Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platin...Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platinum group metal(PGM)catalysts creates a barrier for the large-scale application of PEMFC.Tremendous efforts have been devoted to the development of low-cost PGM-free catalysts,especially the Fe-N-C catalysts,to replace the expensive PGM catalysts.However,the characterization methods and evaluation standards of the catalysts varies,which is not conducive to the comparison of PGM-free catalysts.U.S.Department of energy(DOE)is the only authority that specifies the testing standards and activity targets for PGM-free catalysts.In this review,the major breakthroughs of Fe-N-C catalysts are outlined with the reference of DOE standards and targets.The preparation and characteristics of these highly active Fe-N-C catalysts are briefly introduced.Moreover,the efforts on improving the mass transfer and the durability issue of Fe-N-C fuel cell are discussed.Finally,the prospective directions concerning the comprehensive evaluation of the Fe-N-C catalysts are proposed.展开更多
以煅烧三聚氰胺后形成的C3N4材料为氮源,柠檬酸为碳源,六水合三氯化铁为铁源,通过两步法合成FeN/C催化剂,并考察该催化剂对氧还原反应的电催化能力。采用XRD、SEM、Raman、XPS等表征手段对Fe-N/C催化剂的晶体结构和元素化学状态进行综...以煅烧三聚氰胺后形成的C3N4材料为氮源,柠檬酸为碳源,六水合三氯化铁为铁源,通过两步法合成FeN/C催化剂,并考察该催化剂对氧还原反应的电催化能力。采用XRD、SEM、Raman、XPS等表征手段对Fe-N/C催化剂的晶体结构和元素化学状态进行综合评价;以CV和LSV等电化学测试手段探究Fe-N/C催化剂的氧还原电催化能力。研究结果表明,Fe-N/C催化剂具有管状形貌、较高的石墨氮含量和较佳的氧还原电催化能力。通过对电化学性能关键参数进行分析发现,Fe-N/C催化剂的起始电位是1.071 V vs. RHE,半波电位是0.911 V vs. RHE,极限电流密度是5.943 mA/cm2。展开更多
A novel gas-phase electrocatalytic cell containing a low-temperature proton exchange membrane(PEM)was developed to electrochemically convert CO_2into organic compounds.Two different Cu-based cathode catalysts(Cu and C...A novel gas-phase electrocatalytic cell containing a low-temperature proton exchange membrane(PEM)was developed to electrochemically convert CO_2into organic compounds.Two different Cu-based cathode catalysts(Cu and Cu–C)were prepared by physical vapor deposition method(sputtering)and subsequently employed for the gas-phase electroreduction of CO_2at different temperatures(70–90°C).The prepared electrodes Cu and Cu–C were characterized by X-ray diffraction(XRD),X-ray photoemission spectroscopy(XPS)and scanning electron microscopy(SEM).As revealed,Cu is partially oxidized on the surface of the samples and the Cu and Cu–C cathodic catalysts were comprised of a porous,continuous,and homogeneous film with nanocrystalline Cu with a grain size of 16 and 8 nm,respectively.The influence of the applied current and temperature on the electro-catalytic activity and selectivity of these materials was investigated.Among the two investigated electrodes,the pure Cu catalyst film showed the highest CO_2specific electrocatalytic reduction rates and higher selectivity to methanol formation compared to the Cu–C electrode,which was attributed to the higher particle size of the former and lower Cu O/Cu ratio.The obtained results show potential interest for the possible use of electrical renewable energy for the transformation of CO_2into valuable products using low metal loading Cu based electrodes(0.5 mg Cu cm^(-2))prepared by sputtering.展开更多
Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination o...Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.展开更多
Green and economical CO_(2)utilization is significant for CO_(2)emission reduction and energy development.Here,the 1D Mo_(2)C nanowires with dominant(101)crystal surfaces were modified by the deposition of atomic func...Green and economical CO_(2)utilization is significant for CO_(2)emission reduction and energy development.Here,the 1D Mo_(2)C nanowires with dominant(101)crystal surfaces were modified by the deposition of atomic functional components Rh and K.While unmodifiedβMo_(2)C could only convert CO_(2)to methanol,the designed catalyst of K_(0.2)Rh_(0.2)/β-Mo_(2)C exhibited up to 72.1%of ethanol selectivity at 150℃.It was observed that the atomically dispersed Rh could form the bifunctional active centres with the active carrierβMo_(2)C with the synergistic effects to achieve highly specific controlled C–C coupling.By promoting the CO_(2)adsorption and activation,the introduction of an alkali metal(K)mainly regulated the balanced performance of the two active centres,which in turn improved the hydrogenation selectivity.Overall,the controlled modification ofβMo_(2)C provides a new design strategy for the highly efficient,lowtemperature hydrogenation of CO_(2)to ethanol with single-atom catalysts,which provides an excellent example for the rational design of the complex catalysts.展开更多
Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-mi...Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.展开更多
The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The ca...The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.展开更多
The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based so...The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.展开更多
Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were ...Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were carried out to characterize the morphology, composition and the electrochemical properties of the PtRu/C catalyst. The results revealed that the PtRu nanoparticles with small average particle size (≈2.5 nm), and highly dispersed on the carbon support. The PtRu/C catalyst exhibited high catalytic activity and anti poisoned performance than that of the JM PtRu/C. It is imply that the modified polyol method is efficient for PtRu/C catalyst preparation.展开更多
The activity of Mo_(2) C-based catalyst on vegetable oil conversion into biofuel could be greatedly promoted by tuning the carbon content,while its modification mechanism on the surface properties remained elusive.Her...The activity of Mo_(2) C-based catalyst on vegetable oil conversion into biofuel could be greatedly promoted by tuning the carbon content,while its modification mechanism on the surface properties remained elusive.Herein,the exposed active sites,the particle size and Lewis acid amount of Ni-Mo_(2) C/MCM-41 catalysts were regulated by varying CH_(4) content in carbonization gas.The activity of Ni-Mo_(2) C/MCM-41 catalysts in jatropha oil(JO)conversion showed a volcano-like trend over the catalysts with increasing CH_(4) content from 15%to 50%in the preparation process.The one prepared by 25%CH_(4) content(NiMo_(2) C(25)/MCM-41)exhibited the outstanding catalytic performance with 83.9 wt%biofuel yield and95.2%C_(15)-C_(18) selectivity.Such a variation of activity was ascribed to the most exposed active sites,the smallest particle size,and the lowest Lewis acid amount from Ni^(0) on the Ni-Mo_(2) C(25)/MCM-41 catalyst surface.Moreover,the Ni-Mo_(2) C(25)/MCM-41 catalyst could also effectively catalyze the conversion of crude waste cooking oil(WCO)into green diesel.This study offers an effective strategy to improve catalytic performance of molybdenum carbide catalyst on vegetable oil conversion.展开更多
Carbonate-modified metal-support interfaces allow Ru/MnCO_(3) catalyst to exhibit over 99% selectivity,great specific activity and long-term anti-CO poisoning stability in atmospheric CO_(2) methanation.As a contrast,...Carbonate-modified metal-support interfaces allow Ru/MnCO_(3) catalyst to exhibit over 99% selectivity,great specific activity and long-term anti-CO poisoning stability in atmospheric CO_(2) methanation.As a contrast,Ru/MnO catalyst with metal-oxide interfaces prefers reverse water-gas shift rather than methanation route,along with a remarkably lower activity and a less than 15% CH_(4) selectivity.The carbonatemodified interfaces are found to stabilize the Ru species and activate CO_(2) and H_(2) molecules.Ru-CO^(4) species are identified as the reaction intermediates steadily formed from CO_(2) dissociation,which show moderate adsorption strength and high reactivity in further hydrogenation to CH_(4),Furthermore,carbonates of Ru/MnCO_(3) are found to be consumed by hydrogenation to form CH_(4) and replenished by exchange with CO_(2),which are in a dynamic equilibrium during the reaction.Modification with surface carbonates is proved as an efficient strategy to endow metal-support interfaces of Ru-based catalysts with unique catalytic functions for selective CO_(2) hydrogenation.展开更多
Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehy...Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.展开更多
