Gold-based catalysts are promising in CO preferential oxidation(CO-PROX)reaction in H_(2)-rich stream on account of their high intrinsic activity for CO elimination even at ambient temperature.However,the decrease of ...Gold-based catalysts are promising in CO preferential oxidation(CO-PROX)reaction in H_(2)-rich stream on account of their high intrinsic activity for CO elimination even at ambient temperature.However,the decrease of CO conversion at elevated temperature due to the competition of H_(2)oxidation,together with the low stability of gold nanoparticles,has posed a dear challenge.Herein,we report that Au-Cu bimetallic catalyst prepared by galvanic replacement method shows a wide temperature window for CO total conversion(30-100℃)and very good catalyst stability without deactivation in a 200-h test.Detailed characterizations combined with density functional theory(DFT)calculation reveal that the synergistic effect of Au-Cu,the electron transfer from Au to Cu,leads to not only strengthened chemisorption of CO but also weakened dissociation of H_(2),both of which are helpful in inhibiting the competition of H_(2)oxidation thus widening the temperature window for CO total conversion.展开更多
Activated carbon （AC） supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation （PROX） in excess H2 was evaluated. Ag/AC cataly...Activated carbon （AC） supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation （PROX） in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures （≤200 ℃） following heat treatment in He at 200 ℃ （He200H200）, exhibited the best catalytic properties. Temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and temperature-programmed reduction （TPR） results indicated that silver oxides were produced during heat treatment in He at 200 ℃ which were reduced to metal silver nanoparticles in H2 at low temperatures （≤200 ℃）, simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 ℃. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.展开更多
采用浸渍法以Cu(CH3COO)2为前驱体,在N2气氛下于不同温度下焙烧,制备了CuOx/CeO2催化剂。结合XRD,H2-TPR,XPS等表征技术,以及CO-PROX(Preferential Oxidation of CO)反应测试,获得了CuOx/CeO2催化剂中不同Cu物种随焙烧温度变化的分布信...采用浸渍法以Cu(CH3COO)2为前驱体,在N2气氛下于不同温度下焙烧,制备了CuOx/CeO2催化剂。结合XRD,H2-TPR,XPS等表征技术,以及CO-PROX(Preferential Oxidation of CO)反应测试,获得了CuOx/CeO2催化剂中不同Cu物种随焙烧温度变化的分布信息及其对CO-PROX催化活性的影响。结果表明:CuOx/CeO2催化剂CO-PROX催化活性变化的趋势与催化剂表面分散态Cu+物种变化趋势一致,随着焙烧温度从200℃升至500℃,催化剂表面的分散态Cu+先增加后减少,当分散态Cu+在焙烧温度250～400℃达到最多时,其催化活性最好,随后下降,说明分散态Cu+对CO-PROX反应活性起关键作用。展开更多
Copper and cobalt oxides supported on CeO2 were investigated for preferential oxidation of carbon monoxide(CO-PROX)in the presence of excess hydrogen and CO2.(Cuo)1-x(Co3 O4)x/3-(CeO2)2.5(x=0,0.25,0.50,0.75,0.85 and 1...Copper and cobalt oxides supported on CeO2 were investigated for preferential oxidation of carbon monoxide(CO-PROX)in the presence of excess hydrogen and CO2.(Cuo)1-x(Co3 O4)x/3-(CeO2)2.5(x=0,0.25,0.50,0.75,0.85 and 1)catalysts were prepared by coprecipitation method.These mixed oxide catalysts were characterized by several physicochemical techniques,such as BET surface area(SBET),X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),temperature programmed reduction(TPR)and X-ray photoelectron spectroscopy(XPS).XRD studies show the peaks related to CuO and Co3 O4 phases in copper and cobalt containing CeO2 catalysts.The average particle size of the CeO2 crystallites is in the range of 8-10 nm as evaluated from HRTEM studies.XPS studies demonstrate that Cu,Co and Ce in(cuO)1-x(Co3O4)x/3-(CeO2)2.5 catalysts are presented in+2 and+1,+3 and+2 and+4 and+3 oxidation states,respectively.The catalyst with x=0.75 shows better activity and selectivity towards CO-PROX.Though the catalyst with only copper(CuO-CeO2,x=0)shows good activity but reverse water gas shift(RWGS)reaction is noticed at high temperature.On the other hand,RWGS reaction is suppressed on the cobalt containing CuO-ceO2 catalyst.Cobalt on CeO2 with x=1 shows hardly any activity for PRoX reaction at low temperatures.No methanation activity is observed on CuO-CeO2 or Co3O4-CeO2 catalysts.In contrast,combination of copper and cobalt on CeO2 shows methanation of CO where enhanced activity is observed with increasing in cobalt content.展开更多
