石墨烯负载MnOx催化剂的制备及其低温NH3-SCR活性

doi:10.3866/PKU.WHXB201504292

物理化学学报 >> 2015, Vol. 31 >> Issue (7): 1383-1390.doi: 10.3866/PKU.WHXB201504292

石墨烯负载MnO_x催化剂的制备及其低温NH₃-SCR活性

焦金珍¹, 李时卉¹, 黄碧纯^1,2

1 华南理工大学环境与能源学院, 广州510006;
2 华南理工大学工业聚集区污染控制与生态修复教育部重点实验室, 广州510006

收稿日期:2015-01-07 修回日期:2015-04-27 发布日期:2015-07-08
通讯作者: 黄碧纯 E-mail:cebhuang@scut.edu.cn
基金资助:
国家自然科学基金(51478191)资助项目

Preparation of Manganese Oxides Supported on Graphene Catalysts and Their Activity in Low-Temperature NH₃-SCR

JIAO Jin-Zhen¹, LI Shi-Hui¹, HUANG Bi-Chun^1,2

1 College of Environment and Energy, South China University of Technology, Guangzhou 510006, P. R. China;
2 Key Laboratory of the Ministry of Education for Pollution Control and Ecosystem Restoration in Industry Clusters, South China University of Technology, Guangzhou 510006, P. R. China

Received:2015-01-07 Revised:2015-04-27 Published:2015-07-08
Contact: HUANG Bi-Chun E-mail:cebhuang@scut.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (51478191).

摘要/Abstract

摘要：

通过改进的Hummers法合成氧化石墨烯(GO), 随后采用水热法制备石墨烯负载锰氧化物(MnO_x/GR)催化剂. 考察了催化剂的低温NH₃选择性催化还原(NH₃-SCR)去除NO_x的性能, 并通过傅里叶变换红外(FTIR)光谱, 拉曼(Raman)光谱, X射线衍射(XRD), 透射电镜(TEM), N₂吸附-脱附, X射线光电子能谱(XPS)及H₂程序升温还原(H₂-TPR)等多种表征手段对催化剂的结构及NH₃-SCR性能进行分析. 结果显示, 不同MnO_x负载量的MnO_x/GR催化剂均展现了较好的低温SCR催化活性, 且在负载量为20%(w)时活性最优. 表征分析结果表明, 制备的GO表面含有丰富的含氧基团, 锰可以通过与含氧基团结合而负载到GO上; MnO_x/GR催化剂中MnO_x以纳米颗粒分散于石墨烯载体表面, 且以多种氧化物(MnO、Mn₃O₄和MnO₂)共同存在; 负载量为20%(w)的催化剂中高价锰和表面吸附氧含量增加, 低温区氧化还原能力增强及活性位点数量增加是其SCR活性提高的原因.

关键词: 选择性催化还原, 氮氧化物, 石墨烯, 氧化石墨烯, 锰氧化物

Abstract:

Graphene oxide (GO) was synthesized using an improved Hummers method. Subsequently, catalysts of manganese oxides (at varying loadings) supported on graphene (MnO_x/GR) were prepared by hydrothermal reaction for application in the selective catalytic reduction (SCR) of NO_x with NH₃ at low temperatures. The structural properties and catalytic performance were evaluated by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption, X-ray photoelectron spectroscopy (XPS), and H₂ temperature-programmed reduction (H₂-TPR). The characterization results indicated that abundant functional groups existed on the surface of the prepared GO that could combine with manganese during preparation of the catalysts. Manganese oxide entities, with different crystallinities (MnO, Mn₃O₄, or MnO₂), were dispersed on the surface of graphene. The results of the catalytic studies showed that the MnO_x/GR catalysts prepared with different MnO_x loadings all exhibited excellent low-temperature SCR activities. The catalyst with 20%(w) MnO_x displayed the best activity, which was attributed to the high content of high-valent manganese and oxygen adsorbed onto the catalyst surface, as well as to the enhancement in redox abilities and the addition of active sites at low temperatures.

