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
Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth met...Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth metals on the physicochemical characteristics and catalytic activities of Ru/ATiO_(3)for NH_(3)decomposition were investigated using various techniques.The order of Ru/ATiO_(3)for NH_(3)conversion is Ru/BaTiO_(3)>Ru/SrTiO_(3)>Ru/CaTiO_(3)>Ru/TiO_(2)at the identical conditions,with the Ru/BaTiO_(3)catalyst demonstrating the highest NH_(3)conversion of 77.8%at 450℃and a gas hourly space velocity of 30,000 mL/gcat/h,which is 8.7,2.1,and 1.3 times of that over Ru/TiO_(2),Ru/CaTiO_(3),and Ru/SrTiO_(3),respectively.The formation of the ATiO_(3)phase can enrich the concentration of basic sites and oxygen vacancies compared with TiO_(2),which can induce the presence of strong metal-support interaction(SMSI)through the formation of Ru-O-Ti bonds.This SMSI effect increased the dispersion and electron density of Ru nano-particles on ATiO_(3)supports,and the electron-rich Ru nano-particles could weaken the chemisorptive strength of N_(2)and H_(2)on the Ru/ATiO_(3)catalysts,thereby promoting the reaction rate for NH_(3)decomposition.展开更多
Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-perform...Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.展开更多
To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were en...To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.展开更多
The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction tempera...The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.展开更多
The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previou...The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),w...The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx.The results show that Ru1@Mo_(2)CO_(x)exhibits excellent stability,and can effectively adsorb and activate N2,owing to up to0.87|e|charge transfer from it to N2.The optimal pathway of N2-to-NH_(3) conversion is association pathway I,of which the rate-determining step is*NH_(2)→*NH_(3) with the barrier energy of 1.26 eV.Especially,the Mo_(2)CO_(x)center functions as an electron reservoir,donating electrons to the NxHy species,while the Ru single atom serves as a charge transfer pathway,thereby enhancing the reaction activity.This finding provides a theoretical foundation for the rational design of MXene-based SACs for thermal catalytic NH_(3) synthesis.展开更多
Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are ...Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.展开更多
Metal-free carbon catalysts have garnered significant attention since their inception.Despite substantial advancements,including widely adopted strategies such as heteroatom doping and defect engineering,their catalyt...Metal-free carbon catalysts have garnered significant attention since their inception.Despite substantial advancements,including widely adopted strategies such as heteroatom doping and defect engineering,their catalytic performance remains inferior to that of metal-based catalysts.In this study,we have predicted and demonstrated that the curvature of carbon plays a pivotal role in the adsorption of acetylene and the overall catalytic performance.First-principles calculations suggest that a tip-enhanced local electric field at the defect site on the curved carbon catalyst enhances the reaction kinetics for acetylene hydrochlorination.The experimental results highlight the structural advantages of the curved defect site,revealing that high-curvature defective carbon(HCDC)demonstrates an adsorption capacity for acetylene that is almost two orders of magnitude higher than that of defective carbon.Notably,HCDC achieves an acetylene conversion of up to 90%at 220℃under a gas hourly space velocity of 300 h^(-1),significantly surpassing the performance of the benchmark 0.25%Au/AC catalyst.This proof-of-concept study reveals the fundamental mechanisms driving the superior performance of carbon catalysts with curved nanostructures and presents a straightforward,environmentally friendly method for large-scale production of carbon materials with precisely controlled nanostructures.It highlights the potential for commercializing metal-free carbon catalysts in acetylene hydrochlorination and related heterogenous catalytic reactions.展开更多
The catalytic performance of supported metal catalysts is highly dependent on the interfacial contact between the metal centers and support materials,which could dynamically adapt to the chemical environment in the re...The catalytic performance of supported metal catalysts is highly dependent on the interfacial contact between the metal centers and support materials,which could dynamically adapt to the chemical environment in the reactions.Herein,the well-known Ru/TiO_(x)interface of the Ru/TiO_(2)catalyst is shown to be transformed into Ru/TiO_(x)N_(y)during the NH_(3)decomposition,which is derived from the nitridation of the support by N^(*)species.Through a series of characterizations and density functional theory(DFT)calculations,it is found that such a nitrogenous interface primarily blocks the cleavage of N-H bonds with a higher energy barrier,leading to the deactivation of Ru/TiO_(2)in NH_(3)decomposition.Nevertheless,the Ru/TiO_(x)interface can be easily restored by oxidation and a subsequent H2 reduction,contributing to the recovery of the catalytic activity toward NH_(3)decomposition.Our study provides a new insight into the deactivation mechanism of Ru/TiO_(2)in NH_(3)decomposition and highlights the significance of the dynamic evolution of the metal-support interfaces in the reactions.展开更多
Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such ...Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.展开更多
Room-temperature sodium-sulfur(RT Na-S)batteries have been regarded as promising energy storage technologies in grid-scale stationary energy storage systems due to their low cost,natural abundance,and high-energy dens...Room-temperature sodium-sulfur(RT Na-S)batteries have been regarded as promising energy storage technologies in grid-scale stationary energy storage systems due to their low cost,natural abundance,and high-energy density.However,the practical application of RT Na-S batteries is hindered by low reversible capacity and unsatisfying long-cycling performance arising from the severe shuttle effect and sluggish S redox kinetics.This review provides an overview of recent efforts for the optimization strategies of the electronic structure of catalysts via catalyst engineering to enhance the adsorption and catalytic activity toward soluble long-chain sodium polysulfides(NaPSs).Finally,the current challenges and prospects for further optimization strategies of catalysts,understanding catalysis and structural evolution mechanism,and achieving practical applications are highlighted to meet the commercial requirements of RT Na-S batteries.展开更多
The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics...The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics,thermodynamic stability,inadequate cycling stability,and difficulties in activation impede the commercial utilization of Mg-based composites.Research indicates that reducing material dimensions to the nanoscale represents an efficacious strategy to address these issues.In this work,we systematically analyze the impact of nanosizing on Mg-based composites from three perspectives:nano-substrate modulation,nano-catalyst construction,and nano-catalytic mechanism.This analysis aims to provide guidance for the optimization and development of nanosizing strategies.For the regulation of nanosizing of Mg-based composites,the nanosizing of multi-element micro-alloyed Mg-rich systems,the integrated synthesis of multi-element multi-component nano-catalysts,and the coexistence of multiple nano-catalytic mechanisms are proposed in the light of the current state of the art research,artificial intelligence technology,and advanced characterization technology to achieve efficient,multidimensional,and simultaneous regulation of the hydrogen storage performance of Mg-based composites.This paper also envisions future directions and potential applications,emphasizing the importance of interdisciplinary approaches that integrate material science,chemistry,and computational modeling to overcome existing limitations and unlock the full potential of Mg-based hydrogen storage technologies.展开更多
Metal(oxide)-zeolite bifunctional catalysts have been the subject of considerable attention from researchers in both academic and industry,due to their superior activity and stability in various heterogeneous catalyti...Metal(oxide)-zeolite bifunctional catalysts have been the subject of considerable attention from researchers in both academic and industry,due to their superior activity and stability in various heterogeneous catalytic processes[1–3].Based on the different metal loading sites,these bifunctional catalysts can be categorized as follows:(a)metal species loaded on the outer surface of zeolite crystals,(b)metal species encapsulated within the channels or cavities of zeolites,and(c)metal species incorporated into the zeolite framework(Fig.1).Metal species in type(b)and(c)samples are stabilized by the zeolite frameworks,resulting in excellent thermal and hydrothermal stability during catalytic reactions,especially under harsh conditions,as well as unique shape-selectivity.However,the complex synthesis procedures make large-scale preparation of these catalysts impractical.In contrast,a type(a)sample can be achieved via the simple impregnation;nevertheless,migration of metal species and their aggregation into larger particles often occur during the calcination and reduction processes.展开更多
SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guai...SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.展开更多
Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was con...Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was constructed by an active dicyandiamide(DCA)linker,Mn^(2+),Co^(2+)centers,and an 1-ethylimidazole(EIM)ligand.1 possesses good thermal stability(Tp=205℃),high energy density(Eg=24.34 kJ/g,Ev=35.93 kJ/cm^(3)),and insensitivity to impact and frictional stimulus.The catalytic effects of 1 contrasted to monometallic coordination compounds Mn(EIM)_(4)(DCA)_(2)(2)and Co(EIM)_(4)(DCA)_(2)(3)on the thermal decomposition of AP/RDX composite were investigated by a DSC method.The decomposition peak temperatures of AP and RDX of the composite decreased to 335.8℃ and 206.4℃,respectively,and the corresponding activation energy decreased by 27.3%and 43.6%,respectively,which are better than the performances of monometallic complexes 2 and 3.The gas products in the whole thermal decomposition stage of the sample were measured by TG-MS and TG-IR,and the catalytic mechanism of 1 to AP/RDX was further analyzed.This work reveal potential application of bimetallic MOFs in the composite solid propellants.展开更多
Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a...Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.展开更多
Preferential oxidation of CO is an effective process to clean up CO in hydrogen for proton exchange membrane fuel cells(PEMFCs).Herein,we synthesis a highly efficient catalyst for preferential oxidation(PROX)of CO thr...Preferential oxidation of CO is an effective process to clean up CO in hydrogen for proton exchange membrane fuel cells(PEMFCs).Herein,we synthesis a highly efficient catalyst for preferential oxidation(PROX)of CO through the deposition of Ru/Ir nanojunctions on Fe_(2)O_(3) nanoparticles.The as-prepared catalyst shows 90%CO conversion at 80℃ within the working temperature of PEMFCs and the total CO conversion in the temperature range of 140℃ to 160℃under gas flow velocity of 36000 mL·g^(−1)h^(−1) while maintaining good stability for 24 h.Density functional theory calculations reveal that the substrate Fe_(2)O_(3) not only serves as a source of lattice oxygen atoms for the catalytic process but also acts as an electron acceptor from Ru/Ir,thereby regulating its valence state.This regulation is beneficial for the adsorption of reaction intermediates and reduces the activation energy of PROX.展开更多
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financially supported by the National Natural Science Foundation of China(21968028)the Xinjiang Tianchi Talent Project(CZ002732)。
文摘Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth metals on the physicochemical characteristics and catalytic activities of Ru/ATiO_(3)for NH_(3)decomposition were investigated using various techniques.The order of Ru/ATiO_(3)for NH_(3)conversion is Ru/BaTiO_(3)>Ru/SrTiO_(3)>Ru/CaTiO_(3)>Ru/TiO_(2)at the identical conditions,with the Ru/BaTiO_(3)catalyst demonstrating the highest NH_(3)conversion of 77.8%at 450℃and a gas hourly space velocity of 30,000 mL/gcat/h,which is 8.7,2.1,and 1.3 times of that over Ru/TiO_(2),Ru/CaTiO_(3),and Ru/SrTiO_(3),respectively.The formation of the ATiO_(3)phase can enrich the concentration of basic sites and oxygen vacancies compared with TiO_(2),which can induce the presence of strong metal-support interaction(SMSI)through the formation of Ru-O-Ti bonds.This SMSI effect increased the dispersion and electron density of Ru nano-particles on ATiO_(3)supports,and the electron-rich Ru nano-particles could weaken the chemisorptive strength of N_(2)and H_(2)on the Ru/ATiO_(3)catalysts,thereby promoting the reaction rate for NH_(3)decomposition.
基金supported by the National Natural Science Foundation of China(No.21571062)the Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher Learning to JGL,and the Fundamental Research Funds for the Central Universities(No.222201717003)。
文摘Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.
基金supported by the National Natural Science Foundation of China(Nos.22025604 and 22276204)the National Key R&D Program of China(Nos.2023YFC3708401 and 2022YFC3800404).
文摘To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.
文摘The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.
基金financially supported by the National Natural Science Foundation of China (No.21905266)the Fundamental Research Funds for the Central Universities (WK3530000013)。
文摘The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金the financial support from National Natural Science Foundation of China(22479032,22363001 and 22250710677)the NSFC Center for Single-Atom Catalysis(22388102)+2 种基金the National Key R&D Project(2022YFA1503900)the Natural Science Special Foundation of Guizhou University(No.202140)Guizhou Provincial Key Laboratory Platform Project(ZSYS[2025]008).
文摘The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx.The results show that Ru1@Mo_(2)CO_(x)exhibits excellent stability,and can effectively adsorb and activate N2,owing to up to0.87|e|charge transfer from it to N2.The optimal pathway of N2-to-NH_(3) conversion is association pathway I,of which the rate-determining step is*NH_(2)→*NH_(3) with the barrier energy of 1.26 eV.Especially,the Mo_(2)CO_(x)center functions as an electron reservoir,donating electrons to the NxHy species,while the Ru single atom serves as a charge transfer pathway,thereby enhancing the reaction activity.This finding provides a theoretical foundation for the rational design of MXene-based SACs for thermal catalytic NH_(3) synthesis.
文摘Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.
