SY509-3-127 [篇名] Characterization of spontaneously formed cerium-based conversion coatings on aluminum;SY509-3-128 [篇名] Effect of 2.2-dipyridine on borate-buffered electroless copper deposition……
The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities ...The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 °C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction (H2‐TPR), Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions (>97%) and CO2 selectivities (>50%) in the temperature range 80–150 °C.展开更多
CO methanation on Ni/CeO2 has recently received increasing attention.However,the low-temperature activity and carbon resistance of Ni/CeO2 still need to be improved.In this study,plasma decomposition of nickel nitrate...CO methanation on Ni/CeO2 has recently received increasing attention.However,the low-temperature activity and carbon resistance of Ni/CeO2 still need to be improved.In this study,plasma decomposition of nickel nitrate was performed at ca.150℃ and atmospheric pressure.This was followed by hydrogen reduction at 500 ℃ in the absence of plasma,and a highly dispersed Ni/CeO2 catalyst was obtained with improved CO adsorption and enhanced metal-support interaction.The plasma-decomposed catalyst showed significantly improved low-temperature activity with high methane selectivity(up to 100%)and enhanced carbon resistance for CO methanation.For example,at 250 ℃,the plasma-decomposed catalyst showed a CO conversion of 96.8% with high methane selectivity(almost 100%),whereas the CO conversion was only 14.7% for a thermally decomposed catalyst.展开更多
The supported Au nanoparticles have been regarded as promising catalysts for CO oxidation but still suffer from unsatisfactory catalytic activity and durability.Herein,we show a simple and efficient strategy to simult...The supported Au nanoparticles have been regarded as promising catalysts for CO oxidation but still suffer from unsatisfactory catalytic activity and durability.Herein,we show a simple and efficient strategy to simultaneously enhance the catalytic activity and durability for CO oxidation.Key to the success is modification of the supported Au nanoparticle catalyst with nanosized CeOx to construct abundant Au‐CeOx interface.Owing to the maximized interfacial effect on the Ce‐Ox‐modified Au nanoparticles,the concentration of positively‐charged Au species(Auδ+)was remarkably improved,leading to enhanced catalytic activities in the oxidation of CO.Importantly,the stability of Au nanoparticles is remarkably increased by CeOx modification,exhibiting good durability in a continuous test of CO oxidation at higher temperatures.展开更多
Solar-powered carbon dioxide (CO_2)-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiati...Solar-powered carbon dioxide (CO_2)-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiation onto a bed of supported nickel (Ni) catalyst was utilized to facilitate CO_2 conversion. Ceria (CeO_2)-titania (TiO_2) oxide supports of different compositions were employed and their effects on photothermal CO_2 conver- sion examined, Two factors are shown to be crucial for instigating photothermal CO_2 methanation activity: ① Fine nickel deposits are required for both higher active catalyst area and greater light absorption capacity for the initial heating of the catalyst bed; and ② the presence of defect sites on the support are necessary to promote adsorption of C02 for its subsequent activation, Titania inclusion within the support plays a crucial role in maintaining the oxygen vacancy defect sites on the (titanium-doped) cerium oxide. The combination of elevated light absorption and stabilized reduced states for CO_2 adsorption subsequently invokes effective Dhotothermal CO_2 methanation when the ceria and titania are blended in the ideal ratio(s).展开更多
A copper-ceria solid solution and ceria-supported copper catalysts were prepared and used for the catalytic hydrogenation of CO2 to CH3OH.According to site-specific classification and quantitative analyses(X-ray diffr...A copper-ceria solid solution and ceria-supported copper catalysts were prepared and used for the catalytic hydrogenation of CO2 to CH3OH.According to site-specific classification and quantitative analyses(X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,and CO adsorption),the interfaces of the prepared catalysts were classified as Cu incorporated into ceria(Cu-Ov-Cex),dispersed Cu O(D-Cu O-Ce O2),and bulk Cu O(B-Cu O-Ce O2)over the Ce O2 surface.These results,together with those of activity tests,showed that the Cu-Ov-Cex species was closely related to the CO2 hydrogenation activity and resulted in a much higher turnover frequency of CH3OH production than that observed with the D-Cu O-Ce O2 and B-Cu O-Ce O2 species.Thus,the copper-ceria solid solution exhibited improved activity due to the higher Cu-Ov-Cex fraction.展开更多