Key words: Selective catalytic reduction, Nitrogen oxide, Graphene, Graphene oxide, Manganese oxide

焦金珍, 李时卉, 黄碧纯. 石墨烯负载MnO_x催化剂的制备及其低温NH₃-SCR活性[J]. 物理化学学报, 2015, 31(7), 1383-1390. doi: 10.3866/PKU.WHXB201504292

JIAO Jin-Zhen, LI Shi-Hui, HUANG Bi-Chun. Preparation of Manganese Oxides Supported on Graphene Catalysts and Their Activity in Low-Temperature NH₃-SCR[J]. Acta Phys. -Chim. Sin. 2015, 31(7), 1383-1390. doi: 10.3866/PKU.WHXB201504292

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201504292

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I7/1383

参考文献

(1) Qi, G.; Yang, R.T. Appl. Catal. B: Environ. 2003, 44, 217. doi: 10.1016/S0926-3373(03)00100-0
(2) Park, T. S.; Jeong, S. K.; Hong, S. H.; Hong, S. C. Ind. Eng. Chem. Res. 2001, 40, 4491. doi: 10.1021/ie010218+
(3) Huang, B. C.; Huang, R.; Jin, D. J.; Ye, D. Q. Catal. Today 2007, 126, 279. doi: 10.1016/j.cattod.2007.06.002
(4) Thirupathi, B.; Smirniotis, P. G. Appl. Catal. B: Environ. 2011, 110, 195. doi: 10.1016/j.apcatb.2011.09.001
(5) Huang, P.; Pan, S.W.; Huang, B. C.; Cheng, H.; Ye, D. Q.; Wu, J. L.; Fu, M. L.; Lu, S. L. Acta Phys. -Chim. Sin. 2013, 29, 176. [黄萍, 盘思伟, 黄碧纯, 程华, 叶代启, 吴军良, 付名利, 卢圣良. 物理化学学报, 2013, 29, 176.] doi: 10.3866/PKU.WHXB201210094
(6) Ma, Z. X.; Yang, H. S.; Liu, F.; Zhang, X. B. Appl. Catal. A: Gen. 2013, 467, 450. doi: 10.1016/j.apcata.2013.08.020
(7) Tang, X. L.; Hao, J. M.; Yi, H. H.; Li, J. H. Catal. Today 2007, 126, 406. doi: 10.1016/j.cattod.2007.06.013
(8) Masaaki, Y.; Akinori, Y.; Isao, Mochida. Appl. Catal. A 1998, 173, 239. doi: 10.1016/S0926-860X(98)00182-3
(9) Wang, L. S.; Huang, B. C.; Su, Y. X.; Zhou, G. Y.; Wang, K. L.; Luo, H. C.; Ye, D. Q. Chem. Eng. J. 2012, 192, 232. doi: 10.1016/j.cej.2012.04.012
(10) Fang, C.; Zhang, D. S.; Cai, S. X.; Zhang, L.; Huang, L.; Li, H. R.; Maitarad, P.; Shi, L. Y.; Gao, R. H.; Zhang, J. P. Nanoscale 2013, 5, 9199. doi: 10.1039/c3nr02631k
(11) Pourkhalil, M.; Moghaddam, A. Z.; Rashidi, A.; Towfighi, J.; Mortazavi, Y. Appl. Surf. Sci. 2013, 279, 250. doi: 10.1016/j.apsusc.2013.04.076
(12) Li, N.; Geng, Z. F.; Cao, M. H.; Ren, L.; Zhao, X. Y.; Liu, B.; Tian, Y.; Hu, C.W. Carbon 2013, 54, 124. doi: 10.1016/j.carbon.2012.11.009
(13) Bruno, F. M.; Philippe, S. Catal. Sci. Technol. 2012, 2, 54.
(14) Moussa, S. O.; Panchakarla, L. S.; Ho, M. Q.; El-Shall, M. S. ACS Catal. 2014, 4, 535. doi: 10.1021/cs4010198
(15) Gilje, S.; Han, S.; Wang, M. S.; Wang, K. L.; Kaner, R. B. Nano Lett. 2007, 7, 3394. doi: 10.1021/nl0717715
(16) Chen, D. Y.; Chen, W. X.; Ma, L.; Ji, G.; Chang, K.; Lee, J. Y. Mater.Today 2014, 17, 184. doi: 10.1016/j.mattod.2014.04.001
(17) Li, L.; Seng, K. H.; Liu, H. K.; Nevirkovets, I. P.; Guo, Z. P. Electrochim. Acta 2013, 87, 801. doi: 10.1016/j.electacta.2012.08.127
(18) Li, M.; Liu, Q.; Jia, Z. J.; Xu, X. C.; Cheng, Y. F.; Zheng, Y. F.; Xi, T. F.; Wei, S. C. Carbon 2014, 67, 185. doi: 10.1016/j.carbon.2013.09.080
(19) Lu, X.; Song, C.; Chang, C.; Teng, Y.; Tong, Z.; Tang, X. Ind. Eng. Chem. Res. 2014, 53, 11601. doi: 10.1021/ie5016969