Controlling the growth of nanocrystals is one of the most challenged issues in current catalytic field, which helps to further understand the size and morphology related behaviors for catalytic applications. In this w...Controlling the growth of nanocrystals is one of the most challenged issues in current catalytic field, which helps to further understand the size and morphology related behaviors for catalytic applications. In this work, we investigated the plane growth kinetics of Mg（OH）2 for catalytic application in preferential CO oxidation. Nanoflakes were synthesized through hydrothermal method. The morphology and structure of nanoflakes were characterized by TEM, SEM, and XRD. By varying the reaction temperature and time, Mg（OH）2 nanoflakes un- derwent an anisotropic growth. Benefited from the Ostwald ripening process, the thickness of nanoflake corre- sponding to the （110） plane of Mg（OH）2 was tuned from 7.6 nm to 24.0 nm, while the diameter of （001） plane in- creased from 18.2 nm to 30.2 nm. The grain growth kinetics for the thickness was well described in terms of an equation, D5= 7.65＋ 6.9 × 10^8exp（-28.14/RT）. After depositing Pt nanoparticles onto these Mg（OH）2 nanoflakes, an excellent catalytic performance was achieved for preferential CO oxidation in H2-rich streams with a wide temper- ature window from 140 ℃ to 240 ℃ for complete CO conversion due to the interaction between Pt and hydroxyl groups. The findings reported here would be helpful in discovering novel catalysts for application of proton ex- change membrane fuel cells.展开更多
基金This work was financially supported by the“Transformational Technologies for Clean Energy and Demonstration”,the Strategic Priority Research Program of the Chinese Academy of Sciences(CAS,No.XDA21030900)DNL Cooperation Fund,CAS(No.DNL201903)the National Natural Science Foundation of China(No.51701201).
文摘Gold-based catalysts are promising in CO preferential oxidation(CO-PROX)reaction in H_(2)-rich stream on account of their high intrinsic activity for CO elimination even at ambient temperature.However,the decrease of CO conversion at elevated temperature due to the competition of H_(2)oxidation,together with the low stability of gold nanoparticles,has posed a dear challenge.Herein,we report that Au-Cu bimetallic catalyst prepared by galvanic replacement method shows a wide temperature window for CO total conversion(30-100℃)and very good catalyst stability without deactivation in a 200-h test.Detailed characterizations combined with density functional theory(DFT)calculation reveal that the synergistic effect of Au-Cu,the electron transfer from Au to Cu,leads to not only strengthened chemisorption of CO but also weakened dissociation of H_(2),both of which are helpful in inhibiting the competition of H_(2)oxidation thus widening the temperature window for CO total conversion.
基金supported by the National Natural Science Foundation of China (No. 21207039)the Natural Science Foundation of Guangdong Province, China (Grant No. S2011010000737)+2 种基金the Doctoral Fund of Ministry of Education of China (20110172120017)the Fundamental Research Funds for the Central Universities (Grant No. 2011zm 0048)the Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences (No. Y007K1)
文摘Activated carbon （AC） supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation （PROX） in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures （≤200 ℃） following heat treatment in He at 200 ℃ （He200H200）, exhibited the best catalytic properties. Temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and temperature-programmed reduction （TPR） results indicated that silver oxides were produced during heat treatment in He at 200 ℃ which were reduced to metal silver nanoparticles in H2 at low temperatures （≤200 ℃）, simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 ℃. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.
