The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanor...The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance(yield of styrene oxide and TOF value)followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes(73.3 and 93.4 k J/mol). The high resolution transmission electron microscopy results indicated that(100) and(110) crystal planes are predominantly exposed for Zr-doped CeOnanorods while(100)and(111) for nanocubes,(111) for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed(100) and(110) crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.展开更多
Direct synthesis of dimethyl carbonate(DMC)from CO2 is critical for achieving carbon neutrality,yet the sluggish formation and conversion of the key*CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit ...Direct synthesis of dimethyl carbonate(DMC)from CO2 is critical for achieving carbon neutrality,yet the sluggish formation and conversion of the key*CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields.Herein,we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO2 hollow nanospheres,which serve as an efficient catalyst for CO2 to DMC synthesis.The introduction of grain-boundary(GBs)induced the electron redistribution,which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface.This unique electronic landscape promoted reactive methoxy formation and stronger CO2 adsorption,thereby enabling more efficient coupling of*CH3O and*CO2 to form the*CH3OCOO.Concurrently,the enhanced CO2 adsorption facilitated the dissociation of*CH3OCOO and subsequent DMC formation.As a result,the 4%BCeO2-GBs achieved an advantageous DMC yield of 19.8 mmol/g.In the assistance of dehydrating agent,the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12%methanol conversion,which was 32 times higher than commercial CeO2.This study elucidated the intrinsic mechanisms governing*CH3OCOO intermediate behavior and offers valuable guidance for CO2 converting into high-value organic chemicals.展开更多
With great superiorities in energy density,rate capability and structural stability,Na3V2(PO4)2 F3(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges o...With great superiorities in energy density,rate capability and structural stability,Na3V2(PO4)2 F3(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism.Herein,a series of Zr-doped NVPF coated by N-doped carbon layer(~5 nm in thickness,homogenously)materials are fabricated by a sol-gel method,and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity,respectively.Specifically,among all samples of Na3 V2-xZrx(PO4)2 F3/NC(NVPF-Zr-x/NC,x=0,0.01,0.02,0.05,and 0.1),the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities(119.2 mAh g-1 at0.5 C),superior rate capability(98.1 mA h g-1 at 20 C)and excellent cycling performance.The structural evolution of NVPF-Zr-0.02/NC electrode,in-situ monitored by X-ray diffractometer,follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes,not just a solid-solutionreaction one.Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity(99.8 mA h g-1 at 0.5 C),high out-put voltage(3.5 V)and good cycling stability.This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.展开更多
Zr-doped TiO2 was prepared from TiOSO4 and ZrOCO3 by a co-precipitation method using NH3H2O as the precipitation agent. The Zr-doped TiO2 was characterized by X-ray diffraction(XRD), low temperature N2adsorption–de...Zr-doped TiO2 was prepared from TiOSO4 and ZrOCO3 by a co-precipitation method using NH3H2O as the precipitation agent. The Zr-doped TiO2 was characterized by X-ray diffraction(XRD), low temperature N2adsorption–desorption measurement, and UV–Vis diffuse reflectance spectroscopy technology. Appropriate amounts of ZrO2 addition can greatly improve the TiO2 microstructure properties and its photocatalytic activities. In addition, polyethylene glycol(PEG) was used as a surfactant for templating the pore structure of samples. A bimodal pore structure can be controlled using PEG6000 and PEG20000 surfactants simultaneously during the preparation. The rate constant of benzene degradation over the Zr-doped TiO2 linearly decreases with the increase of photocatalytic reaction temperature and decreases in a polynomial relation with the benzene concentration.Moreover, it increases approximately linearly with the increase of the illumination intensity or area.展开更多
The oxidative properties and characterization of CuO, CeO 2 and CuO/CeO 2 cata lysts were examined by means of a CO micro-reactor GC system, TPR, XPS and X-r ay diffraction Rietveld methods. The results show that eith...The oxidative properties and characterization of CuO, CeO 2 and CuO/CeO 2 cata lysts were examined by means of a CO micro-reactor GC system, TPR, XPS and X-r ay diffraction Rietveld methods. The results show that either CuO or CeO 2 ac tivity is quite low for CO oxidation. However, when CuO and CeO 2 are mixed, the oxidative activity of the catalyst increases significantly, probably owing to the valency status of copper species (Cu 2+ and Cu+) on the CeO 2 surfa ce, the dispersion and reducibility. XPS surface analysis shows that CuO loading is very important in forming of either Cu 2+ or Cu+. Rietveld analysis s hows that some CuO, which has smaller ion radius than Ce 4+, enters the Ce O 2 lattice after CuO and CeO 2 are mixed. When the CuO loading reaches 5.0%, the size of CuO crystals is a minimum (6.1 nm) and the micro-strain value i s a maximum (2.86×10 -3), resulting in high surface energy and the best ac tivity for CO oxidation.展开更多