A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 month...A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 months’ shelf life) from single batch preparation with activated carbon ethylene glycol suspension.21 wt%, 42 wt% and 61 wt% Pt loadings are employed to showcase the advantages of the improved polyol process. The ultraviolet(UV)–visible spectra and ζ-potential measurements are conducted to monitor the wet chemistry process during catalyst preparation. The powder X-ray diffraction(XRD), transmission electron microscopy(TEM) and thermogravimetric analysis(TGA) characterizations are carried out on catalysts. The catalyst activities are investigated using electrochemical and single cell tests. The stability of Pt nanoparticle colloid is explored by ORR, cyclic voltammetry(CV) and ζ-potential measurements. The TEM results show the Pt particle sizes of the colloid, and the sizes of the 21 wt%, 42 wt% and 61 wt%Pt/C samples are 2.1–3.9 nm. Because of the high Pt dispersion, the Pt/C catalysts exhibit superior electroactivity toward ORR. In addition, four 61 wt% Pt/C catalysts made from the Pt colloid with 0–3 months’ shelf life show almost the same performance, which exhibits superior stability of the Pt colloid system without surfactant protection.展开更多
基金supported by the National Thousand Talents Plan of Chinathe National Natural Science Foundation of China(Grant Nos.21673014 and U1766216)+1 种基金the 111 project(B17002)funded by the Ministry of Education of Chinathe Fundamental Research Funds for the Central Universities of China
文摘Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platinum group metal(PGM)catalysts creates a barrier for the large-scale application of PEMFC.Tremendous efforts have been devoted to the development of low-cost PGM-free catalysts,especially the Fe-N-C catalysts,to replace the expensive PGM catalysts.However,the characterization methods and evaluation standards of the catalysts varies,which is not conducive to the comparison of PGM-free catalysts.U.S.Department of energy(DOE)is the only authority that specifies the testing standards and activity targets for PGM-free catalysts.In this review,the major breakthroughs of Fe-N-C catalysts are outlined with the reference of DOE standards and targets.The preparation and characteristics of these highly active Fe-N-C catalysts are briefly introduced.Moreover,the efforts on improving the mass transfer and the durability issue of Fe-N-C fuel cell are discussed.Finally,the prospective directions concerning the comprehensive evaluation of the Fe-N-C catalysts are proposed.
文摘以煅烧三聚氰胺后形成的C3N4材料为氮源,柠檬酸为碳源,六水合三氯化铁为铁源,通过两步法合成FeN/C催化剂,并考察该催化剂对氧还原反应的电催化能力。采用XRD、SEM、Raman、XPS等表征手段对Fe-N/C催化剂的晶体结构和元素化学状态进行综合评价;以CV和LSV等电化学测试手段探究Fe-N/C催化剂的氧还原电催化能力。研究结果表明,Fe-N/C催化剂具有管状形貌、较高的石墨氮含量和较佳的氧还原电催化能力。通过对电化学性能关键参数进行分析发现,Fe-N/C催化剂的起始电位是1.071 V vs. RHE,半波电位是0.911 V vs. RHE,极限电流密度是5.943 mA/cm2。
基金Financial support from the "Spanish Ministry of Economy, Industry, and Competitiveness" (Project CTQ2016-75491-R)from Abengoa Researchthe Spanish Ministry of Economy, Industry, and Competitiveness for financial support through the Ramón y Cajal Program, Grant: RYC-2015-19230
文摘A novel gas-phase electrocatalytic cell containing a low-temperature proton exchange membrane(PEM)was developed to electrochemically convert CO_2into organic compounds.Two different Cu-based cathode catalysts(Cu and Cu–C)were prepared by physical vapor deposition method(sputtering)and subsequently employed for the gas-phase electroreduction of CO_2at different temperatures(70–90°C).The prepared electrodes Cu and Cu–C were characterized by X-ray diffraction(XRD),X-ray photoemission spectroscopy(XPS)and scanning electron microscopy(SEM).As revealed,Cu is partially oxidized on the surface of the samples and the Cu and Cu–C cathodic catalysts were comprised of a porous,continuous,and homogeneous film with nanocrystalline Cu with a grain size of 16 and 8 nm,respectively.The influence of the applied current and temperature on the electro-catalytic activity and selectivity of these materials was investigated.Among the two investigated electrodes,the pure Cu catalyst film showed the highest CO_2specific electrocatalytic reduction rates and higher selectivity to methanol formation compared to the Cu–C electrode,which was attributed to the higher particle size of the former and lower Cu O/Cu ratio.The obtained results show potential interest for the possible use of electrical renewable energy for the transformation of CO_2into valuable products using low metal loading Cu based electrodes(0.5 mg Cu cm^(-2))prepared by sputtering.
