MnOx/CeO2纳米棒催化剂在低温NH3-SCR反应中的阳离子(Zr4+,Al3+,Si4+)掺杂效应

doi:10.1016/S1872-2067(18)63204-8

催化学报 ›› 2019, Vol. 40 ›› Issue (5): 733-743.DOI: 10.1016/S1872-2067(18)63204-8

MnO_x/CeO₂纳米棒催化剂在低温NH₃-SCR反应中的阳离子(Zr⁴⁺,Al³⁺,Si⁴⁺)掺杂效应

姚小江^a, 曹俊^a, 陈丽^a, 亢科科^a, 陈阳^a, 田密^a, 杨复沫^b,c

a 中国科学院重庆绿色智能技术研究院水库水环境重点实验室大气环境研究中心, 重庆 400714;
b 四川大学建筑与环境学院烟气脱硫国家工程研究中心, 四川成都 610065;
c 中国科学院城市环境研究所区域大气环境研究卓越创新中心, 福建厦门 361021

收稿日期:2018-10-24 修回日期:2018-11-22 出版日期:2019-05-18 发布日期:2019-03-30
通讯作者: 姚小江
基金资助:
国家自然科学基金（21876168，21507130）；中国科学院青年创新促进会项目（2019376）；重庆市科学技术委员会项目（cstc2016jcyjA0070，cstckjcxljrc13）.

Doping effect of cations (Zr⁴⁺, Al³⁺, and Si⁴⁺) on MnO_x/CeO₂ nano-rod catalyst for NH₃-SCR reaction at low temperature

Xiaojiang Yao^a, Jun Cao^a, Li Chen^a, Keke Kang^a, Yang Chen^a, Mi Tian^a, Fumo Yang^b,c

a Research Center for Atmospheric Environment, Key Laboratory of Reservoir Aquatic Environment of CAS, Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;
b National Engineering Research Center for Flue Gas Desulfurization, School of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan, China;
c Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, Fujian, China

Received:2018-10-24 Revised:2018-11-22 Online:2019-05-18 Published:2019-03-30
Contact: 10.1016/S1872-2067(18)63204-8
Supported by:
This work was supported by National Natural Science Foundation of China (21876168, 21507130), Youth Innovation Promotion Association of CAS (2019376), and the Chongqing Science & Technology Commission (cstc2016jcyjA0070, cstckjcxljrc13).

摘要/Abstract

摘要：

低温脱硝技术由于具有无需再加热烟气、方便燃煤电厂脱硝改造以及适用于一些烟气温度较低的非电力行业脱硝场合等优点，吸引了越来越多研究者的关注.低温脱硝催化剂是该技术中最关键的单元，因此其配方开发及相关工作已成为近年来的研究热点之一.
商业化V₂O₅-WO₃/TiO₂催化剂在300-400℃的固定源烟气脱硝中表现出优异的性能，然而其低温脱硝性能却差强人意.并且，V₂O₅具有生物毒性，会造成二次污染.因此，低温脱硝催化剂的开发主要集中在环境友好的非钒基催化剂上.其中，MnO_x基催化剂由于具有优异的低温脱硝性能而成为重点研究对象.特别是MnO_x/CeO₂催化剂由于CeO₂良好的氧化还原性能和较高的储释氧容量，引起了低温脱硝领域越来越多研究者的兴趣.然而，众所周知，CeO₂的比表面积和热稳定性并不令人满意.幸运的是，研究表明，阳离子掺杂可有效地克服CeO₂的上述缺点.
此外，随着纳米材料制备科学与技术的发展，不同形貌的CeO₂已经能可控合成.研究表明，CeO₂纳米棒比其它形貌的CeO₂更适合用作载体，因为CeO₂纳米棒主要暴露的{110}晶面易于形成氧空位以及与表面分散组分产生强相互作用.因此，在本工作中，我们在CeO₂纳米棒的晶格中掺入热稳定的Zr⁴⁺，Al³⁺，Si⁴⁺等阳离子以提高其比表面积和热稳定性，并以该CeO₂纳米棒为载体负载MnO_x，考察了Zr⁴⁺，Al³⁺，Si⁴⁺等阳离子掺杂对MnO_x/CeO₂纳米棒催化剂低温脱硝性能的影响，筛选出最佳的掺杂离子.
对制备的样品进行了透射电子显微镜、高分辨透射电子显微镜、X射线衍射、拉曼光谱、氮气物理吸附、氢气程序升温还原、氨气程序升温脱附、氨气吸附原位漫反射红外光谱和X射线光电子能谱等一系列表征分析，并利用氨气-选择性催化还原（NH₃-SCR）反应评价了其脱硝性能和抗水抗硫性能.结果表明，Si⁴⁺掺杂的MnO_x/CeO₂纳米棒（MnO_x/CS-NR）催化剂具有最多的氧空位、表面酸性位和Mn⁴⁺因而表现出最佳的脱硝活性.由于其氧化还原性能适当减弱，有效地抑制了氨气的非选择性催化氧化，从而表现出最低的N₂O生成量.此外，MnO_x/CS-NR催化剂还显示出最佳的抗水抗硫性能.综上所述，Si⁴⁺是MnO_x/CeO₂纳米棒催化剂的最佳掺杂离子.

