The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O...The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.展开更多
The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development ...The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.展开更多
The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition beha...The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition behavior and SO2 poisoning over V2 O5-MoO3/TiO2 catalysts modified with CeO2 and SiO2 were investigated.By the means of characterization analysis,it was found that the addition of SiO2 into VMo/Ti-Ce had an impact on the interaction existed between catalyst surface atoms and NH4 HSO4.Temperatureprogrammed methods and in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments indicated that the doping of SiO2 promoted the decomposition of deposited NH4 HSO4 on VMo/Ti-Ce catalyst surface by reducing the thermal stability of NH4 HSO4 and enhancing the NH4 HSO4 reactivity with NO in low temperature.And this improvement may be the reason for the better catalytic activity than VMo/Ti-Ce in the case of NH4 HSO4 deposition.Accompanied with cerium sulfate species generated over catalyst surface,the conversion of SO2 to SO3 was inhibited in SiCe mixed catalyst.The addition of SiO2 could promote the decomposition of cerium sulfate,which may be a potential strategy to enhance the resistance of SO2 poisoning over CeO2-modifed catalysts.展开更多
CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （...CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.展开更多
Pt-CeO2-ZrO2/MgO （Pt-CZ/MgO） catalysts with 0.8 wt% Pt, 3.0 wt% CeO2 and 3.0 wt% ZrO2 were prepared by wet impregnation method. Support MgO was obtained using ion exchange resin method or using commercial MgO. XRD, ...Pt-CeO2-ZrO2/MgO （Pt-CZ/MgO） catalysts with 0.8 wt% Pt, 3.0 wt% CeO2 and 3.0 wt% ZrO2 were prepared by wet impregnation method. Support MgO was obtained using ion exchange resin method or using commercial MgO. XRD, BET, SEM, TEM, DTA-TG and CO2-TPD were used to characterize the catalysts. CH4-CO2 reforming to synthesis gas （syngas） was performed to test the catalytic behavior of the catalysts. The catalyst Pt-CZ/MgO-IE（D） prepared using ion exchange resin exhibits more regular structure, smaller and more unique particle sizes, and stronger basicity than the catalyst Pt-CZ/MgO prepared from commercial MgO. At 1073 K and atmospheric pressure, Pt-CZ/MgO-IE（D） catalyst has a higher activity and greater stability than Pt-CZ/MgO catalyst for CH4-CO2 reforming reaction at high gas hourly space velocity of 36000 mL/（g.h） with a stoichiometric feed of CH4 and C02. Activity measurement and characterization results demonstrate that modification of the support using ion exchange resin method can promote the surface structural property and stability, therefore enhancing the activity and stability for CH4-CO2 reforming reaction.展开更多
XRD, Raman, TEM, and N2-adsorption were utilized to characterize CeO2/SiO2 prepared by coprecipi-tation and surfactant-assisted method. The results show that nanocrystalline CeO2 can be uniformly supported on the surf...XRD, Raman, TEM, and N2-adsorption were utilized to characterize CeO2/SiO2 prepared by coprecipi-tation and surfactant-assisted method. The results show that nanocrystalline CeO2 can be uniformly supported on the surface of SiO2 particles, when the molar ratio of Si4+/(Ce3++Si4+) is less than 35% in coprecipitation samples. At higher Si content, the surface of SiO2 can not be fully covered by CeO2. With surfactant (CTAB) added, the u-iformly supported structure can even exist when the molar ratio of Si4+/(Ce3++Si4+) is as high as 53%. It is because Ce and Si complexes can be well dispersed in precursor solution in present of CTAB. However, the uniformly supported structure can not be synthesised through surfactant-assisted approch for its hydrothermal threatment, which can easily lead to separate aggregation of nanocrystalline CeO2 and SiO2 particles.展开更多
The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with eth...The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.展开更多
基金the National Key Project for Basic Research of China(973 Project)(No.2005CB221402)the China National Petroleum Corporation.
文摘The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.
