Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AAC...Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AACH) and their mixture were obtained, and then, different kinds of alumina were obtained after calcination. Three catalysts supported on the different alumina were obtained via impregnating cobalt and ruthenium by incipient wetness. The effects of different precipitants on composition of precursors were?studied by XRD, FTIR, and TGA. The property and structure of alumina were studied by XRD and BET. The supported catalysts were studied by characterizations of XRD and H2-TPR, and the catalytic performance for Fischer-Tropsch synthesis (FTS) were evaluated at a fix-bed reactor. The relations among the composition of precursors, the property of alumina and the catalytic performance of supported catalysts were researched thoroughly.展开更多
The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(wate...The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.展开更多
A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based cataly...A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based catalysts were characterized by XRD, TEM and BET techniques. Their catalytic performances were tested in a slurry-bed reactor under FTS reaction conditions. The drying and crystallization were carried out simultaneously during SCFD, therefore, the catalysts prepared by SCFD method have ideal structure and show the FTS performance superior to the others prepared by CD method. The FTS activity and selectivity were improved via adding Zn, Mn and K promoters, and less CH4 and CO2 as well as higher yield of C5＋ products were achieved. The optimal performance of a 92% CO conversion and a 65% C5＋ product yield was obtained over a catalyst with the component of Co/Zn/Mn/K = 100/50/10/7. Furthermore, the catalytic performance was studied under the conditions of liquid-phase and supercritical phase slurry-bed, and C5＋ product yield were 57.4% and 65.4%, respectively. In summary, better catalytic performance was obtained using the nanosized catalyst prepared by SCFD method under supercritical reaction conditions, resulting in higher conversion of CO, less CO2 byproduct, and higher yield of C5＋ products.展开更多
The development of cost-effective and environmentally benign catalysts for propane dehydrogenation(PDH)is critical for sustainable propylene production.In this study,cobalt-based catalysts supported on mesoporous MCM-...The development of cost-effective and environmentally benign catalysts for propane dehydrogenation(PDH)is critical for sustainable propylene production.In this study,cobalt-based catalysts supported on mesoporous MCM-41 were systematically modified via incorporation and impregnation of tin species with distinct oxidation states(Sn(II)and Sn(IV))to investigate their influence upon catalytic activity and stability.Comprehensive physicochemical characterization,including XRD,BET-BJH,Raman,XPS,H_(2)-TPR,NH_(3)-TPD,and DRS,demon-strated that Sn(II)doping significantly enhanced the i)metal dispersion,ii)Co^(2+)stabilization,and iii)meso-porous framework integrity.Amongst the synthesized catalysts,Co/Sn(II)@MCM-41 exhibited the highest Co^(2+)/Co^(3+)ratio(of 2.846),optimal acid site distribution,and superior textural properties,correlating with the best catalytic performance(of 18.5%and 92%for conversion and propylene selectivity,respectively),and the lowest deactivation rate(kd=0.068 h^(-1))at 580◦C.In contrast,Sn(IV)incorporation results in a lower Co^(2+)/Co^(3+)ratio and weaker metal-support interactions,leading to a reduced population of active sites and inferior catalytic performance compared to that of Sn(II).These results highlighted the critical role of the tin oxidation state in tuning surface chemistry and catalyst durability.This work offers valuable insights toward the rational design of robust,non-noble metal catalysts for industrially relevant PDH processes.展开更多
We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various re...We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various reaction conditions under microwave irradiation(0-50 W).These conditions included reaction temperatures(300-600℃),oxygen concentrations(0-6%),and varying K^(+)doping levels on the catalysts'activity.The crystalline phase,microstructure,and the catalytic activity of the catalyst were analyzed by XRD,TEM,H_2-TPR,and O_(2)-TPD.The experimental results reveal that La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts consistently form homogeneous perovskite nanoparticles across different doping levels.The NO decomposition efficiency on these catalysts initially increases and then decreases with variations in doping amount,temperature,and microwave power.Additionally,an increase in oxygen concentration positively influences NO conversion rates.The optimal performance is observed with La_(0.7)K_(0.3)CoO_(3)catalyst under conditions of x=0.3,400℃,10 W microwave power,and 4%oxygen concentration,achieving a peak NO conversion rate of La_(0.7)K_(0.3)CoO_(3)catalyst is 93.1%.展开更多
