CuO调配SnO2表面用于碳烟颗粒燃烧:单层分散阈值效应对催化性能的影响

doi:10.1016/S1872-2067(19)63354-1

催化学报 ›› 2019, Vol. 40 ›› Issue (6): 905-916.DOI: 10.1016/S1872-2067(19)63354-1

CuO调配SnO₂表面用于碳烟颗粒燃烧:单层分散阈值效应对催化性能的影响

沈家庭^a, 冯小辉^a, 刘瑞^a, 徐香兰^a, 饶成^a, 刘建军^b, 方修忠^a, 谭超^c, 谢有畅^d, 王翔^a

a 南昌大学化学学院, 江西南昌 330031;
b 江西宝安新材料科技有限公司, 江西萍乡 337000;
c 宜宾学院, 过程分析与控制四川省高校重点实验室, 四川宜宾 644000;
d 北京大学化学与分子工程学院, 北京1000871

收稿日期:2019-01-29 修回日期:2019-03-12 出版日期:2019-06-18 发布日期:2019-04-26
通讯作者: 王翔
基金资助:
国家自然科学基金（21567016，21666020）；江西省自然科学基金（20181ACB20005，20171BAB213013，20181BCD40004，20181BAB203017）；江西省研究生创新基金（YC2018-B015）；江西省教育厅基金（KJLD14005）；四川省高校过程分析与控制重点实验室开放基金（2017002）.

Tuning SnO₂ surface with CuO for soot particulate combustion:The effect of monolayer dispersion capacity on reaction performance

Jiating Shen^a, Xiaohui Feng^a, Rui Liu^a, Xianglan Xu^a, Cheng Rao^a, Jianjun Liu^b, Xiuzhong Fang^a, Chao Tan^c, Youchang Xie^d, Xiang Wang^a

a Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, College of Chemistry, Nanchang University, Nanchang 330031, Jiangxi, China;
b Jiangxi Baoan New Material Technology Corporation, LTD, Pingxiang 337000, Jiangxi, China;
c Key Laboratory of Process Analysis and Control of Sichuan Universities, Yibin University, Yibin 644000, Sichuan, China;
d College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2019-01-29 Revised:2019-03-12 Online:2019-06-18 Published:2019-04-26
Contact: S1872-2067(19)63354-1
Supported by:
This work is supported by the National Natural Science Foundation of China (21567016, 21666020), the Natural Science Foundation of Jiangxi Province (20181ACB20005, 20171BAB213013, 20181BCD40004, 20181BAB203017), the Innovation Fund Designated for Graduate Students of Jiangxi Province (YC2018-B015), the Education Department Foundation of Jiangxi Province (KJLD14005), and the Opening Fund of Key Laboratory of Process Analysis and Control of Sichuan Universities (2017002), which are greatly acknowledged by the authors.

摘要/Abstract

摘要：

柴油发动机由于具有良好的动力和经济性等优势而得到广泛的应用，但排放的尾气中碳烟颗粒物（PM）却给人类健康和环境带来了严重的危害.目前PM污染的治理引起了广大科研工作者的关注.催化燃烧成为PM污染消除技术中最有效的方法.
金属氧化物负载到载体上时，通常会出现单层分散现象，其单层分散容量可以通过XRD，XPS和Raman等外推法测定.此外，当负载体系用作某种反应的催化剂时，往往会表现出单层分散阈值效应，即阈值附近的催化剂通常具有较高的活性和选择性等.目前单层分散理论已被广泛接受，成为设计高性能催化材料的重要指导思想.
在过去八年本课题组将SnO₂基催化材料用于多种环保和能源反应，并系统地探究了其催化性能.结果表明，SnO₂含有丰富的表面活泼氧和晶格氧，且热稳定性高，是一种优良的催化剂载体.基于单层分散理论，为获得更实用的PM燃烧催化剂，我们利用浸渍法设计制备了系列不同CuO负载量的CuO/SnO₂催化剂，并使用XRD，XPS，Raman，TEM，STEM-mapping，H₂-TPR，soot-TPR和O₂-TPD等手段深入研究了其构效关系.利用XRD和XPS外推法测得的CuO高度分散在SnO₂载体表面，其单层分散阈值为2.09mmol 100 m^-2，即相当于4.8% CuO负载量.低于该负载量时，CuO以亚单层分散态存在；而高于该负载量时，形成的CuO微晶和单层分散态的CuO共存.在单层分散阈值之前，催化剂的碳烟燃烧活性随CuO负载量的升高而上升；进一步提高CuO负载量对其活性无明显的影响.Raman结果表明，在单层分散阈值之前，CuO负载到SnO₂载体上可有效形成表面活泼氧中心，且其含量随CuO负载量升高而增加；进一步提高CuO负载量则对其含量无明显改变.因此，CuO/SnO₂催化剂用于碳烟颗粒燃烧具有明显的阈值效应.以上结果表明，表面活泼氧中心含量是决定该催化剂活性的主要因素.

关键词: 氧化锡负载的氧化铜, 碳烟颗粒燃烧, 单层分散, XRD和XPS外推法, 阈值效应

Abstract:

With the objective to investigate the structure-reactivity relationship of CuO/SnO₂ and eventually design more applicable catalysts for soot combustion, catalysts with different CuO loadings have been prepared by impregnation method. By using X-ray diffraction and X-ray photoelectron spectroscopy extrapolation methods, it is disclosed that CuO disperses finely on the SnO₂ support to form a monolayer with a capacity of 2.09 mmol 100 m^?2, which equals 4.8 wt% CuO loading. When the CuO loading is below the capacity, it is in a sub-monolayer state. However, when the loading is above the capacity, CuO micro-crystallites will be formed that coexist with the CuO monolayer. The soot combustion activity of the catalyst increases with the CuO loading until it reaches the monolayer dispersion capacity. A further increase in the CuO loading has no evident influence on the activity. Raman results have testified that with the addition of CuO onto the SnO₂ support, a surface-active oxygen species can be formed, the amount of which also increases significantly with the increase in the CuO loading until it reaches the monolayer dispersion capacity. Increasing the CuO loading further has no evident impact on the amount of surface oxygen. Therefore, an apparent monolayer dispersion threshold effect is observed for soot combustion over CuO/SnO₂ catalysts. It is concluded that the amount of surface-active oxygen sites is the major factor determining the activity of the catalyst.

Key words: CuO supported on SnO₂, Soot particulate combustion, Monolayer dispersion, X-ray diffraction and X-ray photoelectron spectroscopy extrapolation, Threshold effect

沈家庭, 冯小辉, 刘瑞, 徐香兰, 饶成, 刘建军, 方修忠, 谭超, 谢有畅, 王翔. CuO调配SnO₂表面用于碳烟颗粒燃烧:单层分散阈值效应对催化性能的影响[J]. 催化学报, 2019, 40(6): 905-916.

Jiating Shen, Xiaohui Feng, Rui Liu, Xianglan Xu, Cheng Rao, Jianjun Liu, Xiuzhong Fang, Chao Tan, Youchang Xie, Xiang Wang. Tuning SnO₂ surface with CuO for soot particulate combustion:The effect of monolayer dispersion capacity on reaction performance[J]. Chinese Journal of Catalysis, 2019, 40(6): 905-916.

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CuO调配SnO₂表面用于碳烟颗粒燃烧:单层分散阈值效应对催化性能的影响

Tuning SnO₂ surface with CuO for soot particulate combustion:The effect of monolayer dispersion capacity on reaction performance

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