Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the perform...Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.展开更多
Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discu...Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.展开更多
In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(...In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.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
Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit...Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.展开更多
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian Univers...Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.展开更多
Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for d...Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.展开更多
With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.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
Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and exp...Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.展开更多
A solution of 0.1 mol/L to 1.0 mol/L H2SO4 can dissolve alkali metals and alkaline earth metals which weaken an active site of SCR catalyst. The waste catalyst washed with 0.5 mol/L H2SO4 regained the best catalytic a...A solution of 0.1 mol/L to 1.0 mol/L H2SO4 can dissolve alkali metals and alkaline earth metals which weaken an active site of SCR catalyst. The waste catalyst washed with 0.5 mol/L H2SO4 regained the best catalytic activity. When a concentration of the sulfuric acid is less than 0.5 mol/L, sufficient cleaning effects cannot be obtained. In contrast, when the concentration is greater than 1.0 tool/L, the active components, vanadium and tungsten are undesirably eluted. The total BET surface of the catalyst regenerated by air lift loop reactor showed almost the same as that of fresh catalyst due to the removal of insoluble compounds which may be penetrated into pores of catalyst. The addition of a solution of 0.075 mol/L ammonium vanadate （NHnVO3） and 0.075 mol/L ammonium paratungstate （5（NH4）20· 12WO3-5H20） to 0.1 mol/L H2SO4 significantly increases the activity of the waste catalyst.展开更多
The ternary catalyst Pt75Ru5Ni20 was conducted on various types of carbon supports including functionalized Vulcan XC-72R(f-CB),functionalized multi-walled carbon nanotubes(f-MWCNT),and mesoporous carbon(PC-Zn-succini...The ternary catalyst Pt75Ru5Ni20 was conducted on various types of carbon supports including functionalized Vulcan XC-72R(f-CB),functionalized multi-walled carbon nanotubes(f-MWCNT),and mesoporous carbon(PC-Zn-succinic)by sodium borohydride chemical reduction method to improve the ethanol electrooxidation reaction(EOR)for direct ethanol fuel cell(DEFC).It was found that the particle size of the metals on f-MWCNT was 5.20 nm with good particle dispersion.The alloy formation of ternary catalyst was confirmed by XRD and more clearly described by SEM element mapping,which was relevant to the efficiency of the catalysts.Moreover,the mechanism of ethanol electrooxidation reaction based on the surface reaction was more understanding.The activity and stability for ethanol electrooxidation reaction(EOR)were investigated using cyclic voltammetry and chronoamperometry,respectively.The highest activity and stability for EOR were observed from Pt75Ru5Ni20/f-MWCNT due to a good metal-carbon interaction.Ru and Ni presented in Pt-Ru-Ni alloy improved the activity and stability of ternary catalysts for EOR.Moreover,the reduction of Pt content in ternary catalyst led to the catalyst cost deduction in DEFC.展开更多
Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovs...Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovskites were synthetized by the citrate method.Ni segregation is evident for a substitution level higher than 0. 2. The segregation of Ni as NiO generated species interacts with different metal-support after the reduction step. The y = 0.1 catalyst presents the highest H_2 yield value about 85% during reaction time,with low mean values of CH_4 and CO selectivities of 3.4% and 11%,respectively and a low carbon formation. The better performance of y = 0.1 catalyst could be attributed to the minor proportion of segregated phases,thus a controlled expulsion of Ni is successfully reached.展开更多
Fe-ZSM-5 catalysts modified by Cu and Ce by aqueous solution ion-exchange and incipient wetness impregnation methods were tested in the selective catalytic reduction of NO_(x) with NH_(3).A variety of characterization...Fe-ZSM-5 catalysts modified by Cu and Ce by aqueous solution ion-exchange and incipient wetness impregnation methods were tested in the selective catalytic reduction of NO_(x) with NH_(3).A variety of characterization techniques(NH_(3)-SCO,BET,XRD,XPS,UV-Vis,NH_(3)-TPD,H_(2)-TPR)were used to explore the changes of the active sites,acid sites and pore structure of the catalyst.It was found that the dispersion of active Cu species and Fe species had great influences on the catalytic activity in the whole catalytic process.The Cu doping into the Fe-ZSM-5 catalyst produced new active species,isolated Cu ions and CuO particles,resulting in the improved low-temperature catalytic activity.However,the NH_(3) oxidation was enhanced,and part of the Fe^(3+)active sites and more Brønsted acidic sites in the catalyst were occupied by Cu species,which causes the decrease of the high-temperature activity.The recovery of hightemperature activity could be attributed to the recovery of active Cu species and Fe species promoted by Ce and the promotion of active species dispersion.The results provide theoretical support for adjusting the active window of Febased SCR catalyst by multi-metal doping.展开更多
基金supported by Fundamental Research Program of Shanxi Province(202203021221303)。
文摘Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.
基金supported by National Natural Science Foundation of China(22276144).
文摘Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.
文摘In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.
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supported by the National Natural Science Foundation of China(22472023,22202037)the Jilin Province Science and Technology Development Program(20250102077JC)the Fundamental Research Funds for the Central Universities(2412024QD014,2412023QD019).