The selective catalytic reduction(SCR) of NOx using MnOx and CeO2 supported on viscose-based active carbon fibers(ACF) at 120 ℃~270 ℃ relatively lower than the temperature when using V2O5/TiO2-anatase catalyst was ...The selective catalytic reduction(SCR) of NOx using MnOx and CeO2 supported on viscose-based active carbon fibers(ACF) at 120 ℃~270 ℃ relatively lower than the temperature when using V2O5/TiO2-anatase catalyst was studied.As a result,CeO2/ACF shows a better catalysis than MNOx/ACF,which is not affected by the reaction temperature. NO conversion of 85% is reached with the 10%-CeO2/ACF catalyst at the whole temperature window.Furthermore,a series of MnOx-CeO2/ACF composite catalysts were studied.The results show that the loading method of catalyst affects its activity.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
Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and cat...Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and catalytic activity in CO oxidation of CuOx species on CeO2 rods, cubes and polyhedra predominantly exposing {110}+{100}, {100} and {111} facets by the incipient wetness impregnation method with the lowest Cu loading of 0.025%. The structural evolution of CuOx species was found to depend on both the Cu loading and the CeO2 morphology. As the Cu loading increases, CuOx species are deposited preferentially on the surface defect of CeO2 and then aggregate and grow, accompanied by the formation of isolated Cu ions, CuOx clusters strongly/weakly interacting with the CeO2, highly dispersed Cu O nanoparticles, and large Cu O nanoparticles. The isolated Cu^+ species and CuOx clusters weakly interacting with the CeO2 were observed mainly on the O-terminated CeO2{100} facets. Meanwhile, more Cu(I) species are stabilized during CO reduction processes in CuOx/c-CeO2 catalysts than in CuOx-CeO2 and CuOx/p-CeO2 catalysts. The catalytic activities of various CuOx/CeO2 catalysts in CO oxidation vary with both the CuOx species and the CeO2 morphology. These results comprehensively elucidate the CuOx-CeO2 interactions and exemplify their morphology-dependence.展开更多
Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibilit...Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), CO chemi- sorption and H2 temperature-programmed reduction (H2-TPR). The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.展开更多
CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were ...CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.展开更多
基金the financial support from NNSFC(Project 21373054,21303023,21173052)the Natural Science Foundation of Shanghai Science and Technology Committee(08DZ2270500)
摘要The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance(yield of styrene oxide and TOF value)followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes(73.3 and 93.4 k J/mol). The high resolution transmission electron microscopy results indicated that(100) and(110) crystal planes are predominantly exposed for Zr-doped CeOnanorods while(100)and(111) for nanocubes,(111) for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed(100) and(110) crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.
摘要Direct synthesis of dimethyl carbonate(DMC)from CO2 is critical for achieving carbon neutrality,yet the sluggish formation and conversion of the key*CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields.Herein,we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO2 hollow nanospheres,which serve as an efficient catalyst for CO2 to DMC synthesis.The introduction of grain-boundary(GBs)induced the electron redistribution,which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface.This unique electronic landscape promoted reactive methoxy formation and stronger CO2 adsorption,thereby enabling more efficient coupling of*CH3O and*CO2 to form the*CH3OCOO.Concurrently,the enhanced CO2 adsorption facilitated the dissociation of*CH3OCOO and subsequent DMC formation.As a result,the 4%BCeO2-GBs achieved an advantageous DMC yield of 19.8 mmol/g.In the assistance of dehydrating agent,the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12%methanol conversion,which was 32 times higher than commercial CeO2.This study elucidated the intrinsic mechanisms governing*CH3OCOO intermediate behavior and offers valuable guidance for CO2 converting into high-value organic chemicals.
基金the National Natural Science Foundation of China(21975154)the Shanghai Municipal Education Commission(Innovation Program(2019-01-07-00-09E00021)+2 种基金Innovative Research Team of High-level Local Universities in Shanghaisupported by The Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher LearningShanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power。
摘要With great superiorities in energy density,rate capability and structural stability,Na3V2(PO4)2 F3(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism.Herein,a series of Zr-doped NVPF coated by N-doped carbon layer(~5 nm in thickness,homogenously)materials are fabricated by a sol-gel method,and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity,respectively.Specifically,among all samples of Na3 V2-xZrx(PO4)2 F3/NC(NVPF-Zr-x/NC,x=0,0.01,0.02,0.05,and 0.1),the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities(119.2 mAh g-1 at0.5 C),superior rate capability(98.1 mA h g-1 at 20 C)and excellent cycling performance.The structural evolution of NVPF-Zr-0.02/NC electrode,in-situ monitored by X-ray diffractometer,follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes,not just a solid-solutionreaction one.Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity(99.8 mA h g-1 at 0.5 C),high out-put voltage(3.5 V)and good cycling stability.This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.