基金supported by the Scholarship from China Scholarship Council(CSC)(Grant no.201604910621)。
文摘Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.
基金financially supported by the National Natural Science Foundation of China(21925803,U19A2015)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB36030200)the Liao Ning Revitalization Talents Program(XLYC1907170).
文摘Green and economical CO_(2)utilization is significant for CO_(2)emission reduction and energy development.Here,the 1D Mo_(2)C nanowires with dominant(101)crystal surfaces were modified by the deposition of atomic functional components Rh and K.While unmodifiedβMo_(2)C could only convert CO_(2)to methanol,the designed catalyst of K_(0.2)Rh_(0.2)/β-Mo_(2)C exhibited up to 72.1%of ethanol selectivity at 150℃.It was observed that the atomically dispersed Rh could form the bifunctional active centres with the active carrierβMo_(2)C with the synergistic effects to achieve highly specific controlled C–C coupling.By promoting the CO_(2)adsorption and activation,the introduction of an alkali metal(K)mainly regulated the balanced performance of the two active centres,which in turn improved the hydrogenation selectivity.Overall,the controlled modification ofβMo_(2)C provides a new design strategy for the highly efficient,lowtemperature hydrogenation of CO_(2)to ethanol with single-atom catalysts,which provides an excellent example for the rational design of the complex catalysts.
基金supported by the National Natural Science Foundation of China (22008098, 21978156, 42002040)the Program for Innovative Research Team (in Science and Technology) in University of Henan Province (21IRTSTHN004)+1 种基金the Program for Science & Technology Innovation Talents in Universities of Henan Province (22HASTIT008)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2022-K34)。
文摘Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.
基金supported by a Post Doc grant of the German Academic Exchange Service(Deutscher Akademischer Austauschdienst,DAAD grant no.91552012)by the European Research Council(EU FP7 ERC advanced grant no.338846)
文摘The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.
文摘The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.
文摘Supported PtRu/C catalysts used in direct methanol fuel cells (DMFCs) were prepared by a new modified polyol method. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and cyclic voltammograms (CVs) were carried out to characterize the morphology, composition and the electrochemical properties of the PtRu/C catalyst. The results revealed that the PtRu nanoparticles with small average particle size (≈2.5 nm), and highly dispersed on the carbon support. The PtRu/C catalyst exhibited high catalytic activity and anti poisoned performance than that of the JM PtRu/C. It is imply that the modified polyol method is efficient for PtRu/C catalyst preparation.
