近年来,以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中,氮氧化物(NOx)的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原(NH3-SCR)是目前消除氮氧化物的主流技术,低温NH3-SCR更是广泛应用于钢铁、焦化、水泥...近年来,以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中,氮氧化物(NOx)的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原(NH3-SCR)是目前消除氮氧化物的主流技术,低温NH3-SCR更是广泛应用于钢铁、焦化、水泥、玻璃、陶瓷和垃圾焚烧等行业的烟气排放治理.传统的V2O5-WO3/Ti O2催化剂活性温度高(300–400 oC)且钒具有生物毒性,因此亟待开发环境友好的低温非钒基脱硝催化剂.最近, Ce Ti Ox基催化剂由于在中高温段(250–400 oC)表现出优异的脱硝性能而得到广泛关注.然而,该催化剂仍面临低温活性差及抗硫性能差的问题,制约了其工业化应用.研究显示,添加过渡金属可提高Ce Ti Ox基催化剂的脱硝活性和抗硫中毒性能,这主要是因为过渡金属的添加可以有效改善催化剂的氧化还原性能和表面酸性.Mo O3作为一种可以提供大量酸性位的氧化物,常被用作助剂改善钒钨钛催化剂的活性.研究显示, Mo O3的引入可以促进催化剂中钒物种的分散度以及提高表面酸性.基于此,我们制备了一系列不同Mo含量的Mo O3/Ce Ti Ox催化剂,以期提高Ce Ti Ox催化剂的低温脱硝性能及抗SO2中毒能力,并着重研究表面Mo的修饰对Ce Ti Ox催化剂物理化学性质的影响.研究发现,表面Mo修饰可以显著提高Ce Ti Ox的低温催化活性,其脱硝效率在150 oC即可达到80%,同时抗SO2中毒能力也得到增强.进一步借助X射线衍射、比表面积测定、氢气程序升温还原、氨气程序升温脱附和X射线光电子能谱等方法对催化剂进行了全面表征分析.结果显示,表面Mo修饰对Ce Ti Ox催化剂物理化学性质的影响与其脱硝性能有着密不可分的关系.首先,钼物种主要是以Mo O3的形式存在于Ce Ti Ox表面,其最佳的负载量为4wt.%.其次,表面Mo的沉积显著提高了催化剂的表面酸量,尤其是Br?nsted酸位的数量,而表面酸位的增加有利于催化剂吸附与活化反应物种NH3;同时,表面Mo修饰还减弱了硝酸盐在催化剂表面的吸附,进一步促使NH3-SCR反应按照Eley-Rideal机理顺利进行.最后,该催化剂在H2O和SO2存在的条件下仍具有最佳的脱硝性能,因而有望用于实际含SO2的低温烟气脱硝.展开更多
The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier t...The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier transform infrared spectroscopy （FTIR） and NO＋CO reaction. The results revealed that the low temperature （〈150℃） catalytic performances were enhanced for CO pretreated samples. During CO pretreatment, the surface Cu＋/Cu0 and oxygen vacancies on ceria surface were present. The low va- lence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation. These effects in turn led to higher activities of CuO/CeO2 for NO reduction. The current study provided helpful understandings of active sites and reaction mechanism in NO＋CO reaction.展开更多
In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO, two series of catalysts （xCuyMn/Ce and xCu/yMn/Ce） were prepared by co-imp...In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO, two series of catalysts （xCuyMn/Ce and xCu/yMn/Ce） were prepared by co-impregnation and step- wise-impregnation methods, and characterized by means of X-ray diffraction （XRD）, Raman spectra, H2-temperature programmed reduction （H2-TPR）, in situ diffuse reflectance infrared Fourier transform spectra （in situ DRIFTS） techniques. Furthermore, the cata- lytic performances of these catalysts were evaluated by NO＋CO model reaction. The obtained results indicated that： （1） The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method, which was beneficial to the improvement of the reduction behavior; （2） The excellent reduction behavior was conducive to the formation of low valence state copper species （Cu＋/Cu0） and more oxygen vacancies （especially the surface synergetic oxygen vacancies （SSOV, Cu＋-n-Mn（4-x）-）） during the reaction process, which were beneficial to the adsorption of CO species and the dissociation of NO species, respectively, and further promoted the en- hancement of the catalytic performance. Finally, in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods, a possible reaction mechanism （schematic diagram） was tentatively proposed.展开更多
基金supported by the National Natural Foundation of China(21607019,21503115)the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control(OVEC013)the Talent Introduction Project of Chongqing Three Gorges University~~
基金supported by the National Natural Science Foundation of China(21773106,21707066,21677069,and 21806077)the China Postdoctoral Science Foundation(2018M642206)~~