(20) Romero, H. E.; Joshi, P.; Gupta, A. K.; Gutierrez, H. R.; Cole, M.W.; Tadigadapa, S. A.; Ekluud, P. C. Nanotechnology 2009, 20, 245501. doi: 10.1088/0957-4484/20/24/245501
(21) Chen, S.; Zhu, J.W.; Wu, X. D.; Han, Q. F.; Wang, X. ACS Nano 2010, 4, 2822. doi: 10.1021/nn901311t
(22) Marcano, D. C.; Kosynkin, D. V.; Berlin, J. M.; Sinitskii, A.; Sun, Z. Z.; Slesarev, A.; Alemany, L. B.; Lu, W.; Tour, J. M. ACS Nano 2010, 4, 4806. doi: 10.1021/nn1006368
(23) Tang, X. L.; Hao, J. M.; Yi, H. H.; Ning, P. J. Rare Earths 2007, 25, 240. doi: 10.1016/S1002-0721(07)60479-7
(24) Jeong, H.; Lee, Y. P.; Jin, M. H.; Kim, E. S.; Bae, J. J.; Lee, Y. H. Chem. Phys. Lett. 2009, 470, 255. doi: 10.1016/j.cplett.2009.01.050
(25) Gu, Z.; Li, C.; Wang, G.; Zhang, L.; Li, X.; Wang, W.; Jin, S. J. Polym. Sci. Part B: Polym. Phys. 2010, 48, 1329. doi: 10.1002/polb.v48:12
(26) Kai, K.; Yoshida, Y.; Kobayashi, Y.; Kageyama, H.; Saito, G. Dalton Trans. 2011, 41, 825.
(27) Buciuman, F.; Patcas, F.; Craciun, R.; Zahn, D. R. T. Phys. Chem. Chem. Phys. 1999, 1, 185. doi: 10.1039/a807821a
(28) Ferrari, A. C.; Basko, D. M. Nat. Nanotechnology 2013, 8, 235. doi: 10.1038/nnano.2013.46
(29) Li, B.; Zhou, L.; Wu, D.; Peng, H. L.; Yan, K.; Zhou, Y.; Liu, Z. F. ACS Nano 2011, 5, 5957. doi: 10.1021/nn201731t
(30) Voggu, R.; Das, B.; Rout, C. S.; Rao, C. N. R. J. Phys.: Condens. Matter 2008, 20, 472204. doi: 10.1088/0953-8984/20/47/472204
(31) Lee, J.; Novoselov, K. S.; Shin, H. S. ACS Nano 2011, 5, 608. doi: 10.1021/nn103004c
(32) Jiang, L.; Yao, M.; Liu, B.; Li, Q.; Liu, R.; Lv, H.; Lu, S.; Gong, C.; Zou, B.; Cui, T.; Liu, B. B. Crystengcomm 2013, 15, 3739. doi: 10.1039/c3ce27109a
(33) Han, Y. F.; Chen, F. X.; Zhong, Z. Y.; Ramesh, K.; Widjaja, E.; Chen, L.W. Catal. Commun. 2006, 7, 739. doi: 10.1016/j.catcom.2006.08.006
(34) Huang, H. C.; Ye, D. Q.; Huang, B. C.; Wei, Z. L. Catal. Today 2008, 139, 100. doi: 10.1016/j.cattod.2008.08.028
(35) Lu, P.; Li, C. T.; Zeng, G. M.; He, L. J.; Peng, D. L.; Cui, H. F.; Li, S. H.; Zhai, Y. B. Appl. Catal. B 2010, 96, 157. doi: 10.1016/j.apcatb.2010.02.014
(36) Zhang, J. T.; Xiong, Z. G.; Zhao, X. S. J. Mater. Chem. 2011, 21, 3634. doi: 10.1039/c0jm03827j
(37) Park, E.; Kim, M.; Jung, H.; Chin, S.; Jurng, J. ACS Catal. 2013, 3, 1518. doi: 10.1021/cs3007846
(38) Ponce, S.; Peña, M. A.; Fierro, J. L. G. Appl. Catal. B: Environ. 2000, 24, 193. doi: 10.1016/S0926-3373(99)00111-3
(39) Kang, M.; Park, E. D.; Kim, J. M.; Yie, J. E. Appl. Catal. A: Gen. 2007, 327, 261. doi: 10.1016/j.apcata.2007.05.024
(40) Yang, C.; Liu, X. Q.; Huang, B. C.; Wu, Y. M. Acta Phys. -Chim. Sin. 2014, 30, 1805. [杨超, 刘小青, 黄碧纯, 吴友明. 物理化学学报, 2014, 30, 1805.] doi: 10.3866/PKU.WHXB201407162

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石墨烯负载MnO_x催化剂的制备及其低温NH₃-SCR活性

Preparation of Manganese Oxides Supported on Graphene Catalysts and Their Activity in Low-Temperature NH₃-SCR

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