关键词: MnO_x/CeO₂纳米棒催化剂, 掺杂效应, 氧空位, 表面酸性, 低温氨气选择性催化还原反应

Abstract:

Thermally stable Zr⁴⁺, Al³⁺, and Si⁴⁺ cations were incorporated into the lattice of CeO₂ nano-rods (i.e., CeO₂-NR) in order to improve the specific surface area. The undoped and Zr⁴⁺, Al³⁺, and Si⁴⁺ doped nano-rods were used as supports to prepare MnO_x/CeO₂-NR, MnO_x/CZ-NR, MnO_x/CA-NR, and MnO_x/CS-NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high-resolution TEM, X-ray diffraction, Raman and N₂-physisorption analyses, hydrogen temperature-programmed reduction, ammonia temperature-programmed desorption, in situ diffuse reflectance infrared Fourier-transform spectroscopic analysis of the NH₃ adsorption, and X-ray photoelectron spectroscopy. Moreover, the catalytic performance and H₂O+SO₂ tolerance of these samples were evaluated through NH₃-selective catalytic reduction (NH₃-SCR) in the absence or presence of H₂O and SO₂. The obtained results show that the MnO_x/CS-NR catalyst exhibits the highest NO_x conversion and the lowest N₂O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn⁴⁺ content, and the lowest redox ability. The MnO_x/CS-NR catalyst also presents excellent resistance to H₂O and SO₂. All of these phenomena suggest that Si⁴⁺ is the optimal dopant for the MnO_x/CeO₂-NR catalyst.

Key words: MnO_x/CeO₂ nano-rod catalyst, Doping effect, Oxygen vacancy, Surface acidity, Low-temperature NH₃-SCR reaction

姚小江, 曹俊, 陈丽, 亢科科, 陈阳, 田密, 杨复沫. MnO_x/CeO₂纳米棒催化剂在低温NH₃-SCR反应中的阳离子(Zr⁴⁺,Al³⁺,Si⁴⁺)掺杂效应[J]. 催化学报, 2019, 40(5): 733-743.

Xiaojiang Yao, Jun Cao, Li Chen, Keke Kang, Yang Chen, Mi Tian, Fumo Yang. Doping effect of cations (Zr⁴⁺, Al³⁺, and Si⁴⁺) on MnO_x/CeO₂ nano-rod catalyst for NH₃-SCR reaction at low temperature[J]. Chinese Journal of Catalysis, 2019, 40(5): 733-743.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(18)63204-8