文摘近年来,以雾霾为代表的大气污染问题严重影响到经济社会的可持续发展.其中,氮氧化物(NOx)的大量排放是导致雾霾天气的重要原因之一.氨选择性催化还原(NH3-SCR)是目前消除氮氧化物的主流技术,低温NH3-SCR更是广泛应用于钢铁、焦化、水泥、玻璃、陶瓷和垃圾焚烧等行业的烟气排放治理.传统的V2O5-WO3/Ti O2催化剂活性温度高(300–400 oC)且钒具有生物毒性,因此亟待开发环境友好的低温非钒基脱硝催化剂.最近, Ce Ti Ox基催化剂由于在中高温段(250–400 oC)表现出优异的脱硝性能而得到广泛关注.然而,该催化剂仍面临低温活性差及抗硫性能差的问题,制约了其工业化应用.研究显示,添加过渡金属可提高Ce Ti Ox基催化剂的脱硝活性和抗硫中毒性能,这主要是因为过渡金属的添加可以有效改善催化剂的氧化还原性能和表面酸性.Mo O3作为一种可以提供大量酸性位的氧化物,常被用作助剂改善钒钨钛催化剂的活性.研究显示, Mo O3的引入可以促进催化剂中钒物种的分散度以及提高表面酸性.基于此,我们制备了一系列不同Mo含量的Mo O3/Ce Ti Ox催化剂,以期提高Ce Ti Ox催化剂的低温脱硝性能及抗SO2中毒能力,并着重研究表面Mo的修饰对Ce Ti Ox催化剂物理化学性质的影响.研究发现,表面Mo修饰可以显著提高Ce Ti Ox的低温催化活性,其脱硝效率在150 oC即可达到80%,同时抗SO2中毒能力也得到增强.进一步借助X射线衍射、比表面积测定、氢气程序升温还原、氨气程序升温脱附和X射线光电子能谱等方法对催化剂进行了全面表征分析.结果显示,表面Mo修饰对Ce Ti Ox催化剂物理化学性质的影响与其脱硝性能有着密不可分的关系.首先,钼物种主要是以Mo O3的形式存在于Ce Ti Ox表面,其最佳的负载量为4wt.%.其次,表面Mo的沉积显著提高了催化剂的表面酸量,尤其是Br?nsted酸位的数量,而表面酸位的增加有利于催化剂吸附与活化反应物种NH3;同时,表面Mo修饰还减弱了硝酸盐在催化剂表面的吸附,进一步促使NH3-SCR反应按照Eley-Rideal机理顺利进行.最后,该催化剂在H2O和SO2存在的条件下仍具有最佳的脱硝性能,因而有望用于实际含SO2的低温烟气脱硝.
基金supported by the National Natural Science Foundation of China(21876168,21507130)the Key Projects for Common Key Technology Innovation in Key Industries in Chongqing(cstc2016zdcy-ztzx0020-01)+2 种基金the Chongqing Science&Technology Commission(cstc2016jcyjA0070,cstckjcxljrc13)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University(1456029)the Graduate Innovation Project of Chongqing Technology and Business University(yjscxx201803-028-22)~~
基金supported by National Basic Research Program of China(2010CB732300)National Natural Science Foundation of China(21273110,20973091)Natural Science Foundation for the Youth(21203091)
文摘The CuO/CeO2 catalysts were investigated by means of X-ray diffraction （XRD）, laser Raman spectroscopy （LRS）, X-ray photoelectronic spectroscopy （XPS）, temperature-programmed reduction （TPR）, in situ Fourier transform infrared spectroscopy （FTIR） and NO＋CO reaction. The results revealed that the low temperature （〈150℃） catalytic performances were enhanced for CO pretreated samples. During CO pretreatment, the surface Cu＋/Cu0 and oxygen vacancies on ceria surface were present. The low va- lence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation. These effects in turn led to higher activities of CuO/CeO2 for NO reduction. The current study provided helpful understandings of active sites and reaction mechanism in NO＋CO reaction.
基金supported by National Natural Science Foundation of China(20973091,21273110)National Basic Research Program of China(973 Program,2009CB623500,2010CB732300)+1 种基金Jiangsu Province Science and Technology Support Program(Industrial,BE2011167)Jiangsu Province Scientific Research Foundation for Graduate(CXZZ12_0038)
文摘In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO, two series of catalysts （xCuyMn/Ce and xCu/yMn/Ce） were prepared by co-impregnation and step- wise-impregnation methods, and characterized by means of X-ray diffraction （XRD）, Raman spectra, H2-temperature programmed reduction （H2-TPR）, in situ diffuse reflectance infrared Fourier transform spectra （in situ DRIFTS） techniques. Furthermore, the cata- lytic performances of these catalysts were evaluated by NO＋CO model reaction. The obtained results indicated that： （1） The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method, which was beneficial to the improvement of the reduction behavior; （2） The excellent reduction behavior was conducive to the formation of low valence state copper species （Cu＋/Cu0） and more oxygen vacancies （especially the surface synergetic oxygen vacancies （SSOV, Cu＋-n-Mn（4-x）-）） during the reaction process, which were beneficial to the adsorption of CO species and the dissociation of NO species, respectively, and further promoted the en- hancement of the catalytic performance. Finally, in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods, a possible reaction mechanism （schematic diagram） was tentatively proposed.
