hainan Province Science and Technology Special Fund(ZDYF2023GXJS165)the National Natural Science Foundation of China(52164028,22109035,52274297)+2 种基金the Foundation of State Key Laboratory of Marine Resource Utilization in South China Sea(Hainan University,MRUKF2021029)the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20084,21170)the Specific Research Fund of the Innovation Platform for Academicians of Hainan Province。
文摘The development of catalysts with highly efficient oxygen evolution performance and low-Ir loading is key to scaling up the application of proton exchange membrane(PEM)water electrolysis technology.Here,an Ir-skin catalyst(Ir@KM)is realized on a potassium-manganese oxide(K_(0.25)MnO_(x)(KM))using an ion-exchange method.The Ir-skin over the prepared Ir@KM has a low Ir-Ir atomic distance,endowing an energetically favorable oxide path mechanism to allow a low theoretical overpotential of 0.13 V.Ir@KM offers a low overpotential of~280 mV at a current density of 10 mA cm^(-2)and provides a high mass activity of up to 18,500 A at a cell voltage of 1.8 V in PEM,which is 17.6 times higher than that of IrO_(2),demonstrating a significant advantage in reducing the cost of the membrane electrode.The presented Ir-skin concept represents a promising strategy to fabricate low-Ir catalyst with high activity and durability for practical applications of PEM.
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supported by the National Natural Science Foundation of China(No.52300170).
文摘Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
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 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 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supported by the Taishan Scholar Program of Shandong Province(tsqn202507090)Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(CPSF)(GZB20250022)+1 种基金Natural Science Foundation of Shandong Province(ZR2025QC1086)Young Talents Project at Ocean University of China。
文摘The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.
