Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platin...Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platinum group metal(PGM)catalysts creates a barrier for the large-scale application of PEMFC.Tremendous efforts have been devoted to the development of low-cost PGM-free catalysts,especially the Fe-N-C catalysts,to replace the expensive PGM catalysts.However,the characterization methods and evaluation standards of the catalysts varies,which is not conducive to the comparison of PGM-free catalysts.U.S.Department of energy(DOE)is the only authority that specifies the testing standards and activity targets for PGM-free catalysts.In this review,the major breakthroughs of Fe-N-C catalysts are outlined with the reference of DOE standards and targets.The preparation and characteristics of these highly active Fe-N-C catalysts are briefly introduced.Moreover,the efforts on improving the mass transfer and the durability issue of Fe-N-C fuel cell are discussed.Finally,the prospective directions concerning the comprehensive evaluation of the Fe-N-C catalysts are proposed.展开更多
An extensive analysis of iron-nitrogen-carbon(Fe-N-C)electrocatalysts synthesis and activity is presented concerning synthesis conditions such as initial Fe content,pyrolysis temperature and atmosphere(inert N_(2),red...An extensive analysis of iron-nitrogen-carbon(Fe-N-C)electrocatalysts synthesis and activity is presented concerning synthesis conditions such as initial Fe content,pyrolysis temperature and atmosphere(inert N_(2),reducing NH_(3),oxidizing Cl_(2) and their sequential combinations)and the influence of an external magnetic field on their performance in oxygen reduction reaction(ORR).Thermosetting porous polymers doped with FeCl_(3) were utilized as the Fe-N-C catalysts precursors.The pyrolysis temperature was varied within a 700-900℃range.The temperature and atmosphere of pyrolysis strongly affect the porosity and compositi on of the resultant Fe-N-C catalysts,while the in itial amount of Fe precursor shows much weaker impact.Pyrolysis under NH_(3) yields materials similar to those pyrolyzed under an inert atmosphere(N_(2)).In contrast,pyrolysis under Cl_(2) yields carbon of peculiar character with highly disordered structure and extensive microporosity.The application of a static external magnetic field strongly enhances the ORR process(herein studied in an alkaline environment)and the enhancement correlates with the Fe content in the Fe-N-C catalysts.The Fe-N-C materials containing ferromagnetic iron phase embedded in N-doped microporous carbon constitute attractive catalysts for magnetic field-aided anion exchange membrane fuel cell technology.展开更多
Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies ope...Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.展开更多
Non-precious metal electrocatalysts(such as Fe-N-C materials) for the oxygen(O_(2)) reduction reaction demand a high catalyst loading in fuel cell devices to achieve workable performance. However, the extremely low so...Non-precious metal electrocatalysts(such as Fe-N-C materials) for the oxygen(O_(2)) reduction reaction demand a high catalyst loading in fuel cell devices to achieve workable performance. However, the extremely low solubility of O_(2) in water creates severe mass transport resistance in the thick catalyst layer of Fe-N-C catalysts. Here, we introduce silicalite-1 nanocrystals with hydrophobic cavities as sustainable O_(2) reservoirs to overcome the mass transport issue of Fe-N-C catalysts. The extra O_(2) supply to the adjacent catalysts significantly alleviated the negative effects of the severe mass transport resistance. The hybrid catalyst(Fe-N-C@silicalite-1) achieved a higher limiting current density than Fe-N-C in the half-cell test. In the H_(2)-O_(2) and H_2-air proton exchange membrane fuel cells, Fe-N-C@silicalite-1 exhibited a 16.3% and 20.2% increase in peak power density compared with Fe-N-C, respectively. The O_(2)-concentrating additive provides an effective approach for improving the mass transport imposed by the low solubility of O_(2) in water.展开更多
Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the ac...Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the active site hosts, its hostility to electron/mass transfer could lead to the incomplete fulfillment of the catalytic activity. Besides, the formation of inactive metallic Fe particles during the conventional catalyst synthesis could also decrease the active site density and complicate the identification of real active site. Herein, we developed a facial hydrogen etching methodology to yield single site Fe-N-C catalysts featured with micro/mesoporous hierarchical structure. The hydrogen concentration in pyrolysis process was designated to effectively regulate the pore structure and active site density of the resulted catalysts.The optimized sample achieves excellent ORR catalytic performance with an ultralow H2O2 yield(1%)and superb stability over 10,000 cycles. Our finding provides new thoughts for the rational design of hierarchically porous carbon-based materials and highly promising non-precious metal ORR catalysts.展开更多
Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct intera...Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.展开更多
Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysi...Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysis.Considering the challenge of serious aggregation,rational synthesis of an atomic catalyst with good dispersion of atoms is paramount to the development of these catalysts.Herein,we report an enhanced confinement strategy to synthesize a catalyst comprised of atomically dispersed Fe supported on porous nitrogen-doped graphitic carbon from the novel and more cross-linkable Melamine-Glyoxal Resin.Densified isolated grid trapping,excessive melamine restricting,and nitrogen anchoring are strongly combined to ensure the final atomic-level dispersion of metal atoms.Experimental studies revealed enhanced kinetics of the obtained catalyst towards oxygen reduction reaction(ORR).This catalytic activity originates from the highly active surface with atomically dispersed iron sites as well as the multi-level three-dimensional structure with fast mass and electron transfer.The enhanced confinement strategy endows the resin-derived atomic catalyst with a great prospect to develop for commercialization in future.展开更多
Fe-N-C catalysts,as promising non-precious metal alternatives for the oxygen reduction reaction(ORR),still suffer from severe mass transport limitations in proton exchange membrane fuel cells(PEMFCs)due to water flood...Fe-N-C catalysts,as promising non-precious metal alternatives for the oxygen reduction reaction(ORR),still suffer from severe mass transport limitations in proton exchange membrane fuel cells(PEMFCs)due to water flooding of active sites embedded in micropores.Although pore engineering through a selected template is a general strategy,the structural features of an ideal template,particularly those governing the exposure of active sites and thus affecting mass transport,remain elusive.Here,we demonstrate that low-porosity carbon templates maximize the ratio of active sites distributed at or near the surface,thereby enhancing their exposure and accessibility while reducing mass transport resistance during the ORR process.The C_(lp-1)@PPy and C_(lp-2)@PPy(PPy=polypyrrole)catalysts,derived from low-porosity carbon templates,achieve peak power densities of 0.96 and 1.03 W·cm^(-2) under H_(2)/O_(2)and 0.50 and 0.52 W·cm^(-2) under H_(2)/air,demonstrating excellent performance in PEMFC tests.Structural and electrochemical characterizations reveal that the enhanced surface exposure of active sites effectively mitigates mass transport resistance during the ORR,thereby offering a general design principle for overcoming mass transport limitations in Fe-N-C catalysts for PEMFC applications.展开更多
Developing high-performance,durable,and cost-effective oxygen reduction reaction(ORR)catalysts is essential for advancing next-generation energy devices like zinc-air batteries(ZABs).Herein,we engineer a hybrid Fe-N-C...Developing high-performance,durable,and cost-effective oxygen reduction reaction(ORR)catalysts is essential for advancing next-generation energy devices like zinc-air batteries(ZABs).Herein,we engineer a hybrid Fe-N-C catalyst(FeSA-Fe_(NP)/CeO_(2)@NC)integrating atomically dispersed Fe-Nx sites,Fe nanoparticles,and oxygen vacancy-rich CeO_(2) nanoparticles within a nitrogen-doped carbon matrix.Interfacial charge transfer and oxygen vacancy-mediated electron redistribution,synergistically enhanced by strong metal-support interactions(SMSI),optimize the electronic configuration of Fe-Nx sites and reduce their electron density.The resulting catalyst exhibits exceptional ORR activity and stability,featuring a half-wave potential of 0.925 V(vs.RHE)in alkaline media and minimal degradation(1%and 2.8%negative shifts after 10,000/20,000 cycles).In ZABs,it achieves a peak power density of 310.29 mW·cm-2 while sustaining stable operation for over 600 h.This work demonstrates dual role of CeO_(2) in enhancing activity and stability,establishing a design principle for high-performance electrocatalysts in energy conversion systems.展开更多
The remediation of nitroaromatic-contaminated water systems remains a critical environmental challenge,creating the urgent need for cost-effective,non-precious metal catalysts to increase wastewater biodegradability.I...The remediation of nitroaromatic-contaminated water systems remains a critical environmental challenge,creating the urgent need for cost-effective,non-precious metal catalysts to increase wastewater biodegradability.In this study,we present an Fe/N-functionalized three-dimensional porous carbon(Fe-N-C)catalyst synthesized via a straightforward pyrolysis approach that enables efficient nitrobenzene(NB)degradation via electrochemical and chemical reduction pathways.The hightemperature pyrolysis process facilitates the iron-catalyzed reconstruction of the carbon matrix,resulting in a hierarchically porous structure with increased graphitization and