Ni‐CeO2 catalysts with a nickel content of 50 mol% were prepared using RF thermal plasma, and their catalytic activities for methane partial oxidation were characterized. For the synthesis of Ni‐CeO2 catalysts, a pr...Ni‐CeO2 catalysts with a nickel content of 50 mol% were prepared using RF thermal plasma, and their catalytic activities for methane partial oxidation were characterized. For the synthesis of Ni‐CeO2 catalysts, a precursor containing Ni(~5‐μm diameter) and CeO2(~200‐nm diameter)powders were heated simultaneously using an RF plasma at a power level of ~52 kVA and a powder feeding rate of ~120 g/h. From the X‐ray diffraction data and transmission electron microscopy images, the precursor formed into high crystalline CeO2 supports with nanosized Ni particles( 50‐nm diameter) on their surfaces. The catalytic performance was evaluated under atmospheric pressure at 500 °C and a CH4:O2 molar ratio of 2:1 with Ar diluent. Although the Ni content was high(~50 mol%), the experimental results reveal a methane conversion rate of 70%, selectivities of CO and H2 greater than 90% and slight carbon coking during an on‐stream test at 550 °C for 24 h.However, at 750 °C, the on‐stream test revealed the formation of filament‐like carbons with an increased methane conversion rate over 90%.展开更多
In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was p...In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was prepared by the calcination method and investigated for the CO oxidation. The microstructure and morphology of CeO2-Co3O4 were investigated by the Scanning Electron Microscope, High-resolution transmission electron microscopy, Raman and X-ray photoelectron spectroscopy characterization. The effect of CeO2 doping on Co3O4 for CO oxidation was characterized by in situ X-ray Diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). In situ XRD was carried out under H2 atmosphere to evaluate the redox property of catalysts. The results indicated that the ceria doping can enhance the reducibility of Co2+ and promote the Co3+-Co2+-Co3+ cycle, owing to the oxygen replenish property of CeO2. Furthermore, adsorbed carbonate species on the surface of CeO2-Co3O4 were investigated by in situ-DRIFTS experiment. It was turned out that carbonate species on ceria promoted cobalt oxide catalysts showed different IR peaks compared with pure cobalt oxide. The carbonate species on ceria promoted catalyst are more active, and similar to free state carbonate species with weak bonding to catalyst surface, which can effectively inhibit catalyst inactivation. This study revealed the mechanism of ceria promoting CO oxidation over cobalt oxide, which will provide theoretical support for the design of efficient CO oxidation catalysts.展开更多
CO self-poisoning and slow surface kinetics pose major challenges to a CO oxidation catalyst that should work at ambient temperature.Furthermore,the presence of moisture would cause passivation of the catalyst A highl...CO self-poisoning and slow surface kinetics pose major challenges to a CO oxidation catalyst that should work at ambient temperature.Furthermore,the presence of moisture would cause passivation of the catalyst A highly active ceria promoted Pt catalyst(4%Pt-12%CeO_2/SiO_2;conversion≥99%at low( 500 ppm) and high( 2500 ppm) CO concentrations was developed for CO oxidation at ambient temperature in humid air.Catalyst preparation variables such as Pt and CeO_2 loading,ceria deposition method,drying and calcination conditions for the ceria and Pt precursors were optimized experimentally.The activity was correlated with surface properties using CO/H_2 chemisorption,O_2-H_2 titration,X-ray diffraction and BET surface area analysis.The method of CeO_2 deposition had a significant impact on the catalytic activity.CeO_2 deposition by impregnation resulted in a catalyst that was three times more active than that prepared by deposition precipitation or CeO_2grafting.O_2-H_2 titration results revealed that the close association of ceria and Pt in the case of CeO_2deposition by impregnation resulted in higher activity.The catalyst support used was also crucial as a silica supported catalyst was five times more active than an alumina supported catalyst.The particle size and pore structure of the catalyst support were also crucial as the reaction was diffusion controlled.The drying and calcination conditions of the ceria and Pt precursors also played a crucial role in determining the catalytic activity.The Pt-CeO_2/SiO_2 catalysts with Pt 2.5 wt%and CeO_2 15 wt%were highly active(TOF 0.02 s^(-1)) and stable(conversion 99%after 15 h) at ambient conditions.展开更多
