A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of ...A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.展开更多
Solid strong base catalysts are highly attractive for diverse reactions owing to their advantages of neglectable corrosion,facile separation,and environmental friendliness.However,their widespread applications are imp...Solid strong base catalysts are highly attractive for diverse reactions owing to their advantages of neglectable corrosion,facile separation,and environmental friendliness.However,their widespread applications are impeded by basic components aggregation and low stability.In this work,we fabricate single calcium atoms on graphene(denoted as Ca1/G)by use of a redox strategy for the first time,producing solid strong base catalyst with high activity and stability.The precursor Ca(NO_(3))_(2)is first reduced to CaO at 400℃ by the support graphene,forming CaO/G with conventional basic sites,and the subsequent reduction at 850℃results in the generation of Ca1/G with atomically dispersed Ca.Various characterizations reveal that Ca single atoms are anchored on graphene in tetra-coordination(Ca-C_(2)-N_(2))where N is in situ doped from Ca(NO_(3))_(2).The atomically dispersed Ca,along with their anchoring on the support,endow Ca1/G with high activity and stability toward the transesterification reaction of ethylene carbonate with methanol.The turnover frequency value reaches 128.0 h^(-1)on Ca1/G,which is much higher than the traditional counterpart CaO/G and various reported solid strong bases(2.9-46.2 h^(-1)).Moreover,the activity of Ca1/G is well maintained during 5 cycles,while 60%of activity is lost for the conventional analogue CaO/G due to the leaching of Ca.展开更多
It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.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 effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the ...The effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H2O and CO2,respectively.The secondary pathway was the water-gas shift reaction.The results indicated that the CO2 production led to an increase in both primary and secondary pathways,and H2O production decreased when surface basicity of the catalyst increased in the order Ca 〉 Mg 〉 La.展开更多
Wormholelike mesoporous carbons (WMCs) with three different pore diameters (D-P), namely WMC-F7 (D-p = 8.5 nm), WMC-F30 (D-p =4.4 nm), and WMC-F0 (D-p =3.1 nm) are prepared via a modified sol-gel process. Then PtRu na...Wormholelike mesoporous carbons (WMCs) with three different pore diameters (D-P), namely WMC-F7 (D-p = 8.5 nm), WMC-F30 (D-p =4.4 nm), and WMC-F0 (D-p =3.1 nm) are prepared via a modified sol-gel process. Then PtRu nanoparticles with the particle size (40 of 3.2 nm supported on WMCs are synthesized with a modified pulse microwave-assisted polyol method. It is found that the pore diameter of WMCs plays an important role in the electrochemical activity of PtRu toward alcohol electrooxidation reaction. PtRu/WMC-F7 with D-p > 2d(pt) exhibits the largest electrochemical surface area (ESA) and the highest activity toward methanol electrooxidation. With the decrease in Dp, PtRu/WMC-F30 and PtRu/WMC-F0 have much lower ESA and electrochemical activity, especially for the isopropanol electrooxidation with a larger molecular size. When D-p is more than twice d(pt), the mass transfer of reactants and electrolyte are easier, and thus more PtRu nanoparticles can be utilized and the catalysts activity can be enhanced. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
基金the National Natural Science Foundation of China (Grant Nos. 21273058, 21673064, 51802059 and 21503059)China Postdoctoral Science Foundation (Grant Nos. 2018M631938, 2018T110307 and 2017M621284)+1 种基金Heilongjiang Postdoctoral Fund (LBH-Z17074)Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2019040 and 2019041)
文摘A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.
基金supported by the National Science Fund for Distinguished Young Scholars(22125804)the National Natural Science Foundation of China(22078155 and 22178163)the National Students'platform for innovation and entrepreneurship training program(20210291013Z).
文摘Solid strong base catalysts are highly attractive for diverse reactions owing to their advantages of neglectable corrosion,facile separation,and environmental friendliness.However,their widespread applications are impeded by basic components aggregation and low stability.In this work,we fabricate single calcium atoms on graphene(denoted as Ca1/G)by use of a redox strategy for the first time,producing solid strong base catalyst with high activity and stability.The precursor Ca(NO_(3))_(2)is first reduced to CaO at 400℃ by the support graphene,forming CaO/G with conventional basic sites,and the subsequent reduction at 850℃results in the generation of Ca1/G with atomically dispersed Ca.Various characterizations reveal that Ca single atoms are anchored on graphene in tetra-coordination(Ca-C_(2)-N_(2))where N is in situ doped from Ca(NO_(3))_(2).The atomically dispersed Ca,along with their anchoring on the support,endow Ca1/G with high activity and stability toward the transesterification reaction of ethylene carbonate with methanol.The turnover frequency value reaches 128.0 h^(-1)on Ca1/G,which is much higher than the traditional counterpart CaO/G and various reported solid strong bases(2.9-46.2 h^(-1)).Moreover,the activity of Ca1/G is well maintained during 5 cycles,while 60%of activity is lost for the conventional analogue CaO/G due to the leaching of Ca.
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
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.
文摘The effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H2O and CO2,respectively.The secondary pathway was the water-gas shift reaction.The results indicated that the CO2 production led to an increase in both primary and secondary pathways,and H2O production decreased when surface basicity of the catalyst increased in the order Ca 〉 Mg 〉 La.
基金supported by the National Natural Science Foundation of China (no. 91434106)
文摘Wormholelike mesoporous carbons (WMCs) with three different pore diameters (D-P), namely WMC-F7 (D-p = 8.5 nm), WMC-F30 (D-p =4.4 nm), and WMC-F0 (D-p =3.1 nm) are prepared via a modified sol-gel process. Then PtRu nanoparticles with the particle size (40 of 3.2 nm supported on WMCs are synthesized with a modified pulse microwave-assisted polyol method. It is found that the pore diameter of WMCs plays an important role in the electrochemical activity of PtRu toward alcohol electrooxidation reaction. PtRu/WMC-F7 with D-p > 2d(pt) exhibits the largest electrochemical surface area (ESA) and the highest activity toward methanol electrooxidation. With the decrease in Dp, PtRu/WMC-F30 and PtRu/WMC-F0 have much lower ESA and electrochemical activity, especially for the isopropanol electrooxidation with a larger molecular size. When D-p is more than twice d(pt), the mass transfer of reactants and electrolyte are easier, and thus more PtRu nanoparticles can be utilized and the catalysts activity can be enhanced. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
