Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carri...Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.展开更多
SO2-4–Mo O3–Zr O2–Nd2O3/Si O2(SMZN/Si O2) catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffr...SO2-4–Mo O3–Zr O2–Nd2O3/Si O2(SMZN/Si O2) catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffraction(XRD),scanning electron microscopy(SEM),thermogravimetry analysis(TGA),ammonia adsorption Fourier transform infrared spectra(NH3-FTIR),and ammonia adsorption temperature programmed desorption(NH3-TPD) to reveal the dependence of the stable catalytic activity on calcination time. The reason for catalyst deactivation was also studied. The calcination time remarkably affected the types of active centers on SMZN/Si O2-2,and 4 h was found to be the optimal calcination time. SO4 species bonded with small size Zr O2 were found to be the stable active centers,where the leaching of SO2-4and the deposition of coke were inhibited. The deposition of coke was easier on large size Zr O2 than on small size ones. Calcination in air flow could eliminate the deposited coke to recover the deactivated catalysts.展开更多
A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of app...A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows: calcination temperature of the catalyst 600 ℃, n(lactic acid):n(n-butyl alcohol)=1.0:3.0, w(S2O8^2-/ZrO2- CeO2)=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.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
Amorphous Ni-Ru-B/ZrO2 catalyst was prepared by the means of chemical reduction,and selective CO methanation as a strategy for CO removal in fuel processing applications was investigated over the amorphous Ni-Ru-B/ZrO...Amorphous Ni-Ru-B/ZrO2 catalyst was prepared by the means of chemical reduction,and selective CO methanation as a strategy for CO removal in fuel processing applications was investigated over the amorphous Ni-Ru-B/ZrO2 catalyst.The result showed that,at the temperature of 210-230℃,the catalyst was shown to be capable of reducing CO in a hydrogen-rich reformate to less than 10 ppm,while keeping the CO2conversion below 1.55%and the hydrogen consumption below 6.50%.?2009 Xin Fa Dong.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.展开更多
Amorphous Ni-B/ZrO2 catalysts were prepared by coprecipitation-chemical reduction with KBH4 aqueous solution,and various crystalline phase ZrO2(amorphous-ZrO2,tetragonal-ZrO2 and monoclinic-ZrO2) supported Ni-B cataly...Amorphous Ni-B/ZrO2 catalysts were prepared by coprecipitation-chemical reduction with KBH4 aqueous solution,and various crystalline phase ZrO2(amorphous-ZrO2,tetragonal-ZrO2 and monoclinic-ZrO2) supported Ni-B catalysts were obtained by thermal treatment in 5%H2-N2 stream at different temperature.The effect of ZrO2 polymorphs and the treatment temperature on the catalytic performance for the CO selective methanation were investigated,and the catalysts were characterized by N2 physisorption,Powder X-ray diffraction(XRD), Temperature-Programmed Desorption(CO-TPD and H2-TPD),and Differential Scanning Calorimeter(DSC).The treatment temperature affected strongly the crystalline structure of ZrO2,and the CO methanation activity and selectivity of the Ni-B/ZrO2 catalysts were significantly influenced by the crystalline phase of ZrO2.Of the three forms of ZrO2 polymorphs(amorphou-ZrO2,tetragonal-ZrO2 and monoclinic-ZrO2),the amorphous-ZrO2 supported nickle catalyst showed highest CO methanation activity,attributing in large part to the largest specific surface area and the optimum CO/H2 absorption intensity of the Ni-B/amorphous-ZrO2 catalyst.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
Copper supported over silica exhibited very high activity and selectivity for the direct synthesis of indole at atmospheric pressure. Under the reaction temperature of 325C,the yield of indole could obtain 88%.
With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase compos...With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.展开更多
基金E.L.,K.L.,P.W.,and S.T.are supported by the SCCER-Heat and Energy Storage program
摘要Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.