文摘采用浸渍法以Cu(CH3COO)2为前驱体,在N2气氛下于不同温度下焙烧,制备了CuOx/CeO2催化剂。结合XRD,H2-TPR,XPS等表征技术,以及CO-PROX(Preferential Oxidation of CO)反应测试,获得了CuOx/CeO2催化剂中不同Cu物种随焙烧温度变化的分布信息及其对CO-PROX催化活性的影响。结果表明:CuOx/CeO2催化剂CO-PROX催化活性变化的趋势与催化剂表面分散态Cu+物种变化趋势一致,随着焙烧温度从200℃升至500℃,催化剂表面的分散态Cu+先增加后减少,当分散态Cu+在焙烧温度250～400℃达到最多时,其催化活性最好,随后下降,说明分散态Cu+对CO-PROX反应活性起关键作用。
基金Project supported by Council of Scientific and Industrial Research,Government of India through a Senior Research Fellowship。
文摘Copper and cobalt oxides supported on CeO2 were investigated for preferential oxidation of carbon monoxide(CO-PROX)in the presence of excess hydrogen and CO2.(Cuo)1-x(Co3 O4)x/3-(CeO2)2.5(x=0,0.25,0.50,0.75,0.85 and 1)catalysts were prepared by coprecipitation method.These mixed oxide catalysts were characterized by several physicochemical techniques,such as BET surface area(SBET),X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),temperature programmed reduction(TPR)and X-ray photoelectron spectroscopy(XPS).XRD studies show the peaks related to CuO and Co3 O4 phases in copper and cobalt containing CeO2 catalysts.The average particle size of the CeO2 crystallites is in the range of 8-10 nm as evaluated from HRTEM studies.XPS studies demonstrate that Cu,Co and Ce in(cuO)1-x(Co3O4)x/3-(CeO2)2.5 catalysts are presented in+2 and+1,+3 and+2 and+4 and+3 oxidation states,respectively.The catalyst with x=0.75 shows better activity and selectivity towards CO-PROX.Though the catalyst with only copper(CuO-CeO2,x=0)shows good activity but reverse water gas shift(RWGS)reaction is noticed at high temperature.On the other hand,RWGS reaction is suppressed on the cobalt containing CuO-ceO2 catalyst.Cobalt on CeO2 with x=1 shows hardly any activity for PRoX reaction at low temperatures.No methanation activity is observed on CuO-CeO2 or Co3O4-CeO2 catalysts.In contrast,combination of copper and cobalt on CeO2 shows methanation of CO where enhanced activity is observed with increasing in cobalt content.
基金This work was financially supported by the National Natural Science Foundation of China （Nos. 21025104, 21271171, and 91022018）.
文摘Controlling the growth of nanocrystals is one of the most challenged issues in current catalytic field, which helps to further understand the size and morphology related behaviors for catalytic applications. In this work, we investigated the plane growth kinetics of Mg（OH）2 for catalytic application in preferential CO oxidation. Nanoflakes were synthesized through hydrothermal method. The morphology and structure of nanoflakes were characterized by TEM, SEM, and XRD. By varying the reaction temperature and time, Mg（OH）2 nanoflakes un- derwent an anisotropic growth. Benefited from the Ostwald ripening process, the thickness of nanoflake corre- sponding to the （110） plane of Mg（OH）2 was tuned from 7.6 nm to 24.0 nm, while the diameter of （001） plane in- creased from 18.2 nm to 30.2 nm. The grain growth kinetics for the thickness was well described in terms of an equation, D5= 7.65＋ 6.9 × 10^8exp（-28.14/RT）. After depositing Pt nanoparticles onto these Mg（OH）2 nanoflakes, an excellent catalytic performance was achieved for preferential CO oxidation in H2-rich streams with a wide temper- ature window from 140 ℃ to 240 ℃ for complete CO conversion due to the interaction between Pt and hydroxyl groups. The findings reported here would be helpful in discovering novel catalysts for application of proton ex- change membrane fuel cells.