Exploring the anodic reaction to substitute conventional oxygen evolution reaction(OER)for the synthesis of complex pharmaceutical molecules is highly attractive.Here,we report an electrocatalytic strategy for dehydro...Exploring the anodic reaction to substitute conventional oxygen evolution reaction(OER)for the synthesis of complex pharmaceutical molecules is highly attractive.Here,we report an electrocatalytic strategy for dehydrogenative[4+2]cycloaddition of N,N-dialkylanilines with maleimides via dual functionalization of both C(sp3)-H and C(sp2)-H bonds,by using an electrochemically activated cobalt carbonate hydroxide hydrate supported on carbon cloth(CCHH-A/CC),affording various tetrahydroquinolines with high yields.This electrochemical transformation proceeds with high activity and stability,as well as good substrate compatibility.Mechanism study shows thatα-aminoalkyl radical exists in the electrooxidation reaction.This strategy shows significant potential for the synthesis of valuable chemicals by using an electrocatalytic strategy.展开更多
A cobalt-based catalyst was directly photo-deposited on the surface of a widely used n-type nano-structured semiconductor(TiO_(2)).Different thicknesses of the TiO 2 films as well as different time of photo-deposition...A cobalt-based catalyst was directly photo-deposited on the surface of a widely used n-type nano-structured semiconductor(TiO_(2)).Different thicknesses of the TiO 2 films as well as different time of photo-deposition of the Co-based catalyst on TiO_(2) films have been optimized.It was found that the electrode with 3 layers of TiO_(2) film(in 8 m thickness) and 1 hour photo-deposition of the cobalt-based catalyst by light irradiation from a 500 W Xenon lamp gave the highest current density(~5 mA/cm^(2)).Using this cobalt-modified TiO_(2) film as a working electrode in an electrochemical device,highly efficient water oxidation has been demonstrated in a pH 7.0 aqueous solution with low overpotential.展开更多
To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprisi...To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprising Co,Co_(3)O_(4)and CoN,as well as numerous N heteroatoms,on graphene nanosheets(Co/Co_(3)O_(4)/CoN/NG).The Co/Co_(3)O_(4)/CoN nanoparticles with the size of less than 50 nm are homogeneously dispersed on N-doped graphene(NG)substrate,which greatly improve the catalytic behaviors for ORR.The results show that the half-wave potential is as high as 0.80 V vs.RHE and the limiting current density is 4.60 mA·cm^(−2),which are close to those of commercially available platinum/carbon(Pt/C)catalysts.Applying as cathodic catalyst for ZABs,the battery shows large specific capacity and open circuit voltage of 843.0 mAh∙g^(−1) and 1.41 V,respectively.The excellent performance is attributed to the efficient two-dimensional structure with high accessible surface area and the numerous multiple active sites provided by highly scattered Co/Co_(3)O_(4)/CoN particles and doped nitrogen on the carbon matrix.展开更多
Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor ...Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor materials have been intensively explored,some severe issues,such as rapid charge recombination and sluggish redox reaction kinetics,remain.In this regard,cocatalyst modifi cation by trapping charges and boosting surface reactions is one of the most effi cient strategies to improve the effi ciency of semiconductor photocatalysts.This review focuses on recent advances in CO_(2)photoreduction over costeff ective and earth-abundant cobalt(Co)-based cocatalysts,which are competitive candidates of noble metals for practical applications.First,the functions of Co-based cocatalysts for promoting photocatalytic CO_(2)reduction are briefl y discussed.Then,diff erent kinds of Co-based cocatalysts,including cobalt oxides and hydroxides,cobalt nitrides and phosphides,cobalt sulfi des and selenides,Co single-atom,and Co-based metal–organic frameworks(MOFs),are summarized.The underlying mechanisms of these Co-based cocatalysts for facilitating CO_(2)adsorption–activation,boosting charge separation,and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations.In addition,the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO_(2)reduction is highlighted in some selected examples.Finally,the challenges and future perspectives on constructing more effi cient Co-based cocatalysts for practical applications are proposed.展开更多
The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A...The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A major challenge to their performance is the corrosion occurring at phase boundaries under harsh operating conditions.This study investigates the effects of pulsed magnetic field treatment(PMT)on improving corrosion resistance at phase boundaries,specifically at the carbide/matrix Co interface,and seeks to clarify the underlying mechanisms.Advanced characterization techniques,including scanning electron microscopy(SEM),in situ transmission electron microscopy(TEM),in situ scanning kelvin probe force microscopy(SKPFM),and density functional theory(DFT)calculations,were employed.PMT samples exhibited no interface corrosion cracking or carbide spalling and showed a significant reduction in corrosion depth.TEM analysis revealed reduced lattice distortion at phase boundaries and a partial transformation of face-centered cubic(FCC)Co to hexagonal closepacked(HCP)Co.The enhanced corrosion resistance at phase boundaries is attributed to changes in the electronic work function(EWF),as determined by SKPFM measurements and DFT calculations.展开更多