uniformly distributed macrocyclic Fe-N_(4) coordination sites.These structural features give the Fe-N-C catalyst exceptional electron transfer kinetics,catalytic activity,and pH adaptability,surpassing conventional graphite(GR)and nitrogen-doped carbons(NPCs)in NB reduction.Systematic evaluation of the electrochemical reduction performance revealed that the Fe-N-C electrode achieved the highest NB removal efficiency.To further assess the versatility of the catalyst,a functionalized Fe-N-C/zero-valent iron(ZVI)composite was engineered by integrating Fe-N-C as a catalytic layer onto the reductant ZVI.Compared with ZVI alone,this composite markedly increased the NB reduction efficiency.These findings provide valuable insights into the electrochemical reduction process of Fe-N-C and new directions for the rational design of efficient nitrobenzene reduction systems.展开更多
Hydrogen peroxide that is produced through the two-electron pathway during the catalysis of oxygen reduction reaction(ORR)is recognized as harmful to the stability of nitrogen-doped carbon and Fe-based nonprecious cat...Hydrogen peroxide that is produced through the two-electron pathway during the catalysis of oxygen reduction reaction(ORR)is recognized as harmful to the stability of nitrogen-doped carbon and Fe-based nonprecious catalyst(Fe-N-C)for fuel cell application.A major remaining scientific question is how fast the removal of these deleterious intermediates can contribute to stability enhancement.Here,we report that the stability of Fe-N-C catalysts is positively correlated with the kinetic constant of hydrogen peroxide decomposition.Modulation of the H_(2)O_(2) decomposition kinetics by applying the frequency factor of the Arrhenius equation from 800 to 30000 s^(-1) for TiO_(2),CeO_(2) and ZrO_(2) reduced the decay rate of Fe-N-C catalysts from 0.151% to ‒0.1% in a 100-hour stability test.Fe-N-C/ZrO_(2) with a frequency factor of 30000 s^(-1) showed a 10% increase in current density during a 100-hour stability test and almost no decay during 15 hours of continuous fuel cell operation at a high potential of 0.7 V.展开更多
Fe-N-C materials,boasting exceptional catalytic activity,stand out as ideal candidates for replacing platinum-group metals in catalyzing the oxygen reduction reaction(ORR).However,their stability is challenged by the ...Fe-N-C materials,boasting exceptional catalytic activity,stand out as ideal candidates for replacing platinum-group metals in catalyzing the oxygen reduction reaction(ORR).However,their stability is challenged by the attack of oxidative radicals generated from the incomplete reduction of H_(2)O_(2).Inspired by the antioxidant mechanisms of natural organisms,Se dopants were introduced with antioxidant properties into the Fe-N-C materials to serve as effective H_(2)O_(2) scavengers.Experimental results reveal that the Se-doped samples are capable of swiftly catalyzing the H_(2)O disproportion decomposition,markedly diminishing the H_(2)O yield and consequently decreasing the generation of reactive oxygen species(ROs).Furthermore,the incorporation of Se significantly enhances the corrosion resistance of the carbon substrate.Capitalizing on the synergistic impact detailed above,the series of Se-modified Fe-N-C catalysts all exhibit significantly superior stability compared to their undoped counterparts in acidic media.Our work provides a proactive defense strategy for enhancing the durability of the Fe-N-C catalysts and forges a novel route for the development of highly stable non-noble metal ORR catalysts.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
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
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
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
基金supported by the National Thousand Talents Plan of Chinathe National Natural Science Foundation of China(Grant Nos.21673014 and U1766216)+1 种基金the 111 project(B17002)funded by the Ministry of Education of Chinathe Fundamental Research Funds for the Central Universities of China
文摘Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platinum group metal(PGM)catalysts creates a barrier for the large-scale application of PEMFC.Tremendous efforts have been devoted to the development of low-cost PGM-free catalysts,especially the Fe-N-C catalysts,to replace the expensive PGM catalysts.However,the characterization methods and evaluation standards of the catalysts varies,which is not conducive to the comparison of PGM-free catalysts.U.S.Department of energy(DOE)is the only authority that specifies the testing standards and activity targets for PGM-free catalysts.In this review,the major breakthroughs of Fe-N-C catalysts are outlined with the reference of DOE standards and targets.The preparation and characteristics of these highly active Fe-N-C catalysts are briefly introduced.Moreover,the efforts on improving the mass transfer and the durability issue of Fe-N-C fuel cell are discussed.Finally,the prospective directions concerning the comprehensive evaluation of the Fe-N-C catalysts are proposed.