文摘Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.
基金the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
文摘Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.
基金University Synergy Innovation Program of Anhui Province(GXXT-2022-083)Science and Technology Plan Project of Wuhu City,China(2023kx12)Anhui Provincial Department of Education New Era Education Project(2023xscx070)。
文摘Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
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.
基金Project(52174338)supported by the National Natural Science Foundation of ChinaProjects(2022JJ20086,2021JJ30796)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(2023CXQD005)supported by the Central South University Innovation-Driven Research Programme,ChinaProject(23B0841)supported by the Education Department of Hunan Provincial Government,China。
文摘Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.
基金Project(2009T100100602) supported by the Korea Institute of Energy Technology Evaluation and Planning,Korea
文摘A solution of 0.1 mol/L to 1.0 mol/L H2SO4 can dissolve alkali metals and alkaline earth metals which weaken an active site of SCR catalyst. The waste catalyst washed with 0.5 mol/L H2SO4 regained the best catalytic activity. When a concentration of the sulfuric acid is less than 0.5 mol/L, sufficient cleaning effects cannot be obtained. In contrast, when the concentration is greater than 1.0 tool/L, the active components, vanadium and tungsten are undesirably eluted. The total BET surface of the catalyst regenerated by air lift loop reactor showed almost the same as that of fresh catalyst due to the removal of insoluble compounds which may be penetrated into pores of catalyst. The addition of a solution of 0.075 mol/L ammonium vanadate （NHnVO3） and 0.075 mol/L ammonium paratungstate （5（NH4）20· 12WO3-5H20） to 0.1 mol/L H2SO4 significantly increases the activity of the waste catalyst.
基金supported by the Institutional Research Grant(Thailand Research Fund:IRG598004)
文摘The ternary catalyst Pt75Ru5Ni20 was conducted on various types of carbon supports including functionalized Vulcan XC-72R(f-CB),functionalized multi-walled carbon nanotubes(f-MWCNT),and mesoporous carbon(PC-Zn-succinic)by sodium borohydride chemical reduction method to improve the ethanol electrooxidation reaction(EOR)for direct ethanol fuel cell(DEFC).It was found that the particle size of the metals on f-MWCNT was 5.20 nm with good particle dispersion.The alloy formation of ternary catalyst was confirmed by XRD and more clearly described by SEM element mapping,which was relevant to the efficiency of the catalysts.Moreover,the mechanism of ethanol electrooxidation reaction based on the surface reaction was more understanding.The activity and stability for ethanol electrooxidation reaction(EOR)were investigated using cyclic voltammetry and chronoamperometry,respectively.The highest activity and stability for EOR were observed from Pt75Ru5Ni20/f-MWCNT due to a good metal-carbon interaction.Ru and Ni presented in Pt-Ru-Ni alloy improved the activity and stability of ternary catalysts for EOR.Moreover,the reduction of Pt content in ternary catalyst led to the catalyst cost deduction in DEFC.
文摘Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose,La_(1-x)Mg_xAl_(1-y)Ni_yO_3(x = 0.1; y = 0,0.1,0.2,0.3) perovskites were synthetized by the citrate method.Ni segregation is evident for a substitution level higher than 0. 2. The segregation of Ni as NiO generated species interacts with different metal-support after the reduction step. The y = 0.1 catalyst presents the highest H_2 yield value about 85% during reaction time,with low mean values of CH_4 and CO selectivities of 3.4% and 11%,respectively and a low carbon formation. The better performance of y = 0.1 catalyst could be attributed to the minor proportion of segregated phases,thus a controlled expulsion of Ni is successfully reached.
基金Project(51906089)supported by the National Natural Science Foundation of ChinaProject(NELMS2018A18)supported by the National Engineering Laboratory for Mobile Source Emission Control Technology,China+1 种基金Project(XNYQ2021-002)supported by the Provincial Engineering Research Center for New Energy Vehicle Intelligent Control and Simulation Test Technology of Sichuan,ChinaProject(GY2020016)supported by the Zhenjiang City Key R&D Program,China。
文摘Fe-ZSM-5 catalysts modified by Cu and Ce by aqueous solution ion-exchange and incipient wetness impregnation methods were tested in the selective catalytic reduction of NO_(x) with NH_(3).A variety of characterization techniques(NH_(3)-SCO,BET,XRD,XPS,UV-Vis,NH_(3)-TPD,H_(2)-TPR)were used to explore the changes of the active sites,acid sites and pore structure of the catalyst.It was found that the dispersion of active Cu species and Fe species had great influences on the catalytic activity in the whole catalytic process.The Cu doping into the Fe-ZSM-5 catalyst produced new active species,isolated Cu ions and CuO particles,resulting in the improved low-temperature catalytic activity.However,the NH_(3) oxidation was enhanced,and part of the Fe^(3+)active sites and more Brønsted acidic sites in the catalyst were occupied by Cu species,which causes the decrease of the high-temperature activity.The recovery of hightemperature activity could be attributed to the recovery of active Cu species and Fe species promoted by Ce and the promotion of active species dispersion.The results provide theoretical support for adjusting the active window of Febased SCR catalyst by multi-metal doping.