https://www.cjcatal.com/CN/Y2019/V40/I5/733

参考文献

[1] S. G. Wu, X. J. Yao, L. Zhang, Y. Cao, W. X. Zou, L. L. Li, K. L. Ma, C. J. Tang, F. Gao, L. Dong, Chem. Commun., 2015, 51, 3470-3473.
[2] S. C. Deng, T. T. Meng, B. L. Xu, F. Gao, Y. H. Ding, L. Yu, Y. N. Fan, ACS Catal., 2016, 6, 5807-5815.
[3] X. B. Chen, P. L. Wang, P. Fang, T. Y. Ren, Y. Liu, C. P. Cen, H. Q. Wang, Z. B. Wu, Fuel Process. Technol., 2017, 167, 221-228.
[4] R. T. Guo, M. Y. Li, P. Sun, W. G. Pan, S. M. Liu, J. Liu, X. Sun, S. W. Liu, J. Phys. Chem. C, 2017, 121, 27535-27545.
[5] H. Wang, Z. P. Qu, S. C. Dong, C. Tang, ACS Appl. Mater. Interfaces, 2017, 9, 7017-7028.
[6] Y. Geng, X. L. Chen, S. J. Yang, F. D. Liu, W. P. Shan, ACS Appl. Mater. Interfaces, 2017, 9, 16951-16958.
[7] H. Hu, S. X. Cai, H. R. Li, L. Huang, L. Y. Shi, D. S. Zhang, ACS Catal., 2015, 5, 6069-6077.
[8] Y. Dai, J. H. Li, Y. Peng, X. F. Tang, Acta Phys. Chim. Sin., 2012, 28, 1771-1776.
[9] J. Liu, Y. J. Wei, P. Z. Li, P. P. Zhang, W. Su, Y. Sun, R. Q. Zou, Y. L. Zhao, ACS Catal., 2018, 8, 3865-3874.
[10] X. N. Hu, L. Huang, J. P. Zhang, H. R. Li, K. W. Zha, L. Y. Shi, D. S. Zhang, J. Mater. Chem. A, 2018, 6, 2952-2963.
[11] Z. H. Chen, F. R. Wang, H. Li, Q. Yang, L. F. Wang, X. H. Li, Ind. Eng. Chem. Res., 2012, 51, 202-212.
[12] Z. M. Liu, J. Z. Zhu, J. H. Li, L. L. Ma, S. I. Woo, ACS Appl. Mater. Interfaces, 2014, 6, 14500-14508.
[13] L. J. Yan, Y. Y. Liu, K. W. Zha, H. R. Li, L. Y. Shi, D. S. Zhang, ACS Appl. Mater. Interfaces, 2017, 9, 2581-2593.
[14] K. W. Zha, L. Kang, C. Feng, L. P. Han, H. R. Li, T. T. Yan, P. Maitarad, L. Y. Shi, D. S. Zhang, Environ. Sci.:Nano, 2018, 5, 1408-1419.
[15] S. H. Kim, B. C. Park, Y. S. Jeon, Y. K. Kim, ACS Appl. Mater. Interfaces, 2018, 10, 32112-32119.
[16] T. Lee, H. Bai, Ind. Eng. Chem. Res., 2018, 57, 4848-4858.
[17] L. Huang, X. N. Hu, S. Yuan, H. R. Li, T. T. Yan, L. Y. Shi, D. S. Zhang, Appl. Catal. B, 2017, 203, 778-788.
[18] C. Fang, D. S. Zhang, S. X. Cai, L. Zhang, L. Huang, H. R. Li, P. Maitarad, L. Y. Shi, R. H. Gao, J. P. Zhang, Nanoscale, 2013, 5, 9199-9207.
[19] X. J. Yao, T. T. Kong, S. H. Yu, L. L. Li, F. M. Yang, L. Dong, Appl. Surf. Sci., 2017, 402, 208-217.
[20] C. Liu, G. Gao, J. W. Shi, C. He, G. D. Li, N. Bai, C. M. Niu, Catal. Commun., 2016, 86, 36-40.
[21] L. L. Li, B. W. Sun, J. F. Sun, S. H. Yu, C. Y. Ge, C. J. Tang, L. Dong, Catal. Commun., 2017, 100, 98-102.
[22] X. J. Yao, K. L. Ma, W. X. Zou, S. G. He, J. B. An, F. M. Yang, L. Dong, Chin. J. Catal., 2017, 38, 146-159.
[23] Z. M. Liu, Y. Yi, S. X. Zhang, T. L. Zhu, J. Z. Zhu, J. G. Wang, Catal. Today, 2013, 216, 76-81.
[24] C. L. Li, X. L. Tang, H. H. Yi, L. F. Wang, X. X. Cui, C. Chu, J. Y. Li, R. C. Zhang, Q. J. Yu, Appl. Surf. Sci., 2018, 428, 924-932.
[25] G. Qi, R. T. Yang, R. Chang, Appl. Catal. B, 2004, 51, 93-106.
[26] B. X. Shen, X. P. Zhang, H. Q. Ma, Y. Yao, T. Liu, J. Environ. Sci., 2013, 25, 791-800.
[27] X. J. Yao, C. J. Tang, Z. Y. Ji, Y. Dai, Y. Cao, F. Gao, L. Dong, Y. Chen, Catal. Sci. Technol., 2013, 3, 688-698.
[28] Q. Yu, X. X. Wu, C. J. Tang, L. Qi, B. Liu, F. Gao, K. Q. Sun, L. Dong, Y. Chen, J. Colloid Interfaces Sci., 2011, 354, 341-352.
