铈铬比例对CeO2-CrOx复合氧化物催化剂上1,2-二氯乙烷催化氧化性能的影响

引用本文: 孟中华, 杨鹏, 周仁贤. 铈铬比例对CeO₂-CrO_x复合氧化物催化剂上1,2-二氯乙烷催化氧化性能的影响[J]. 物理化学学报, 2013, 29(02): 391-396. doi: 10.3866/PKU.WHXB201212072 shu

Citation: MENG Zhong-Hua, YANG Peng, ZHOU Ren-Xian. Influence of Ce/Cr Ratio on ₂-CrO_x Mixed Oxide Catalysts for the Catalytic Oxidation of 1,2-Dichloroethane[J]. Acta Physico-Chimica Sinica, 2013, 29(02): 391-396. doi: 10.3866/PKU.WHXB201212072 shu

铈铬比例对CeO₂-CrO_x复合氧化物催化剂上1,2-二氯乙烷催化氧化性能的影响

基金项目:
国家自然科学基金(21177110) (21177110)

国家863 重大科研项目(2011AA03A406) (2011AA03A406)

浙江省重点科技创新团队计划资助项目资助

摘要:

采用共沉淀法制备了不同铈铬比例的CeO₂-CrO_x复合氧化物(Ce/Cr 摩尔比分别为9/1、4/1、2/1、1/1、1/2、1/4、1/8)以及单纯的CeO₂和Cr₂O₃, 并研究了各催化剂对1,2-二氯乙烷(DCE)的催化氧化性能. 结果表明,相较于单纯的CeO₂, 不同铈铬比例的复合氧化物催化剂对DCE的催化氧化活性有明显提高, 其中Ce/Cr 摩尔比为2/1的CeO₂-CrO_x复合氧化物上DCE的氧化活性最好, 且只有极微量的含氯等副产物产生; 随着Ce/Cr 摩尔比减小, 对HCl的选择性有下降的趋势. 通过X射线衍射(XRD)、N₂吸附/脱附(BET)、紫外拉曼(UV-Raman)光谱、H₂程序升温还原(H₂-TPR)、NH₃程序升温脱附(NH₃-TPD)等实验技术, 研究了铈铬比例对铈铬复合氧化物的物理化学性质的影响. 结果表明, 适当比例Ce-Cr的复合, 形成了结构较稳定的Ce-Cr-O固溶体, 提高了催化剂活性氧物种的流动性, 催化剂表面酸量及强弱酸比例, 从而有利于DCE的吸附活化, 进一步脱氯降解以及深度氧化.

关键词:

English

Influence of Ce/Cr Ratio on ₂-CrO_x Mixed Oxide Catalysts for the Catalytic Oxidation of 1,2-Dichloroethane

1.
Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China
Received Date: 15 October 2012
Available Online: 14 January 2013
Fund Project:
国家自然科学基金(21177110)

国家863 重大科研项目(2011AA03A406)

浙江省重点科技创新团队计划资助项目资助

Abstract:

CeO₂, Cr2O₃, and CeO₂-CrO_x mixed oxides with molar ratios of Ce to Cr of 9/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8 were prepared by coprecipitation. The catalytic performance of 1,2-dichloroethane (DCE) decomposition was evaluated on all the catalysts. The results indicate that CeO₂-CrO_x mixed oxides with different Ce/Cr molar ratios showed higher performance for the removal of DCE compared with pure CeO₂. The CeO₂-CrO_x mixed oxide with Ce/Cr molar ratio of 2/1 exhibited the highest catalytic activity of the samples, generating only small amounts of chlorinated by-products during the decomposition of DCE. The selectivity for HCl decreased as the molar ratio of Ce to Cr decreased. The catalysts were characterized by N₂ adsorption/desorption, X-ray diffraction (XRD), UV-Raman spectroscopy, hydrogen temperatureprogrammed reduction (H₂-TPR), and ammonia temperature-programmed desorption (NH₃-TPD) to study the effect of the Ce/Cr molar ratio on the physicochemical performance of the catalysts. An appropriate molar ratio of Ce to Cr formed a more stable Ce-Cr-O solid solution, which increased the mobility of reactive oxygen species, oxidative ability, surface acid content and the ratio of strong acidity, promoting the adsorption, activation and deep oxidation of DCE.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

铈铬比例对CeO₂-CrO_x复合氧化物催化剂上1,2-二氯乙烷催化氧化性能的影响

English

Influence of Ce/Cr Ratio on ₂-CrO_x Mixed Oxide Catalysts for the Catalytic Oxidation of 1,2-Dichloroethane

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