The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the mo...The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after-treatment tech-nology,which requires the catalyst to have superior low temperature activity.Compared with cerium oxide which is widely used,cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology.This paper elaborates on the influence of modification techniques such as doping,loading,and solid solution on the catalytic performance of cobalt-based catalysts in soot oxidation.Along the same lines,it further reviews the research progress on cobalt-based oxide catalysts with specific dimensional structures and morphologies in soot oxidation.Finally,it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt-based catalysts in soot oxidation.展开更多
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
Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt...Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.展开更多
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
文摘Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AACH) and their mixture were obtained, and then, different kinds of alumina were obtained after calcination. Three catalysts supported on the different alumina were obtained via impregnating cobalt and ruthenium by incipient wetness. The effects of different precipitants on composition of precursors were?studied by XRD, FTIR, and TGA. The property and structure of alumina were studied by XRD and BET. The supported catalysts were studied by characterizations of XRD and H2-TPR, and the catalytic performance for Fischer-Tropsch synthesis (FTS) were evaluated at a fix-bed reactor. The relations among the composition of precursors, the property of alumina and the catalytic performance of supported catalysts were researched thoroughly.
基金financial support from the National Natural Science Foundation of China(21528302)Zhejiang Province Natural Science Foundation(LQ15B060004)
文摘The Co-based catalysts were prepared with different cobalt acetate solutions.Effects of pH value were studied deeply on Fischer–Tropsch synthesis(FTS)through a semi-batch reactor.Among all impregnation solutions(water,butanol,amyl alcohol,acetic acid,nitric acid and ammonium nitrate),the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree.However,the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS.According to FT-IR spectra results,the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity.Whereas,the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts.The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value.
基金supported by Research Fund for the Doctoral Program of Higher Education (China,No.20050010014)
文摘A series of nanosized Co/Zn/Mn/K composite catalysts for Fischer-Tropsch synthesis （FTS） were prepared by supercritical fluid drying （SCFD） method and common drying （CD） method. The nanosized cobalt-based catalysts were characterized by XRD, TEM and BET techniques. Their catalytic performances were tested in a slurry-bed reactor under FTS reaction conditions. The drying and crystallization were carried out simultaneously during SCFD, therefore, the catalysts prepared by SCFD method have ideal structure and show the FTS performance superior to the others prepared by CD method. The FTS activity and selectivity were improved via adding Zn, Mn and K promoters, and less CH4 and CO2 as well as higher yield of C5＋ products were achieved. The optimal performance of a 92% CO conversion and a 65% C5＋ product yield was obtained over a catalyst with the component of Co/Zn/Mn/K = 100/50/10/7. Furthermore, the catalytic performance was studied under the conditions of liquid-phase and supercritical phase slurry-bed, and C5＋ product yield were 57.4% and 65.4%, respectively. In summary, better catalytic performance was obtained using the nanosized catalyst prepared by SCFD method under supercritical reaction conditions, resulting in higher conversion of CO, less CO2 byproduct, and higher yield of C5＋ products.
文摘The development of cost-effective and environmentally benign catalysts for propane dehydrogenation(PDH)is critical for sustainable propylene production.In this study,cobalt-based catalysts supported on mesoporous MCM-41 were systematically modified via incorporation and impregnation of tin species with distinct oxidation states(Sn(II)and Sn(IV))to investigate their influence upon catalytic activity and stability.Comprehensive physicochemical characterization,including XRD,BET-BJH,Raman,XPS,H_(2)-TPR,NH_(3)-TPD,and DRS,demon-strated that Sn(II)doping significantly enhanced the i)metal dispersion,ii)Co^(2+)stabilization,and iii)meso-porous framework integrity.Amongst the synthesized catalysts,Co/Sn(II)@MCM-41 exhibited the highest Co^(2+)/Co^(3+)ratio(of 2.846),optimal acid site distribution,and superior textural properties,correlating with the best catalytic performance(of 18.5%and 92%for conversion and propylene selectivity,respectively),and the lowest deactivation rate(kd=0.068 h^(-1))at 580◦C.In contrast,Sn(IV)incorporation results in a lower Co^(2+)/Co^(3+)ratio and weaker metal-support interactions,leading to a reduced population of active sites and inferior catalytic performance compared to that of Sn(II).These results highlighted the critical role of the tin oxidation state in tuning surface chemistry and catalyst durability.This work offers valuable insights toward the rational design of robust,non-noble metal catalysts for industrially relevant PDH processes.