基金supported by the National Science Centre,Poland,UMO-2016/23/B/ST5/00127。
文摘An extensive analysis of iron-nitrogen-carbon(Fe-N-C)electrocatalysts synthesis and activity is presented concerning synthesis conditions such as initial Fe content,pyrolysis temperature and atmosphere(inert N_(2),reducing NH_(3),oxidizing Cl_(2) and their sequential combinations)and the influence of an external magnetic field on their performance in oxygen reduction reaction(ORR).Thermosetting porous polymers doped with FeCl_(3) were utilized as the Fe-N-C catalysts precursors.The pyrolysis temperature was varied within a 700-900℃range.The temperature and atmosphere of pyrolysis strongly affect the porosity and compositi on of the resultant Fe-N-C catalysts,while the in itial amount of Fe precursor shows much weaker impact.Pyrolysis under NH_(3) yields materials similar to those pyrolyzed under an inert atmosphere(N_(2)).In contrast,pyrolysis under Cl_(2) yields carbon of peculiar character with highly disordered structure and extensive microporosity.The application of a static external magnetic field strongly enhances the ORR process(herein studied in an alkaline environment)and the enhancement correlates with the Fe content in the Fe-N-C catalysts.The Fe-N-C materials containing ferromagnetic iron phase embedded in N-doped microporous carbon constitute attractive catalysts for magnetic field-aided anion exchange membrane fuel cell technology.
基金funding from the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Program (Grant No. 681719)the German Research Foundation (Grant No.GSC1070) for financial support。
文摘Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.
基金financially supported by the Natural Science Foundation of Beijing Municipality(No.Z200012)the National Natural Science Foundation of China(Nos.U21A20328 and 21975010)+2 种基金the National Key Research and Development Program of China(No. 2021YFB4000601)the China Postdoctoral Science Foundation(No.2022M720013)the Postdoctoral Fellowship Program of CPSF(No.GZB20230926)。
文摘Non-precious metal electrocatalysts(such as Fe-N-C materials) for the oxygen(O_(2)) reduction reaction demand a high catalyst loading in fuel cell devices to achieve workable performance. However, the extremely low solubility of O_(2) in water creates severe mass transport resistance in the thick catalyst layer of Fe-N-C catalysts. Here, we introduce silicalite-1 nanocrystals with hydrophobic cavities as sustainable O_(2) reservoirs to overcome the mass transport issue of Fe-N-C catalysts. The extra O_(2) supply to the adjacent catalysts significantly alleviated the negative effects of the severe mass transport resistance. The hybrid catalyst(Fe-N-C@silicalite-1) achieved a higher limiting current density than Fe-N-C in the half-cell test. In the H_(2)-O_(2) and H_2-air proton exchange membrane fuel cells, Fe-N-C@silicalite-1 exhibited a 16.3% and 20.2% increase in peak power density compared with Fe-N-C, respectively. The O_(2)-concentrating additive provides an effective approach for improving the mass transport imposed by the low solubility of O_(2) in water.
基金supported by the National Natural Science Foundation of China(21633008,21433003,U1601211,21733004)National Science and Technology Major Project(2016YFB0101202)+1 种基金Jilin Province Science and Technology Development Program(20150101066JC,20160622037JC,20170203003SF,20170520150JH)Hundred Talents Program of Chinese Academy of Sciences and the Recruitment Program of Foreign Experts(WQ20122200077)
文摘Rational regulation on pore structure and active site density plays critical roles in enhancing the performance of Fe-N-C catalysts. As the microporous structure of the carbon substrate is generally regarded as the active site hosts, its hostility to electron/mass transfer could lead to the incomplete fulfillment of the catalytic activity. Besides, the formation of inactive metallic Fe particles during the conventional catalyst synthesis could also decrease the active site density and complicate the identification of real active site. Herein, we developed a facial hydrogen etching methodology to yield single site Fe-N-C catalysts featured with micro/mesoporous hierarchical structure. The hydrogen concentration in pyrolysis process was designated to effectively regulate the pore structure and active site density of the resulted catalysts.The optimized sample achieves excellent ORR catalytic performance with an ultralow H2O2 yield(1%)and superb stability over 10,000 cycles. Our finding provides new thoughts for the rational design of hierarchically porous carbon-based materials and highly promising non-precious metal ORR catalysts.
