用于氯乙烯废气高效催化氧化的Ce-Cu-W-O微球的新颖合成

doi:10.1016/S1872-2067(20)63653-1

催化学报 ›› 2020, Vol. 41 ›› Issue (12): 1864-1872.DOI: 10.1016/S1872-2067(20)63653-1

用于氯乙烯废气高效催化氧化的Ce-Cu-W-O微球的新颖合成

冯晓珊^a, 郑颖滨^a, 林代峰^a, 吴恩惠^a, 罗永晋^a, 游钰锋^a, 薛珲^a, 钱庆荣^a, 陈庆华^a,b

a 福建师范大学环境科学与工程学院, 福建福州 350007;
b 福建师范大学福清分校, 福建福清 350300

收稿日期:2020-03-03 修回日期:2020-04-12 出版日期:2020-12-18 发布日期:2020-08-14
通讯作者: 罗永晋, 陈庆华
基金资助:
国家重点研发计划（2019YFC1904500）；国家自然科学基金（21875037）；福建省新世纪人才计划.

Novel synthetic route to Ce-Cu-W-O microspheres for efficient catalytic oxidation of vinyl chloride emissions

Xiaoshan Feng^a, Yingbin Zheng^a, Daifeng Lin^a, Enhui Wu^a, Yongjin Luo^a, Yufeng You^a, Hun Xue^a, Qingrong Qian^a, Qinghua Chen^a,b

a Fujian Key Laboratory of Pollution Control & Resource Reuse, Fujian Normal University, Fuzhou 350007, Fujian, China;
b Fuqing Branch of Fujian Normal University, Fuqing 350300, Fujian, China

Received:2020-03-03 Revised:2020-04-12 Online:2020-12-18 Published:2020-08-14
Supported by:
This work was supported by the National Key Research and Development Program of China (2019YFC1904500), National Natural Science Foundation of China (21875037), and New Century Talent Project of Fujian Province.

摘要/Abstract

摘要： 含氯挥发性有机物（CVOC）氯乙烯（VC）出现在工业生产聚氯乙烯（PVC）的尾气中，其具有高毒性和环境稳定性，若直接排放到大气中，会引起环境污染和威胁人类健康，因此有效的去除CVOC至关重要.在众多处理技术，催化氧化法具有反应温度低、能耗少、避免二次污染等优点，因而备受关注.用于CVOC催化氧化的催化剂包含贵金属和非贵金属催化剂，后者因为具有较低的成本和较好的抗氯中毒能力而广受研究.CVOC氧化催化剂通常需要具备酸性位和氧化还原位，酸性位用来吸附活化CVOC分子，而氧化还原位对应深度氧化能力.过渡金属氧化物CeO₂具有良好的储氧能力和氧化还原性而被作为催化材料应用于CVOC的催化氧化，但深度氧化能力不佳.研究发现，复合Cu氧化物可以提高CeO₂的氧化还原性，继而提升催化剂对CVOC的氧化能力，但酸性不足仍然限制了氯乙烯低温完全氧化的能力.为此，可以尝试在Ce-Cu复合氧化物中引入氧化钨来提高催化剂的酸性，但往往削弱了催化剂的氧化还原性，且酸性位大多分布在催化剂体相中，无法充分发挥其对VC分子的吸附活化.基于此，本文利用钨酸铵随水热时间延长而逐渐溶解并扩散W离子的这一特性，通过一步水热法设计合成了表面富集W物种和高分散精细Cu物种的Ce-Cu-W-O微球，其相对于Ce-Cu-O催化剂具有同时更好的酸性和氧化还原性，从而表现出对VC优异的深度氧化能力和热稳定性.
通过扫描电子显微镜，X射线能谱和X射线衍射分析，我们解析了Ce-Cu-W-O微球上不同元素组分在水热过程中的生长阶段和物相状态.NH₃程序升温脱附分析验证了W物种的添加将提高Ce-Cu氧化物的酸性.H₂程序升温还原分析表明，共沉淀方式引入W会降低Ce-Cu氧化物的氧化还原性，而水热一步法制备Ce-Cu-W-O微球的氧化还原性却得到了改善，归因细小晶粒尺寸CuO物种的生成.此外，拉曼光谱和XPS分析表明，HW-CeCuW催化剂具有更多的氧空位，有利于活性氧物种的迁移.因此，Ce-Cu-W-O微球表现出优异的低温氧化活性（250℃时的反应速率为2.01×10^-7mol/（g_cat·s））和较高的HCl选择性.同时，Ce-Cu-W-O微球经三次循环测试后性能仅略微下降，且在300℃下进行72h的耐久性实验中保持稳定的VC转化率和矿化率，表明其良好的热稳定性.本合成策略可以为高效的CVOC催化氧化的金属氧化物催化剂的设计和合成提供一些新思路.

关键词: 氯乙烯催化氧化, Ce-Cu-W-O微球, 钨酸铵溶解性, 丰富表面WO₃, 精细CuO纳米颗粒

Abstract: The solubility of ammonium tungstate in a special hydrothermal condition is exploited to synthesize uniform microspheres of Ce-Cu-W-O oxides. Compared to their W-undoped counterparts, they possess more Ce³⁺ and oxygen vacancies, thereby promoting oxygen mobility. The formed rich WO₃ surface can effectively provide acid sites, which is helpful for adsorption of vinyl chloride and interrupting the C-Cl bond. In addition, the presence of WO₃ induces the formation of finer CuO nanoparticles with respect to the traditional coprecipitation method, thereby resulting in a better reducibility. Benefiting from both the enhanced acidity and reducibility, the Ce-Cu-W-O microspheres deliver excellent low-temperature vinyl chloride oxidation activity (a reaction rate of 2.01×10^-7 mol/(g_cat·s) at 250 ℃) and high HCl selectivity. Moreover, subtle deactivation occurs after the three cycling activity tests, and a stable vinyl chloride conversion as well as mineralization are observed during the 72-h durability test at 300 ℃, which demonstrates good thermal stability. Our strategy can provide new insights into the design and synthesis of metal oxides for catalytic oxidation of chlorinated volatile organic compounds.

Key words: Catalytic vinyl chloride oxidation, Ce-Cu-W-Omicrospheres, Solubility of ammonium tungstate, Rich surface WO₃, Fine CuO nanoparticles

冯晓珊, 郑颖滨, 林代峰, 吴恩惠, 罗永晋, 游钰锋, 薛珲, 钱庆荣, 陈庆华. 用于氯乙烯废气高效催化氧化的Ce-Cu-W-O微球的新颖合成[J]. 催化学报, 2020, 41(12): 1864-1872.

Xiaoshan Feng, Yingbin Zheng, Daifeng Lin, Enhui Wu, Yongjin Luo, Yufeng You, Hun Xue, Qingrong Qian, Qinghua Chen. Novel synthetic route to Ce-Cu-W-O microspheres for efficient catalytic oxidation of vinyl chloride emissions[J]. Chinese Journal of Catalysis, 2020, 41(12): 1864-1872.

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用于氯乙烯废气高效催化氧化的Ce-Cu-W-O微球的新颖合成

Novel synthetic route to Ce-Cu-W-O microspheres for efficient catalytic oxidation of vinyl chloride emissions

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