Globin-like mesoporous CeO2 has been constructed by using a CO-assisted synthetic approach based on hydroxide carbonate precursors, in which CO plays a key role in the formation of the globin-like mesoporous precursor...Globin-like mesoporous CeO2 has been constructed by using a CO-assisted synthetic approach based on hydroxide carbonate precursors, in which CO plays a key role in the formation of the globin-like mesoporous precursors as the carbon source because of its preferential adsorption on Ce^3+ under the hydrothermal conditions. The formation mechanism and the thermal transformation process from globin-like mesoporous CeCO3OH to CeO2 have been investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, BET surface area measurements, thermal analysis, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy and X-ray photoelectron spec- troscopy. Rod-like building blocks interconnected by nanoparticles circle around to form each globin-like CeO2 spheres, leading to the formation of a mesoporous structure. The globin-like mesoporous CeO2 shows much better performance in CO catalytic oxidation than ordinary CeO2 nanoparticles obtained by directly calcining cerium nitrate. Moreover, the globin-like mesoporous CeO2 can act as an ideal matrix for supported catalysts. Metallic Au particles can be well dispersed in the globin-like CeO2 matrix to form Au/CeO2 supported catalysts, which exhibit excellent activity for CO oxidation at room temperature.展开更多
文摘SY509-3-127 [篇名] Characterization of spontaneously formed cerium-based conversion coatings on aluminum;SY509-3-128 [篇名] Effect of 2.2-dipyridine on borate-buffered electroless copper deposition……
基金supported by the National Basic Research Program of China (973 Program, 2013CB934104)the National Natural Science Founda-tion of China (21225312, U1303192)~~
文摘The preferential oxidation of CO (CO‐PROX) is a hot topic because of its importance in pro‐ton‐exchange membrane fuel cells (PEMFCs). Au catalysts are highly active in CO oxidation. Howev‐er, their activities still need to be improved at the PEMFC operating temperatures of 80–120 °C. In the present study, Au nanoparticles of average size 2.6 nm supported on ceria‐modified Al2O3 were synthesized and characterized using powder X‐ray diffraction, nitrogen physisorption, transmission electron and scanning transmission electron microscopies, temperature‐programmed hydrogen reduction (H2‐TPR), Raman spectroscopy, and in situ diffuse‐reflectance infrared Fourier‐transform spectroscopy. Highly dispersed Au nanoparticles and strong structures formed by Au–support in‐teractions were the main active species on the ceria surface. The Raman and H2‐TPR results show that the improved catalytic performance of the Au catalysts can be attributed to enhanced strong metal–support interactions and the reducibility caused by ceria doping. The formation of oxygen vacancies on the catalysts increased their activities in CO‐PROX. The synthesized Au catalysts gave excellent catalytic performances with high CO conversions (>97%) and CO2 selectivities (>50%) in the temperature range 80–150 °C.
基金This work was supported by the National Natural Science Foundation of China(21476157,21536008 and 21621004)the National Key R&D Program of China(2016YFB0600902)~~
文摘CO methanation on Ni/CeO2 has recently received increasing attention.However,the low-temperature activity and carbon resistance of Ni/CeO2 still need to be improved.In this study,plasma decomposition of nickel nitrate was performed at ca.150℃ and atmospheric pressure.This was followed by hydrogen reduction at 500 ℃ in the absence of plasma,and a highly dispersed Ni/CeO2 catalyst was obtained with improved CO adsorption and enhanced metal-support interaction.The plasma-decomposed catalyst showed significantly improved low-temperature activity with high methane selectivity(up to 100%)and enhanced carbon resistance for CO methanation.For example,at 250 ℃,the plasma-decomposed catalyst showed a CO conversion of 96.8% with high methane selectivity(almost 100%),whereas the CO conversion was only 14.7% for a thermally decomposed catalyst.