基金supported by the Natural Science Foundation of Beijing Municipality (Z200012)the National Natural Science Foundation of China (U21A20328,22225903)the National Key Research and Development Program of China (2021YFB4000601)。
文摘Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.
基金financially supported by the Hebei Province Natural Science Foundation Innovation Group Project(B2021203016)the National Natural Science Foundation of China(51674221 and 51704261)+1 种基金the Provincial Graduate Innovation Assistant Project of Yanshan University(023000309)partially supported by the ARC Future Fellowship(FT180100705)of Australia。
文摘Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysis.Considering the challenge of serious aggregation,rational synthesis of an atomic catalyst with good dispersion of atoms is paramount to the development of these catalysts.Herein,we report an enhanced confinement strategy to synthesize a catalyst comprised of atomically dispersed Fe supported on porous nitrogen-doped graphitic carbon from the novel and more cross-linkable Melamine-Glyoxal Resin.Densified isolated grid trapping,excessive melamine restricting,and nitrogen anchoring are strongly combined to ensure the final atomic-level dispersion of metal atoms.Experimental studies revealed enhanced kinetics of the obtained catalyst towards oxygen reduction reaction(ORR).This catalytic activity originates from the highly active surface with atomically dispersed iron sites as well as the multi-level three-dimensional structure with fast mass and electron transfer.The enhanced confinement strategy endows the resin-derived atomic catalyst with a great prospect to develop for commercialization in future.
基金the National Key R&D Program of China(No.2024YFA1509500)the National Natural Science Foundation of China(No.22479010)+5 种基金the financial support from the Chongqing Municipal Natural Science Foundation(No.CSTB2024NSCQJQX0034)Shenzhen Science and Technology Program(No.KJZD20240903101359020)the financial support from the National Natural Science Foundation of China(No.22372004)the support from the Experimental Center of Advanced Materials of the Beijing Institute of Technologythe technical support from Biological and Medical Engineering Core Facilities of Beijing Institute of Technologythe Analysis and Testing Center of Beijing Institute of Technology.
文摘Fe-N-C catalysts,as promising non-precious metal alternatives for the oxygen reduction reaction(ORR),still suffer from severe mass transport limitations in proton exchange membrane fuel cells(PEMFCs)due to water flooding of active sites embedded in micropores.Although pore engineering through a selected template is a general strategy,the structural features of an ideal template,particularly those governing the exposure of active sites and thus affecting mass transport,remain elusive.Here,we demonstrate that low-porosity carbon templates maximize the ratio of active sites distributed at or near the surface,thereby enhancing their exposure and accessibility while reducing mass transport resistance during the ORR process.The C_(lp-1)@PPy and C_(lp-2)@PPy(PPy=polypyrrole)catalysts,derived from low-porosity carbon templates,achieve peak power densities of 0.96 and 1.03 W·cm^(-2) under H_(2)/O_(2)and 0.50 and 0.52 W·cm^(-2) under H_(2)/air,demonstrating excellent performance in PEMFC tests.Structural and electrochemical characterizations reveal that the enhanced surface exposure of active sites effectively mitigates mass transport resistance during the ORR,thereby offering a general design principle for overcoming mass transport limitations in Fe-N-C catalysts for PEMFC applications.
基金support from the National Key R&D Program of China:Strategic International Innovation Cooperation(2024YFE020940O)the National Natural Science Foundation of China(52373187,52573228)+1 种基金the National Youth Top-notch Talent Support Program of China,the Natural Science Foundation of Jiangxi Province(20224ACB204006)the"Double Thousand Plan"Science and Technology Innovation High-End Talent Project of Jiangxi Province(jxsq2023201094).
文摘Developing high-performance,durable,and cost-effective oxygen reduction reaction(ORR)catalysts is essential for advancing next-generation energy devices like zinc-air batteries(ZABs).Herein,we engineer a hybrid Fe-N-C catalyst(FeSA-Fe_(NP)/CeO_(2)@NC)integrating atomically dispersed Fe-Nx sites,Fe nanoparticles,and oxygen vacancy-rich CeO_(2) nanoparticles within a nitrogen-doped carbon matrix.Interfacial charge transfer and oxygen vacancy-mediated electron redistribution,synergistically enhanced by strong metal-support interactions(SMSI),optimize the electronic configuration of Fe-Nx sites and reduce their electron density.The resulting catalyst exhibits exceptional ORR activity and stability,featuring a half-wave potential of 0.925 V(vs.RHE)in alkaline media and minimal degradation(1%and 2.8%negative shifts after 10,000/20,000 cycles).In ZABs,it achieves a peak power density of 310.29 mW·cm-2 while sustaining stable operation for over 600 h.This work demonstrates dual role of CeO_(2) in enhancing activity and stability,establishing a design principle for high-performance electrocatalysts in energy conversion systems.