文摘We presented the preparation and analysis of La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts,supported on microwave-absorbing ceramic carriers,using the sol-gel method.We systematically investigated the effects of various reaction conditions under microwave irradiation(0-50 W).These conditions included reaction temperatures(300-600℃),oxygen concentrations(0-6%),and varying K^(+)doping levels on the catalysts'activity.The crystalline phase,microstructure,and the catalytic activity of the catalyst were analyzed by XRD,TEM,H_2-TPR,and O_(2)-TPD.The experimental results reveal that La_(1-x)K_(x)CoO_(3)(x=0.1-0.4)catalysts consistently form homogeneous perovskite nanoparticles across different doping levels.The NO decomposition efficiency on these catalysts initially increases and then decreases with variations in doping amount,temperature,and microwave power.Additionally,an increase in oxygen concentration positively influences NO conversion rates.The optimal performance is observed with La_(0.7)K_(0.3)CoO_(3)catalyst under conditions of x=0.3,400℃,10 W microwave power,and 4%oxygen concentration,achieving a peak NO conversion rate of La_(0.7)K_(0.3)CoO_(3)catalyst is 93.1%.
基金Financial support was provided by the National Natural Science Foundation of China(21978147,21935001,22090030,22105015)the China Postdoctoral Science Foundation(2019M660421)State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC).
文摘Exploring the anodic reaction to substitute conventional oxygen evolution reaction(OER)for the synthesis of complex pharmaceutical molecules is highly attractive.Here,we report an electrocatalytic strategy for dehydrogenative[4+2]cycloaddition of N,N-dialkylanilines with maleimides via dual functionalization of both C(sp3)-H and C(sp2)-H bonds,by using an electrochemically activated cobalt carbonate hydroxide hydrate supported on carbon cloth(CCHH-A/CC),affording various tetrahydroquinolines with high yields.This electrochemical transformation proceeds with high activity and stability,as well as good substrate compatibility.Mechanism study shows thatα-aminoalkyl radical exists in the electrooxidation reaction.This strategy shows significant potential for the synthesis of valuable chemicals by using an electrocatalytic strategy.
基金supported by Swedish Energy Agency,the Knutand Alice Wallenberg Foundation,China Scholarship Council (CSC)the Natural Natural Science Foundation of China (21120102036)the National Basic Research Program of China (2009CB220009)
文摘A cobalt-based catalyst was directly photo-deposited on the surface of a widely used n-type nano-structured semiconductor(TiO_(2)).Different thicknesses of the TiO 2 films as well as different time of photo-deposition of the Co-based catalyst on TiO_(2) films have been optimized.It was found that the electrode with 3 layers of TiO_(2) film(in 8 m thickness) and 1 hour photo-deposition of the cobalt-based catalyst by light irradiation from a 500 W Xenon lamp gave the highest current density(~5 mA/cm^(2)).Using this cobalt-modified TiO_(2) film as a working electrode in an electrochemical device,highly efficient water oxidation has been demonstrated in a pH 7.0 aqueous solution with low overpotential.
基金financially supported by the National Natural Science Foundation of China (No. 52102100)the Industry-University-Research Cooperation Project of Jiangsu Province, China (No. BY2021525)the Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (No. SJCX22_1944)
文摘To improve the efficiency of cathodic oxygen reduction reaction(ORR)in zinc-air batteries(ZABs),an adsorption-complexation-calcination method was proposed to generate cobalt-based multicomponent nanoparticles comprising Co,Co_(3)O_(4)and CoN,as well as numerous N heteroatoms,on graphene nanosheets(Co/Co_(3)O_(4)/CoN/NG).The Co/Co_(3)O_(4)/CoN nanoparticles with the size of less than 50 nm are homogeneously dispersed on N-doped graphene(NG)substrate,which greatly improve the catalytic behaviors for ORR.The results show that the half-wave potential is as high as 0.80 V vs.RHE and the limiting current density is 4.60 mA·cm^(−2),which are close to those of commercially available platinum/carbon(Pt/C)catalysts.Applying as cathodic catalyst for ZABs,the battery shows large specific capacity and open circuit voltage of 843.0 mAh∙g^(−1) and 1.41 V,respectively.The excellent performance is attributed to the efficient two-dimensional structure with high accessible surface area and the numerous multiple active sites provided by highly scattered Co/Co_(3)O_(4)/CoN particles and doped nitrogen on the carbon matrix.