文摘Metal-free carbon catalysts have garnered significant attention since their inception.Despite substantial advancements,including widely adopted strategies such as heteroatom doping and defect engineering,their catalytic performance remains inferior to that of metal-based catalysts.In this study,we have predicted and demonstrated that the curvature of carbon plays a pivotal role in the adsorption of acetylene and the overall catalytic performance.First-principles calculations suggest that a tip-enhanced local electric field at the defect site on the curved carbon catalyst enhances the reaction kinetics for acetylene hydrochlorination.The experimental results highlight the structural advantages of the curved defect site,revealing that high-curvature defective carbon(HCDC)demonstrates an adsorption capacity for acetylene that is almost two orders of magnitude higher than that of defective carbon.Notably,HCDC achieves an acetylene conversion of up to 90%at 220℃under a gas hourly space velocity of 300 h^(-1),significantly surpassing the performance of the benchmark 0.25%Au/AC catalyst.This proof-of-concept study reveals the fundamental mechanisms driving the superior performance of carbon catalysts with curved nanostructures and presents a straightforward,environmentally friendly method for large-scale production of carbon materials with precisely controlled nanostructures.It highlights the potential for commercializing metal-free carbon catalysts in acetylene hydrochlorination and related heterogenous catalytic reactions.
基金supported by the National Key R&D Program of China(2022YFB4300700)National Natural Science Foundation of China(22008230,22208021,21925803)+6 种基金China Postdoctoral Science Foundation funded project(2020M670807)the Doctoral Scientific Research Foundation of Liaoning Province(2022-BS-014)the Innovation Research Fund Project of Dalian Institute of Chemical Physics(DICP I202224)CAS Specific Research Assistant Funding Programthe fund of the State Key Laboratory of Catalysis in Dalian Institute of Chemical Physics(N-22-08)the Youth Innovation Promotion Association CAS(Y2022061)the Young Topnotch Talents of Liaoning Province(XLYC2203108)。
文摘The catalytic performance of supported metal catalysts is highly dependent on the interfacial contact between the metal centers and support materials,which could dynamically adapt to the chemical environment in the reactions.Herein,the well-known Ru/TiO_(x)interface of the Ru/TiO_(2)catalyst is shown to be transformed into Ru/TiO_(x)N_(y)during the NH_(3)decomposition,which is derived from the nitridation of the support by N^(*)species.Through a series of characterizations and density functional theory(DFT)calculations,it is found that such a nitrogenous interface primarily blocks the cleavage of N-H bonds with a higher energy barrier,leading to the deactivation of Ru/TiO_(2)in NH_(3)decomposition.Nevertheless,the Ru/TiO_(x)interface can be easily restored by oxidation and a subsequent H2 reduction,contributing to the recovery of the catalytic activity toward NH_(3)decomposition.Our study provides a new insight into the deactivation mechanism of Ru/TiO_(2)in NH_(3)decomposition and highlights the significance of the dynamic evolution of the metal-support interfaces in the reactions.
文摘Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.
基金supported by the National Natural Science Foundation of China(No.22005201)the Young Scholars Science Foundation of Lanzhou Jiaotong University(No.2022023)the Fundamental Research Funds for the Central Universities,and the Youth Science and Technology Foundation of Gansu Province(Nos.22JR5RA541 and 22JR5RA374).
文摘Room-temperature sodium-sulfur(RT Na-S)batteries have been regarded as promising energy storage technologies in grid-scale stationary energy storage systems due to their low cost,natural abundance,and high-energy density.However,the practical application of RT Na-S batteries is hindered by low reversible capacity and unsatisfying long-cycling performance arising from the severe shuttle effect and sluggish S redox kinetics.This review provides an overview of recent efforts for the optimization strategies of the electronic structure of catalysts via catalyst engineering to enhance the adsorption and catalytic activity toward soluble long-chain sodium polysulfides(NaPSs).Finally,the current challenges and prospects for further optimization strategies of catalysts,understanding catalysis and structural evolution mechanism,and achieving practical applications are highlighted to meet the commercial requirements of RT Na-S batteries.
基金financially supported by the Key Research and Development Projects of Shaanxi Province(Grant Nos.2025CYYBXM-154 and 2024GX-YBXM-213)the Yulin Science and Technology Bureau(Grant Nos.2023-CXY-202 and 2024-CXY-154)the Technology Innovation Leading Program of Shaanxi(Programs 2023GXLH-068)。
文摘The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics,thermodynamic stability,inadequate cycling stability,and difficulties in activation impede the commercial utilization of Mg-based composites.Research indicates that reducing material dimensions to the nanoscale represents an efficacious strategy to address these issues.In this work,we systematically analyze the impact of nanosizing on Mg-based composites from three perspectives:nano-substrate modulation,nano-catalyst construction,and nano-catalytic mechanism.This analysis aims to provide guidance for the optimization and development of nanosizing strategies.For the regulation of nanosizing of Mg-based composites,the nanosizing of multi-element micro-alloyed Mg-rich systems,the integrated synthesis of multi-element multi-component nano-catalysts,and the coexistence of multiple nano-catalytic mechanisms are proposed in the light of the current state of the art research,artificial intelligence technology,and advanced characterization technology to achieve efficient,multidimensional,and simultaneous regulation of the hydrogen storage performance of Mg-based composites.This paper also envisions future directions and potential applications,emphasizing the importance of interdisciplinary approaches that integrate material science,chemistry,and computational modeling to overcome existing limitations and unlock the full potential of Mg-based hydrogen storage technologies.