文摘The supported Au nanoparticles have been regarded as promising catalysts for CO oxidation but still suffer from unsatisfactory catalytic activity and durability.Herein,we show a simple and efficient strategy to simultaneously enhance the catalytic activity and durability for CO oxidation.Key to the success is modification of the supported Au nanoparticle catalyst with nanosized CeOx to construct abundant Au‐CeOx interface.Owing to the maximized interfacial effect on the Ce‐Ox‐modified Au nanoparticles,the concentration of positively‐charged Au species(Auδ+)was remarkably improved,leading to enhanced catalytic activities in the oxidation of CO.Importantly,the stability of Au nanoparticles is remarkably increased by CeOx modification,exhibiting good durability in a continuous test of CO oxidation at higher temperatures.
基金financially supported by the Australian Research Council under the Laureate Fellowship Scheme (FL140100081)
文摘Solar-powered carbon dioxide (CO_2)-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiation onto a bed of supported nickel (Ni) catalyst was utilized to facilitate CO_2 conversion. Ceria (CeO_2)-titania (TiO_2) oxide supports of different compositions were employed and their effects on photothermal CO_2 conver- sion examined, Two factors are shown to be crucial for instigating photothermal CO_2 methanation activity: ① Fine nickel deposits are required for both higher active catalyst area and greater light absorption capacity for the initial heating of the catalyst bed; and ② the presence of defect sites on the support are necessary to promote adsorption of C02 for its subsequent activation, Titania inclusion within the support plays a crucial role in maintaining the oxygen vacancy defect sites on the (titanium-doped) cerium oxide. The combination of elevated light absorption and stabilized reduced states for CO_2 adsorption subsequently invokes effective Dhotothermal CO_2 methanation when the ceria and titania are blended in the ideal ratio(s).
文摘A copper-ceria solid solution and ceria-supported copper catalysts were prepared and used for the catalytic hydrogenation of CO2 to CH3OH.According to site-specific classification and quantitative analyses(X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,and CO adsorption),the interfaces of the prepared catalysts were classified as Cu incorporated into ceria(Cu-Ov-Cex),dispersed Cu O(D-Cu O-Ce O2),and bulk Cu O(B-Cu O-Ce O2)over the Ce O2 surface.These results,together with those of activity tests,showed that the Cu-Ov-Cex species was closely related to the CO2 hydrogenation activity and resulted in a much higher turnover frequency of CH3OH production than that observed with the D-Cu O-Ce O2 and B-Cu O-Ce O2 species.Thus,the copper-ceria solid solution exhibited improved activity due to the higher Cu-Ov-Cex fraction.
基金supported by Renewable Energy Technologies Development Program(No.2008NFC02J0200002009)Technology Innovation Program(No.10048910)funded by the Ministry of Trade,Industry and Energy(MI,Korea)
文摘Ni‐CeO2 catalysts with a nickel content of 50 mol% were prepared using RF thermal plasma, and their catalytic activities for methane partial oxidation were characterized. For the synthesis of Ni‐CeO2 catalysts, a precursor containing Ni(~5‐μm diameter) and CeO2(~200‐nm diameter)powders were heated simultaneously using an RF plasma at a power level of ~52 kVA and a powder feeding rate of ~120 g/h. From the X‐ray diffraction data and transmission electron microscopy images, the precursor formed into high crystalline CeO2 supports with nanosized Ni particles( 50‐nm diameter) on their surfaces. The catalytic performance was evaluated under atmospheric pressure at 500 °C and a CH4:O2 molar ratio of 2:1 with Ar diluent. Although the Ni content was high(~50 mol%), the experimental results reveal a methane conversion rate of 70%, selectivities of CO and H2 greater than 90% and slight carbon coking during an on‐stream test at 550 °C for 24 h.However, at 750 °C, the on‐stream test revealed the formation of filament‐like carbons with an increased methane conversion rate over 90%.