基金supported by the National Nature Science Foundation of China (no.21106089)
摘要SO2-4–Mo O3–Zr O2–Nd2O3/Si O2(SMZN/Si O2) catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffraction(XRD),scanning electron microscopy(SEM),thermogravimetry analysis(TGA),ammonia adsorption Fourier transform infrared spectra(NH3-FTIR),and ammonia adsorption temperature programmed desorption(NH3-TPD) to reveal the dependence of the stable catalytic activity on calcination time. The reason for catalyst deactivation was also studied. The calcination time remarkably affected the types of active centers on SMZN/Si O2-2,and 4 h was found to be the optimal calcination time. SO4 species bonded with small size Zr O2 were found to be the stable active centers,where the leaching of SO2-4and the deposition of coke were inhibited. The deposition of coke was easier on large size Zr O2 than on small size ones. Calcination in air flow could eliminate the deposited coke to recover the deactivated catalysts.
基金supported by the Science and Technique Foundation of Shaaxi Province of China (2008K07-32)the Foundation of Shaanxi Educa- tional Committee of China (08JK228)the Graduate Innovation Fund of Shaanxi University of Science and Technology
摘要A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows: calcination temperature of the catalyst 600 ℃, n(lactic acid):n(n-butyl alcohol)=1.0:3.0, w(S2O8^2-/ZrO2- CeO2)=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.
基金supported by the National Natural Science Foundation of China(No.51576039)
摘要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.
基金supported by the National Natural Science Foundation of China(No.20576023)the Guangdong Province Natural Science Foundation(No.06025660).
摘要Amorphous Ni-Ru-B/ZrO2 catalyst was prepared by the means of chemical reduction,and selective CO methanation as a strategy for CO removal in fuel processing applications was investigated over the amorphous Ni-Ru-B/ZrO2 catalyst.The result showed that,at the temperature of 210-230℃,the catalyst was shown to be capable of reducing CO in a hydrogen-rich reformate to less than 10 ppm,while keeping the CO2conversion below 1.55%and the hydrogen consumption below 6.50%.?2009 Xin Fa Dong.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.
基金Supported by the National Natural Science Foundation of China(21076047)the Natural Science Foundation of Zhongkai University of Agriculture and Engineering(G3100026)
摘要Amorphous Ni-B/ZrO2 catalysts were prepared by coprecipitation-chemical reduction with KBH4 aqueous solution,and various crystalline phase ZrO2(amorphous-ZrO2,tetragonal-ZrO2 and monoclinic-ZrO2) supported Ni-B catalysts were obtained by thermal treatment in 5%H2-N2 stream at different temperature.The effect of ZrO2 polymorphs and the treatment temperature on the catalytic performance for the CO selective methanation were investigated,and the catalysts were characterized by N2 physisorption,Powder X-ray diffraction(XRD), Temperature-Programmed Desorption(CO-TPD and H2-TPD),and Differential Scanning Calorimeter(DSC).The treatment temperature affected strongly the crystalline structure of ZrO2,and the CO methanation activity and selectivity of the Ni-B/ZrO2 catalysts were significantly influenced by the crystalline phase of ZrO2.Of the three forms of ZrO2 polymorphs(amorphou-ZrO2,tetragonal-ZrO2 and monoclinic-ZrO2),the amorphous-ZrO2 supported nickle catalyst showed highest CO methanation activity,attributing in large part to the largest specific surface area and the optimum CO/H2 absorption intensity of the Ni-B/amorphous-ZrO2 catalyst.
基金the financial support from China Postdoctoral Science Foundation (2014M560224)
摘要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.
摘要Copper supported over silica exhibited very high activity and selectivity for the direct synthesis of indole at atmospheric pressure. Under the reaction temperature of 325C,the yield of indole could obtain 88%.
基金the financial support from the National Natural Science Foundation of China (No. 21266022, No. 21466022)the National High Technology Research and Development Program 863 (2014AA022002, 2012AA101800-03, 2012AA021205-6, 2012AA021704)+1 种基金the Key Programs of the National Laboratory (No. SKLFZZB-201312)the International Science & Technology Cooperation Program of China (2014DFA61040)
摘要With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.