基金financially supported by the National Key R&D Program of China(2024YFE0101100)the National Natural Science Foundation of China(22475112,22305132,22305155)+1 种基金the China Postdoctoral Science Foundation(2023M732323)the Postdoctoral Fellowship Program of CPSF(GZC20231679).
文摘Metal(oxide)-zeolite bifunctional catalysts have been the subject of considerable attention from researchers in both academic and industry,due to their superior activity and stability in various heterogeneous catalytic processes[1–3].Based on the different metal loading sites,these bifunctional catalysts can be categorized as follows:(a)metal species loaded on the outer surface of zeolite crystals,(b)metal species encapsulated within the channels or cavities of zeolites,and(c)metal species incorporated into the zeolite framework(Fig.1).Metal species in type(b)and(c)samples are stabilized by the zeolite frameworks,resulting in excellent thermal and hydrothermal stability during catalytic reactions,especially under harsh conditions,as well as unique shape-selectivity.However,the complex synthesis procedures make large-scale preparation of these catalysts impractical.In contrast,a type(a)sample can be achieved via the simple impregnation;nevertheless,migration of metal species and their aggregation into larger particles often occur during the calcination and reduction processes.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LY23B060006 and LY18B060016).
文摘SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.
基金supported by the National Natural Science Foundation of China(Grant No.22175025)State Key Laboratory of Explosion Science and Safety Protection(Grant No.YBKT22-03)+1 种基金the Natural Science Foundation of Chongqing(Grant No.CSTB2023 NSCQ-LZX0098)the Chongqing Municipal Education Commis-sion(Grant No.KJZD-M202301404).
文摘Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was constructed by an active dicyandiamide(DCA)linker,Mn^(2+),Co^(2+)centers,and an 1-ethylimidazole(EIM)ligand.1 possesses good thermal stability(Tp=205℃),high energy density(Eg=24.34 kJ/g,Ev=35.93 kJ/cm^(3)),and insensitivity to impact and frictional stimulus.The catalytic effects of 1 contrasted to monometallic coordination compounds Mn(EIM)_(4)(DCA)_(2)(2)and Co(EIM)_(4)(DCA)_(2)(3)on the thermal decomposition of AP/RDX composite were investigated by a DSC method.The decomposition peak temperatures of AP and RDX of the composite decreased to 335.8℃ and 206.4℃,respectively,and the corresponding activation energy decreased by 27.3%and 43.6%,respectively,which are better than the performances of monometallic complexes 2 and 3.The gas products in the whole thermal decomposition stage of the sample were measured by TG-MS and TG-IR,and the catalytic mechanism of 1 to AP/RDX was further analyzed.This work reveal potential application of bimetallic MOFs in the composite solid propellants.
文摘Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.
基金financially supported by the National Natural Science Foundation of China(No.22072140,No.22272155,and No.22102169)the National Key R&D Program of China(No.2021YFA1600202)。
文摘Preferential oxidation of CO is an effective process to clean up CO in hydrogen for proton exchange membrane fuel cells(PEMFCs).Herein,we synthesis a highly efficient catalyst for preferential oxidation(PROX)of CO through the deposition of Ru/Ir nanojunctions on Fe_(2)O_(3) nanoparticles.The as-prepared catalyst shows 90%CO conversion at 80℃ within the working temperature of PEMFCs and the total CO conversion in the temperature range of 140℃ to 160℃under gas flow velocity of 36000 mL·g^(−1)h^(−1) while maintaining good stability for 24 h.Density functional theory calculations reveal that the substrate Fe_(2)O_(3) not only serves as a source of lattice oxygen atoms for the catalytic process but also acts as an electron acceptor from Ru/Ir,thereby regulating its valence state.This regulation is beneficial for the adsorption of reaction intermediates and reduces the activation energy of PROX.