基金supported by the National Natural Science Foundation of China(Nos.21905049,22178057)the Natural Science Foundation of Fujian Province(Nos.2020J01201,2021J01197)+1 种基金the Research Foundation of the Academy of Carbon Neutrality of Fujian Normal University(TZH2022-07)the Award Program for Minjiang Scholar Professorship。
文摘Conversion of carbon dioxide(CO_(2))into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization.Although various types of semiconductor materials have been intensively explored,some severe issues,such as rapid charge recombination and sluggish redox reaction kinetics,remain.In this regard,cocatalyst modifi cation by trapping charges and boosting surface reactions is one of the most effi cient strategies to improve the effi ciency of semiconductor photocatalysts.This review focuses on recent advances in CO_(2)photoreduction over costeff ective and earth-abundant cobalt(Co)-based cocatalysts,which are competitive candidates of noble metals for practical applications.First,the functions of Co-based cocatalysts for promoting photocatalytic CO_(2)reduction are briefl y discussed.Then,diff erent kinds of Co-based cocatalysts,including cobalt oxides and hydroxides,cobalt nitrides and phosphides,cobalt sulfi des and selenides,Co single-atom,and Co-based metal–organic frameworks(MOFs),are summarized.The underlying mechanisms of these Co-based cocatalysts for facilitating CO_(2)adsorption–activation,boosting charge separation,and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations.In addition,the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO_(2)reduction is highlighted in some selected examples.Finally,the challenges and future perspectives on constructing more effi cient Co-based cocatalysts for practical applications are proposed.
基金financially supported by the National Key Research and Development Program of China(No.2020YFA0714900)the Joint Fund of the Ministry of Education(No.8091B012201)
文摘The corrosion resistance of cobalt-based alloy cladding layers is crucial for the long-term reliability of materials in the nuclear power industry,where they are exposed to highly aggressive environmental conditions.A major challenge to their performance is the corrosion occurring at phase boundaries under harsh operating conditions.This study investigates the effects of pulsed magnetic field treatment(PMT)on improving corrosion resistance at phase boundaries,specifically at the carbide/matrix Co interface,and seeks to clarify the underlying mechanisms.Advanced characterization techniques,including scanning electron microscopy(SEM),in situ transmission electron microscopy(TEM),in situ scanning kelvin probe force microscopy(SKPFM),and density functional theory(DFT)calculations,were employed.PMT samples exhibited no interface corrosion cracking or carbide spalling and showed a significant reduction in corrosion depth.TEM analysis revealed reduced lattice distortion at phase boundaries and a partial transformation of face-centered cubic(FCC)Co to hexagonal closepacked(HCP)Co.The enhanced corrosion resistance at phase boundaries is attributed to changes in the electronic work function(EWF),as determined by SKPFM measurements and DFT calculations.
基金National Natural Science Foundation of China,Grant/Award Number:22406050Top-Notch Personnel Fund of Henan Agricultural University,Grant/Award Number:30501029+2 种基金Natural Science Foundation of Henan Province,Grant/Award Number:232300420293Science and Technology Project of China Tobacco Shaanxi Industrial Co.,Ltd,Grant/Award Number:2024610000340104Postgraduate Education Reform and Quality Improvement Project of Henan Province,Grant/Award Number:YJS2024JD17。
文摘The widespread use of diesel engines results in significant environmental contamination due to emitted pollutants,particularly soot particles.These pollut-ants are detrimental to public health.At present,one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after-treatment tech-nology,which requires the catalyst to have superior low temperature activity.Compared with cerium oxide which is widely used,cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology.This paper elaborates on the influence of modification techniques such as doping,loading,and solid solution on the catalytic performance of cobalt-based catalysts in soot oxidation.Along the same lines,it further reviews the research progress on cobalt-based oxide catalysts with specific dimensional structures and morphologies in soot oxidation.Finally,it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt-based catalysts in soot oxidation.
基金Supported by 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 Natural Science Foundation of China(Grant Nos.:21825201,52401244 and 52201227)Henan Province Key Research and Development and Promotion Program(Scientific and Technological Breakthrough Project:232102240088 and 252102230078)+3 种基金the Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(252102230078)Doctoral Research Startup Fund Project of Henan Open University(BSJH-2025-04)Zhejiang Provincial Natural Science Foundation of China(LQ24B020005,LQ23B030001)China Postdoctoral Science Foundation(2024M762442).
文摘Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.
基金Supported by the 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.