基金financially supported by the National Natural Science Foundation of China(22205205)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y。
文摘The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.
基金supported by the National Natural Science Foundation of China(No.51576039)
文摘The deposition of NH4 HSO4 and the poisoning effect of SO2 on SCR catalyst are the main obstacles that restrict the industrial application of CeO2-doped SCR catalysts.In this work,deposited NH4 HSO4 decomposition behavior and SO2 poisoning over V2 O5-MoO3/TiO2 catalysts modified with CeO2 and SiO2 were investigated.By the means of characterization analysis,it was found that the addition of SiO2 into VMo/Ti-Ce had an impact on the interaction existed between catalyst surface atoms and NH4 HSO4.Temperatureprogrammed methods and in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments indicated that the doping of SiO2 promoted the decomposition of deposited NH4 HSO4 on VMo/Ti-Ce catalyst surface by reducing the thermal stability of NH4 HSO4 and enhancing the NH4 HSO4 reactivity with NO in low temperature.And this improvement may be the reason for the better catalytic activity than VMo/Ti-Ce in the case of NH4 HSO4 deposition.Accompanied with cerium sulfate species generated over catalyst surface,the conversion of SO2 to SO3 was inhibited in SiCe mixed catalyst.The addition of SiO2 could promote the decomposition of cerium sulfate,which may be a potential strategy to enhance the resistance of SO2 poisoning over CeO2-modifed catalysts.
文摘CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method. In combination with the characterization methods of N2 adsorption/desorption, XRD, temperature-programmed reduction （TPR）, and FT-IR, the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated. The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4. The catalyst with the Ce/Co atomic ratio 1 ： 16 exhibits the best activity, which converts 77% of CO at room temperature and completely oxidizes CO at 45 ℃.
基金supported by the National Natural Science Foundation of China (No. 20873013)
文摘Pt-CeO2-ZrO2/MgO （Pt-CZ/MgO） catalysts with 0.8 wt% Pt, 3.0 wt% CeO2 and 3.0 wt% ZrO2 were prepared by wet impregnation method. Support MgO was obtained using ion exchange resin method or using commercial MgO. XRD, BET, SEM, TEM, DTA-TG and CO2-TPD were used to characterize the catalysts. CH4-CO2 reforming to synthesis gas （syngas） was performed to test the catalytic behavior of the catalysts. The catalyst Pt-CZ/MgO-IE（D） prepared using ion exchange resin exhibits more regular structure, smaller and more unique particle sizes, and stronger basicity than the catalyst Pt-CZ/MgO prepared from commercial MgO. At 1073 K and atmospheric pressure, Pt-CZ/MgO-IE（D） catalyst has a higher activity and greater stability than Pt-CZ/MgO catalyst for CH4-CO2 reforming reaction at high gas hourly space velocity of 36000 mL/（g.h） with a stoichiometric feed of CH4 and C02. Activity measurement and characterization results demonstrate that modification of the support using ion exchange resin method can promote the surface structural property and stability, therefore enhancing the activity and stability for CH4-CO2 reforming reaction.
文摘XRD, Raman, TEM, and N2-adsorption were utilized to characterize CeO2/SiO2 prepared by coprecipi-tation and surfactant-assisted method. The results show that nanocrystalline CeO2 can be uniformly supported on the surface of SiO2 particles, when the molar ratio of Si4+/(Ce3++Si4+) is less than 35% in coprecipitation samples. At higher Si content, the surface of SiO2 can not be fully covered by CeO2. With surfactant (CTAB) added, the u-iformly supported structure can even exist when the molar ratio of Si4+/(Ce3++Si4+) is as high as 53%. It is because Ce and Si complexes can be well dispersed in precursor solution in present of CTAB. However, the uniformly supported structure can not be synthesised through surfactant-assisted approch for its hydrothermal threatment, which can easily lead to separate aggregation of nanocrystalline CeO2 and SiO2 particles.
基金the financial support from China Postdoctoral Science Foundation (2014M560224)
文摘The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.