基金financially supported by the National Natural Science Foundation of China(No.21972099)the National Natural Science Foundation of China(National Special Scientific Research Instrument and Equipment Development)(No.21427803-2)the 111 project(No.B17030)。
文摘The activity of Mo_(2) C-based catalyst on vegetable oil conversion into biofuel could be greatedly promoted by tuning the carbon content,while its modification mechanism on the surface properties remained elusive.Herein,the exposed active sites,the particle size and Lewis acid amount of Ni-Mo_(2) C/MCM-41 catalysts were regulated by varying CH_(4) content in carbonization gas.The activity of Ni-Mo_(2) C/MCM-41 catalysts in jatropha oil(JO)conversion showed a volcano-like trend over the catalysts with increasing CH_(4) content from 15%to 50%in the preparation process.The one prepared by 25%CH_(4) content(NiMo_(2) C(25)/MCM-41)exhibited the outstanding catalytic performance with 83.9 wt%biofuel yield and95.2%C_(15)-C_(18) selectivity.Such a variation of activity was ascribed to the most exposed active sites,the smallest particle size,and the lowest Lewis acid amount from Ni^(0) on the Ni-Mo_(2) C(25)/MCM-41 catalyst surface.Moreover,the Ni-Mo_(2) C(25)/MCM-41 catalyst could also effectively catalyze the conversion of crude waste cooking oil(WCO)into green diesel.This study offers an effective strategy to improve catalytic performance of molybdenum carbide catalyst on vegetable oil conversion.
基金the National Key R&D Program of China(2018YFE0122600)the National Natural Science Foundation of China(21802070).
文摘Carbonate-modified metal-support interfaces allow Ru/MnCO_(3) catalyst to exhibit over 99% selectivity,great specific activity and long-term anti-CO poisoning stability in atmospheric CO_(2) methanation.As a contrast,Ru/MnO catalyst with metal-oxide interfaces prefers reverse water-gas shift rather than methanation route,along with a remarkably lower activity and a less than 15% CH_(4) selectivity.The carbonatemodified interfaces are found to stabilize the Ru species and activate CO_(2) and H_(2) molecules.Ru-CO^(4) species are identified as the reaction intermediates steadily formed from CO_(2) dissociation,which show moderate adsorption strength and high reactivity in further hydrogenation to CH_(4),Furthermore,carbonates of Ru/MnCO_(3) are found to be consumed by hydrogenation to form CH_(4) and replenished by exchange with CO_(2),which are in a dynamic equilibrium during the reaction.Modification with surface carbonates is proved as an efficient strategy to endow metal-support interfaces of Ru-based catalysts with unique catalytic functions for selective CO_(2) hydrogenation.
文摘Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.
基金financial supports from National Key R&D Plan of China (2017YFB0102803)the National Natural Science Foundation of China (21676135)+8 种基金Scientific Instrument Develop Major Project of National Natural Science Foundation of China (51627810)Joint Funds of the National Natural Science Foundation and Liaoning of China (U1508202)Key R&D programs in Jiangsu (BE2018051)“333” project of Jiangsu Province (BRA2018007)Natural Science Foundation of Jiangsu Province (BK20161273, BK20181199)the Graduate Innovation Foundation of Nanjing university (2017ZDL05)support of PAPD of Jiangsu Higher Education Institutions“Six Talent Peaks Program” of Jiangsu ProvinceFundamental Research Funds for the Central Universities, China。
文摘A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 months’ shelf life) from single batch preparation with activated carbon ethylene glycol suspension.21 wt%, 42 wt% and 61 wt% Pt loadings are employed to showcase the advantages of the improved polyol process. The ultraviolet(UV)–visible spectra and ζ-potential measurements are conducted to monitor the wet chemistry process during catalyst preparation. The powder X-ray diffraction(XRD), transmission electron microscopy(TEM) and thermogravimetric analysis(TGA) characterizations are carried out on catalysts. The catalyst activities are investigated using electrochemical and single cell tests. The stability of Pt nanoparticle colloid is explored by ORR, cyclic voltammetry(CV) and ζ-potential measurements. The TEM results show the Pt particle sizes of the colloid, and the sizes of the 21 wt%, 42 wt% and 61 wt%Pt/C samples are 2.1–3.9 nm. Because of the high Pt dispersion, the Pt/C catalysts exhibit superior electroactivity toward ORR. In addition, four 61 wt% Pt/C catalysts made from the Pt colloid with 0–3 months’ shelf life show almost the same performance, which exhibits superior stability of the Pt colloid system without surfactant protection.