基金financially supported by the National Natural Science Foundation of China (Nos. J1103315 and J1310008)
摘要Zr-doped TiO2 was prepared from TiOSO4 and ZrOCO3 by a co-precipitation method using NH3H2O as the precipitation agent. The Zr-doped TiO2 was characterized by X-ray diffraction(XRD), low temperature N2adsorption–desorption measurement, and UV–Vis diffuse reflectance spectroscopy technology. Appropriate amounts of ZrO2 addition can greatly improve the TiO2 microstructure properties and its photocatalytic activities. In addition, polyethylene glycol(PEG) was used as a surfactant for templating the pore structure of samples. A bimodal pore structure can be controlled using PEG6000 and PEG20000 surfactants simultaneously during the preparation. The rate constant of benzene degradation over the Zr-doped TiO2 linearly decreases with the increase of photocatalytic reaction temperature and decreases in a polynomial relation with the benzene concentration.Moreover, it increases approximately linearly with the increase of the illumination intensity or area.
摘要The oxidative properties and characterization of CuO, CeO 2 and CuO/CeO 2 cata lysts were examined by means of a CO micro-reactor GC system, TPR, XPS and X-r ay diffraction Rietveld methods. The results show that either CuO or CeO 2 ac tivity is quite low for CO oxidation. However, when CuO and CeO 2 are mixed, the oxidative activity of the catalyst increases significantly, probably owing to the valency status of copper species (Cu 2+ and Cu+) on the CeO 2 surfa ce, the dispersion and reducibility. XPS surface analysis shows that CuO loading is very important in forming of either Cu 2+ or Cu+. Rietveld analysis s hows that some CuO, which has smaller ion radius than Ce 4+, enters the Ce O 2 lattice after CuO and CeO 2 are mixed. When the CuO loading reaches 5.0%, the size of CuO crystals is a minimum (6.1 nm) and the micro-strain value i s a maximum (2.86×10 -3), resulting in high surface energy and the best ac tivity for CO oxidation.
摘要The selective catalytic reduction(SCR) of NOx using MnOx and CeO2 supported on viscose-based active carbon fibers(ACF) at 120 ℃~270 ℃ relatively lower than the temperature when using V2O5/TiO2-anatase catalyst was studied.As a result,CeO2/ACF shows a better catalysis than MNOx/ACF,which is not affected by the reaction temperature. NO conversion of 85% is reached with the 10%-CeO2/ACF catalyst at the whole temperature window.Furthermore,a series of MnOx-CeO2/ACF composite catalysts were studied.The results show that the loading method of catalyst affects its activity.
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)~~
摘要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.
摘要Elucidation of the CuOx-CeO2 interactions is of great interest and importance in understanding complex CuOx-CeO2 interfacial catalysis in various reactions. In the present work, we have investigated structures and catalytic activity in CO oxidation of CuOx species on CeO2 rods, cubes and polyhedra predominantly exposing {110}+{100}, {100} and {111} facets by the incipient wetness impregnation method with the lowest Cu loading of 0.025%. The structural evolution of CuOx species was found to depend on both the Cu loading and the CeO2 morphology. As the Cu loading increases, CuOx species are deposited preferentially on the surface defect of CeO2 and then aggregate and grow, accompanied by the formation of isolated Cu ions, CuOx clusters strongly/weakly interacting with the CeO2, highly dispersed Cu O nanoparticles, and large Cu O nanoparticles. The isolated Cu^+ species and CuOx clusters weakly interacting with the CeO2 were observed mainly on the O-terminated CeO2{100} facets. Meanwhile, more Cu(I) species are stabilized during CO reduction processes in CuOx/c-CeO2 catalysts than in CuOx-CeO2 and CuOx/p-CeO2 catalysts. The catalytic activities of various CuOx/CeO2 catalysts in CO oxidation vary with both the CuOx species and the CeO2 morphology. These results comprehensively elucidate the CuOx-CeO2 interactions and exemplify their morphology-dependence.
基金supported by National Natural Science Foundation of China(51202116)Ministry of Science and Technology,China(2010CB732304,2013AA065302)
摘要Praseodymium (Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), CO chemi- sorption and H2 temperature-programmed reduction (H2-TPR). The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.
基金Projected supported by the National Natural Science Foundation of China (20271028) and Tianjin Natural Science Foundation(033602511)
摘要CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.