基金supported by the State Key Research Development Program of China(2016YFA0204200)the National Natural Science Foundation of China(21822603,21577036,21773062)+3 种基金the Shanghai Pujiang Program(17PJD011)the Zhejiang public welfare technology research plan/rural agriculture(LGN18B010001)the Zhejiang provincial Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing(NO:2016KF0005)the scientific research project of Zhejiang provincial education department(Y201839892)~~
文摘In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was prepared by the calcination method and investigated for the CO oxidation. The microstructure and morphology of CeO2-Co3O4 were investigated by the Scanning Electron Microscope, High-resolution transmission electron microscopy, Raman and X-ray photoelectron spectroscopy characterization. The effect of CeO2 doping on Co3O4 for CO oxidation was characterized by in situ X-ray Diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). In situ XRD was carried out under H2 atmosphere to evaluate the redox property of catalysts. The results indicated that the ceria doping can enhance the reducibility of Co2+ and promote the Co3+-Co2+-Co3+ cycle, owing to the oxygen replenish property of CeO2. Furthermore, adsorbed carbonate species on the surface of CeO2-Co3O4 were investigated by in situ-DRIFTS experiment. It was turned out that carbonate species on ceria promoted cobalt oxide catalysts showed different IR peaks compared with pure cobalt oxide. The carbonate species on ceria promoted catalyst are more active, and similar to free state carbonate species with weak bonding to catalyst surface, which can effectively inhibit catalyst inactivation. This study revealed the mechanism of ceria promoting CO oxidation over cobalt oxide, which will provide theoretical support for the design of efficient CO oxidation catalysts.
基金supported by US Army contract(W56HZV-05-C0686) at Auburn University administered through TARDEC
文摘CO self-poisoning and slow surface kinetics pose major challenges to a CO oxidation catalyst that should work at ambient temperature.Furthermore,the presence of moisture would cause passivation of the catalyst A highly active ceria promoted Pt catalyst(4%Pt-12%CeO_2/SiO_2;conversion≥99%at low( 500 ppm) and high( 2500 ppm) CO concentrations was developed for CO oxidation at ambient temperature in humid air.Catalyst preparation variables such as Pt and CeO_2 loading,ceria deposition method,drying and calcination conditions for the ceria and Pt precursors were optimized experimentally.The activity was correlated with surface properties using CO/H_2 chemisorption,O_2-H_2 titration,X-ray diffraction and BET surface area analysis.The method of CeO_2 deposition had a significant impact on the catalytic activity.CeO_2 deposition by impregnation resulted in a catalyst that was three times more active than that prepared by deposition precipitation or CeO_2grafting.O_2-H_2 titration results revealed that the close association of ceria and Pt in the case of CeO_2deposition by impregnation resulted in higher activity.The catalyst support used was also crucial as a silica supported catalyst was five times more active than an alumina supported catalyst.The particle size and pore structure of the catalyst support were also crucial as the reaction was diffusion controlled.The drying and calcination conditions of the ceria and Pt precursors also played a crucial role in determining the catalytic activity.The Pt-CeO_2/SiO_2 catalysts with Pt 2.5 wt%and CeO_2 15 wt%were highly active(TOF 0.02 s^(-1)) and stable(conversion 99%after 15 h) at ambient conditions.
文摘Globin-like mesoporous CeO2 has been constructed by using a CO-assisted synthetic approach based on hydroxide carbonate precursors, in which CO plays a key role in the formation of the globin-like mesoporous precursors as the carbon source because of its preferential adsorption on Ce^3+ under the hydrothermal conditions. The formation mechanism and the thermal transformation process from globin-like mesoporous CeCO3OH to CeO2 have been investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, BET surface area measurements, thermal analysis, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy and X-ray photoelectron spec- troscopy. Rod-like building blocks interconnected by nanoparticles circle around to form each globin-like CeO2 spheres, leading to the formation of a mesoporous structure. The globin-like mesoporous CeO2 shows much better performance in CO catalytic oxidation than ordinary CeO2 nanoparticles obtained by directly calcining cerium nitrate. Moreover, the globin-like mesoporous CeO2 can act as an ideal matrix for supported catalysts. Metallic Au particles can be well dispersed in the globin-like CeO2 matrix to form Au/CeO2 supported catalysts, which exhibit excellent activity for CO oxidation at room temperature.