基金financial support from the National Natural Science Foundation of China(Nos.22178003,22478427,and 22438001)financial support from Science Foundation of China University of Petroleum,Beijing(Nos.2462023YJRC022 and 2462023BJRC006).
文摘The remediation of nitroaromatic-contaminated water systems remains a critical environmental challenge,creating the urgent need for cost-effective,non-precious metal catalysts to increase wastewater biodegradability.In this study,we present an Fe/N-functionalized three-dimensional porous carbon(Fe-N-C)catalyst synthesized via a straightforward pyrolysis approach that enables efficient nitrobenzene(NB)degradation via electrochemical and chemical reduction pathways.The hightemperature pyrolysis process facilitates the iron-catalyzed reconstruction of the carbon matrix,resulting in a hierarchically porous structure with increased graphitization and uniformly distributed macrocyclic Fe-N_(4) coordination sites.These structural features give the Fe-N-C catalyst exceptional electron transfer kinetics,catalytic activity,and pH adaptability,surpassing conventional graphite(GR)and nitrogen-doped carbons(NPCs)in NB reduction.Systematic evaluation of the electrochemical reduction performance revealed that the Fe-N-C electrode achieved the highest NB removal efficiency.To further assess the versatility of the catalyst,a functionalized Fe-N-C/zero-valent iron(ZVI)composite was engineered by integrating Fe-N-C as a catalytic layer onto the reductant ZVI.Compared with ZVI alone,this composite markedly increased the NB reduction efficiency.These findings provide valuable insights into the electrochemical reduction process of Fe-N-C and new directions for the rational design of efficient nitrobenzene reduction systems.
基金financially supported by the National Key Research and Development Program of China(2021YFA1502000)the National Natural Science Foundation of China(22022502 and 22179012)Natural Science Foundation of Chongqing,China(CSTB2023NSCQLZX0084).
文摘Hydrogen peroxide that is produced through the two-electron pathway during the catalysis of oxygen reduction reaction(ORR)is recognized as harmful to the stability of nitrogen-doped carbon and Fe-based nonprecious catalyst(Fe-N-C)for fuel cell application.A major remaining scientific question is how fast the removal of these deleterious intermediates can contribute to stability enhancement.Here,we report that the stability of Fe-N-C catalysts is positively correlated with the kinetic constant of hydrogen peroxide decomposition.Modulation of the H_(2)O_(2) decomposition kinetics by applying the frequency factor of the Arrhenius equation from 800 to 30000 s^(-1) for TiO_(2),CeO_(2) and ZrO_(2) reduced the decay rate of Fe-N-C catalysts from 0.151% to ‒0.1% in a 100-hour stability test.Fe-N-C/ZrO_(2) with a frequency factor of 30000 s^(-1) showed a 10% increase in current density during a 100-hour stability test and almost no decay during 15 hours of continuous fuel cell operation at a high potential of 0.7 V.
基金supported by the National Natural Science Foundation of China(22209102)the Fundamental Research Program of Shanxi Province(202203021212398).
文摘Fe-N-C materials,boasting exceptional catalytic activity,stand out as ideal candidates for replacing platinum-group metals in catalyzing the oxygen reduction reaction(ORR).However,their stability is challenged by the attack of oxidative radicals generated from the incomplete reduction of H_(2)O_(2).Inspired by the antioxidant mechanisms of natural organisms,Se dopants were introduced with antioxidant properties into the Fe-N-C materials to serve as effective H_(2)O_(2) scavengers.Experimental results reveal that the Se-doped samples are capable of swiftly catalyzing the H_(2)O disproportion decomposition,markedly diminishing the H_(2)O yield and consequently decreasing the generation of reactive oxygen species(ROs).Furthermore,the incorporation of Se significantly enhances the corrosion resistance of the carbon substrate.Capitalizing on the synergistic impact detailed above,the series of Se-modified Fe-N-C catalysts all exhibit significantly superior stability compared to their undoped counterparts in acidic media.Our work provides a proactive defense strategy for enhancing the durability of the Fe-N-C catalysts and forges a novel route for the development of highly stable non-noble metal ORR catalysts.
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.