[29] Z. W. Ma, S. L. Zhao, X. P. Pei, X. M. Xiong, B. Hu, Catal. Sci. Technol., 2017, 7, 191-199.
[30] X. J. Yao, L. Chen, J. Cao, F. M. Yang, W. Tan, L. Dong, Ind. Eng. Chem. Res., 2018, 57, 12407-12419.
[31] S. Putla, M. H. Amin, B. M. Reddy, A. Nafady, K. A. Al Farhan, S. K. Bhargava, ACS Appl. Mater. Interfaces, 2015, 7, 16525-16535.
[32] L. J. Liu, Z. J. Yao, Y. Deng, F. Gao, B. Liu, L. Dong, ChemCatChem, 2011, 3, 978-989.
[33] X. Y. Wang, K. Zhang, W. T. Zhao, Y. Y. Zhang, Z. X. Lan, T. H. Zhang, Y. H. Xiao, Y. F. Zhang, H. Z. Chang, L. L. Jiang, Ind. Eng. Chem. Res., 2017, 56, 14980-14994.
[34] F. Y. Gao, X. L. Tang, H. H. Yi, J. Y. Li, S. Z. Zhao, J. G. Wang, C. Chu, C. L. Li, Chem. Eng. J., 2017, 317, 20-31.
[35] J. Y. Nie, X. D. Wu, Z. R. Ma, T. F. Xu, Z. C. Si, L. Chen, D. Weng, Chin. J. Catal., 2014, 35, 1281-1288.
[36] L. Zhang, J. F. Sun, L. L. Li, S. M. Ran, G. X. Li, C. J. Li, C. Y. Ge, L. Dong, Ind. Eng. Chem. Res., 2018, 57, 490-497.
[37] M. Piumetti, S. Bensaid, N. Russo, D. Fino, Appl. Catal. B, 2016, 180, 271-282.
[38] H. Y. Tan, J. Wang, S. Z. Yu, K. B. Zhou, Environ. Sci. Technol., 2015, 49, 8675-8682.
[39] S. Andreoli, F. A. Deorsola, R. Pirone, Catal. Today, 2015, 253, 199-206.
[40] S. C. Xiong, J. X. Weng, Y. Liao, B. Li, S. J. Zou, Y. Geng, X. Xiao, N. Huang, S. J. Yang, J. Phys. Chem. C, 2016, 120, 15299-15309.
[41] P. J. Gong, J. L. Xie, D. Fang, D. Han, F. He, F. X. Li, K. Qi, Chin. J. Catal., 2017, 38, 1925-1934.
[42] N. Y. Topsøe, Science, 1994, 265, 1217-1219.
[43] Y. Peng, D. Wang, B. Li, C. Z. Wang, J. H. Li, J. Crittenden, J. M. Hao, Environ. Sci. Technol., 2017, 51, 11943-11949.
[44] X. J. Yao, R. D. Zhao, L. Chen, J. Du, C. Y. Tao, F. M. Yang, L. Dong, Appl. Catal. B, 2017, 208, 82-93.
[45] X. J. Yao, L. Chen, T. T. Kong, S. M. Ding, Q. Luo, F. M. Yang, Chin. J. Catal., 2017, 38, 1423-1430.
[46] W. Li, C. Zhang, X. Li, P. Tan, A. L. Zhou, Q. Y. Fang, G. Chen, Chin. J. Catal., 2018, 39, 1653-1663.
[47] X. Li, X. S. Li, T. L. Zhu, Y. Peng, J. H. Li, J. M. Hao, Environ. Sci. Technol., 2018, 52, 8578-8587.
[48] H. Q. Wang, S. Gao, F. X. Yu, Y. Liu, X. L. Weng, Z. B. Wu, J. Phys. Chem. C, 2015, 119, 15077-15084.
[49] J. Kim, D. W. Kwon, S. Lee, H. P. Ha, Appl. Catal. B, 2018, 236, 314-325.
[50] Z. H. Lian, W. P. Shan, Y. Zhang, M. Wang, H. He, Ind. Eng. Chem. Res., 2018, 57, 12736-12741.
[51] L. Chen, D. Weng, J. D. Wang, D. Weng, L. Cao, Chin. J. Catal., 2018, 39, 1804-1813.
[52] J. P. Chen, R. T. Yang, M. A. Buzanowski, J. E. Cichanowicz, Ind. Eng. Chem. Res., 1990, 29, 1431-1435.
[53] J. L. Zuo, Z. H. Chen, F. R. Wang, Y. H. Yu, L. F. Wang, X. H. Li, Ind. Eng. Chem. Res., 2014, 53, 2647-2655.
[54] K. W. Zha, S. X. Cai, H. Hu, H. R. Li, T. T. Yan, L. Y. Shi, D. S. Zhang, J. Phys. Chem. C, 2017, 121, 25243-25254.
[55] Y. Xiong, C. J. Tang, X. J. Yao, L. Zhang, L. L. Li, X. B. Wang, Y. Deng, F. Gao, L. Dong, Appl. Catal. A, 2015, 495, 206-216.
[56] L. W. Xu, C. Z. Wang, H. Z. Chang, Q. R. Wu, T. Zhang, J. H. Li, Environ. Sci. Technol., 2018, 52, 7064-7071.
[57] J. H. Li, H. Z. Chang, L. Ma, J. M. Hao, R. T. Yang, Catal. Today, 2011, 175, 147-156.

