铜负载量对LNT催化剂CuO-K2CO3/TiO2结构与性能的影响

引用本文: 范丰奇, 孟明, 田野, 郑黎荣, 张静, 胡天斗. 铜负载量对LNT催化剂CuO-K₂CO₃/TiO₂结构与性能的影响[J]. 物理化学学报, 2015, 31(9): 1761-1770. doi: 10.3866/PKU.WHXB201507291 shu

Citation: FAN Feng-Qi, MENG Ming, TIAN Ye, ZHENG Li-Rong, ZHANG Jing, HU Tian-Dou. Effect of Cu Loading on the Structure and Catalytic Performance of the LNT Catalyst CuO-K₂CO₃/TiO₂[J]. Acta Physico-Chimica Sinica, 2015, 31(9): 1761-1770. doi: 10.3866/PKU.WHXB201507291 shu

铜负载量对LNT催化剂CuO-K₂CO₃/TiO₂结构与性能的影响

范丰奇 ^1, ,
孟明 ^1, ,
田野 ^1, ,
郑黎荣 ^2, ,
张静 ^2, ,
胡天斗 ^2,

基金项目:
国家自然科学基金(21276184, U1332102, 21476160) (21276184, U1332102, 21476160)

高等学校博士学科点专项科研基金(20120032110014) (20120032110014)

天津市自然科学基金(12JCYBJC14000, 15JCZDJC37400) (12JCYBJC14000, 15JCZDJC37400)

中国大学学科人才引进计划(B06006)资助 (B06006)

摘要:

采用连续浸渍法制备了一系列非贵金属稀燃NO_x阱(LNT)催化剂CuO-K₂CO₃/TiO₂, 考察了Cu负载量对催化剂结构和NO_x储存还原性能的影响. 发现8% (w) CuO-K₂CO₃/TiO₂催化剂的催化性能最佳, 其对NO_x的储存量达到1.559 mmol·g^-1, 对NO_x的还原效率高达99%, 且在NO_x还原过程中无副产物N₂O产生. 应用粉末X射线衍射(XRD), 高分辩透射电子显微镜(HR-TEM), CO₂程序升温脱附(CO₂-TPD), 扩展X射线吸收精细结构(EXAFS), 氢气程序升温还原(H₂-TPR)和原位漫反射红外光谱(in-situ DRIFTS)等技术详细表征了催化剂的结构. 结果表明, 不同Cu负载量的催化剂中, 铜物种均主要以CuO相存在. 铜的负载量直接影响铜物种、钾物种的存在状态, 高分散的CuO相与表面K₂CO₃之间存在较强相互作用, 这种相互作用不仅有利于NO_x的储存, 而且有利于增强催化剂的稳定性. in-situ DRIFTS结果表明, NO_x储存过程中产生的两个负峰(1436和1563 cm^-1)缘于碳酸盐的分解, 这间接证明了碳酸盐作为储存介质参与到NO_x储存反应中. EXAFS结果表明, 经过15个稀燃/富燃循环测试, 催化剂中的CuO相仍保持稳定. 基于以上表征结果, 提出了CuO和K₂CO₃在催化剂表面的分布模型, 并探讨了NO_x储存还原的可能机理.

关键词:

NO_x
/ 储存
/ 还原
/ 氧化铜
/ 碳酸钾

English

Effect of Cu Loading on the Structure and Catalytic Performance of the LNT Catalyst CuO-K₂CO₃/TiO₂

1.
1 Collaborative Innovation Center of Chemical Science and Engineering Tianjin, Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China;
2 Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, P. R. China
Received Date: 17 April 2015
Available Online: 06 September 2015
Fund Project:
国家自然科学基金(21276184, U1332102, 21476160)

高等学校博士学科点专项科研基金(20120032110014)

天津市自然科学基金(12JCYBJC14000, 15JCZDJC37400)

中国大学学科人才引进计划(B06006)资助

Abstract:

A series of non-platinic lean NO_x trap (LNT) CuO-K₂CO₃/TiO₂ catalysts with different Cu loadings were prepared by sequential impregnation, and they showed relatively od performance for lean NO_x storage and reduction. The catalyst containing 8% (w) CuO showed not only the largest NO_x storage capacity of 1.559 mmol·g^-1 under lean conditions, but also the highest NO_x reduction percentage of 99% in cyclic lean/rich atmospheres. Additionally, zero selectivity of NO_x to N₂O was achieved over this catalyst during NO_x reduction. Multiple techniques, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), temperature-programmed desorption of CO₂ (CO₂-TPD), extended X-ray absorption fine structure (EXAFS), temperature-programmed reduction of H₂ (H₂-TPR), and in-situ diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS), were used for catalyst characterization. The results indicate that highly dispersed CuO is the main active phase for oxidation of NO to NO₂ and reduction of NO_x to N₂. The strong interaction between K₂CO₃ and CuO was clearly revealed, which favors NO_x adsorption and storage. The appearance of negative bands at around 1436 and 1563 cm^-1, corresponding to CO₂ asymmetric stretching in bicarbonates and -C=O stretching in bidentate carbonates, showed the involvement of carbonates in NO_x storage. After using the catalysts for 15 cycles of NO_x storage and reduction in alternative lean/rich atmospheres, the CuO species in the catalysts showed little change, indicating high catalytic stability. Based on the results of in-situ DRIFTS and the other characterizations, a model describing the NO_x storage processes and the distribution of CuO and K₂CO₃ species is proposed.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

铜负载量对LNT催化剂CuO-K₂CO₃/TiO₂结构与性能的影响

English

Effect of Cu Loading on the Structure and Catalytic Performance of the LNT Catalyst CuO-K₂CO₃/TiO₂

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