MnO_x/CeO₂纳米棒催化剂在低温NH₃-SCR反应中的阳离子(Zr⁴⁺,Al³⁺,Si⁴⁺)掺杂效应

Doping effect of cations (Zr⁴⁺, Al³⁺, and Si⁴⁺) on MnO_x/CeO₂ nano-rod catalyst for NH₃-SCR reaction at low temperature

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[2]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[3]	宋昕杰, 范世鹏, 蔡泽华, 杨洲, 陈旬, 付贤智, 戴文新. Cu/CeO₂上可见光辅助热催化合成NH₃: H₂O存在下NO通过CO还原的途径[J]. 催化学报, 2023, 49(6): 168-179.
[4]	曾严, 王慧, 杨惠茹, 隽超, 李丹, 温晓东, 张帆, 邹吉军, 彭冲, 胡常伟. 镍纳米粒子耦合氧空位高效催化转化棕榈酸制备烷烃[J]. 催化学报, 2023, 47(4): 229-242.
[5]	王珂然, 罗磊, 王超, 唐军旺. 双反应位点共修饰WO₃光催化活化甲烷[J]. 催化学报, 2023, 46(3): 103-112.
[6]	张志洁, 王雪盛, 唐慧玲, 李德本, 徐家跃. 调控Cs₃Bi₂Br₉@V_O-In₂O₃ S型异质结的费米能级和内建电场促进光生电荷分离和二氧化碳还原[J]. 催化学报, 2023, 55(12): 227-240.
[7]	蒋婷婷, 谢伟伟, 耿仕鹏, 李如春, 宋树芹, 王毅. 构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应[J]. 催化学报, 2022, 43(9): 2434-2442.
[8]	张宪文, 李政, 刘太丰, 李名润, 曾超斌, 松本弘昭, 韩洪宪. Pt/SrTiO₃光催化全分解水过程中水氧化活性位点的研究[J]. 催化学报, 2022, 43(8): 2223-2230.
[9]	姚青, 乐家波, 杨是赜, 程俊, 邵琪, 黄小青. 痕量Pt显著提升RuO₂的酸性水分解性能[J]. 催化学报, 2022, 43(6): 1493-1501.
[10]	邓宇, 李珏, 张如梦, 韩春秋, 陈亿, 周莹, 刘维, Po Keung Wong, 叶立群. 太阳能驱动WO_3‒_x光热催化CO₂还原的C‒C偶联机制[J]. 催化学报, 2022, 43(5): 1230-1237.
[11]	刘珍, 田坚, 余长林, 樊启哲, 刘兴强. 溶剂热合成可调控氧空位的Bi₂MoO₆纳米晶及其光催化氧化制喹啉和抗生素降解[J]. 催化学报, 2022, 43(2): 472-484.
[12]	贾雪梅, 沈紫晨, 韩巧凤, 毕慧平. 相转移有机前驱体BiOAc_0.6Br_0.2I_0.2固溶体合成表面富有氧空位的棒状S型Bi₄O₅I₂/Bi₄O₅Br₂异质结[J]. 催化学报, 2022, 43(2): 288-302.
[13]	王可, 何仕辉, 林云志, 陈旬, 戴文新, 付贤智. 氧空位修饰的暴露TiO₂{001}的Ru/TiO₂增强光热协同CO₂甲烷化活性和稳定性[J]. 催化学报, 2022, 43(2): 391-402.
[14]	李世杰, 蔡铭洁, 刘艳萍, 王春春, 吕康乐, 陈晓波. 新型氮氧化钽/氧空位钨酸铋S型异质结纤维用于高效光催化降解抗生素和还原六价铬: 产物毒性分析和光催化机理研究[J]. 催化学报, 2022, 43(10): 2652-2664.
[15]	杨祥龙, 汪圣尧, 陈婷, 杨楠, 江开, 汪佩, 李淑, 丁星, 陈浩. Cl^-诱导的含氧空位原子层厚Bi₂WO₆的可控合成及其深度氧化NO性能[J]. 催化学报, 2021, 42(6): 1013-1023.