NH3等离子体优化MnOx/MWCNTs催化剂低温选择性催化还原性能

doi:10.16085/j.issn.1000-6613.2015.01.025

化工进展 ›› 2015, Vol. 34 ›› Issue (1): 143-149.DOI: 10.16085/j.issn.1000-6613.2015.01.025

NH₃等离子体优化MnO_x/MWCNTs催化剂低温选择性催化还原性能

胡月霞, 黄碧纯

华南理工大学环境与能源学院, 广东广州 510006

收稿日期:2014-06-04 修回日期:2014-07-12 出版日期:2015-01-05 发布日期:2015-01-05
通讯作者: 黄碧纯,教授,博士生导师,研究方向为环境催化新材料性能及其应用。E-mail cebhuang@scut.edu.cn。
作者简介:胡月霞(1987-),女,硕士研究生,研究方向为大气污染与控制工程。
基金资助:
国家自然科学基金项目(209077034)。

Optimization of the performance of MnO_x/MWCNTs catalyst by NH₃ plasma for low temperature SCR

HU Yuexia, HUANG Bichun

College of Environment and Energy, South China University of Technology, Guangzhou 510006, Guangdong, China

Received:2014-06-04 Revised:2014-07-12 Online:2015-01-05 Published:2015-01-05

摘要/Abstract

摘要： 采用介质阻挡放电产生低温NH₃等离子体对多壁碳纳米管(MWCNTs)进行表面改性,并在其表面上负载活性组分MnO_x,用于低温选择性催化还原脱硝。运用SEM、BET、Raman、FT-IR、XPS和NO-TPD对材料进行表征,结果表明,NH₃等离子体能够增加MWCNTs载体的表面缺陷程度,并且在其表面上引入吡啶类和吡咯类含氮基团;与载体未经过NH₃等离子体改性的催化剂相比,改性的催化剂活性提高,这与载体MWCNTs表面缺陷增多以及含氮基团的引入,进而提高了催化剂对NO的吸附性能有关。

关键词: 多壁碳纳米管, 表面改性, 低温选择性催化还原, 载体, 催化剂活性, 吸附

Abstract: Multi-walled carbon nanotubes(MWCNTs) were modified by low-temperature NH₃ plasma produced by dielectric barrier discharge, and several kinds of MnO_x/MWCNTs catalysts with pristine and modified MWCNTs were prepared for low temperature SCR. Structures of the pristine and plasma modified MWCNTs and the catalysts were characterized by SEM, BET, Raman, FT-IR, XPS and NO-TPD. Experimental results showed that some defects and a certain content of nitrogen containing groups were produced on the surface of MWCNTs by NH₃plasma modification. In addition, the modification of MnO_x/MWCNTs catalyst could somewhat improve the catalyst activation. Data showed that the improvement of NO conversion could be attributed to the increase of surface defects and the adsorption of NO on the MnO_x/MWCNTs catalyst.

Key words: multi-walled carbon nanotubes, surface modification, low-temperature selective catalystic reduction, support, catalyst activation, adsorption

中图分类号:

X511

胡月霞, 黄碧纯. NH₃等离子体优化MnO_x/MWCNTs催化剂低温选择性催化还原性能[J]. 化工进展, 2015, 34(1): 143-149.

HU Yuexia, HUANG Bichun. Optimization of the performance of MnO_x/MWCNTs catalyst by NH₃ plasma for low temperature SCR[J]. Chemical Industry and Engineering Progree, 2015, 34(1): 143-149.

参考文献

[1] Dujardin E,Ebbesen T W,Krishnan A,et al. Purification of single-shell nanotubes[J]. Adv. Mater.,1998,10(8):611-613.

[2] Rinzler A G,Liu J,Dai H,et al. Large-scale purification of single-wall carbon nanotubes:Process,product and characterization [J]. Appl. Phys. A,1998,67(1):29-37.

[3] Datsyuk V,Kalyva M,Papagelis K. Chemical oxidation of multi-walled carbon nanotubes[J]. Carbon,2008,46:833-840.

[4] Sunwoo L,Tetsuji O,Paik K S,et al. Chemical modification of carbon nanotubes for improvement of field emission property[J]. Microelectronic Engineering,2009,86:2110-2113.

[5] Felten A,Bitencourt C,Pireaux J J. Radio-frequency plasma functionalization of carbon nanotubes surface O₂,NH₃,and CF₄ treatments[J]. Applied Physics,2005,98:074308.

[6] Okpalugo T,Papakonstantinou P,Murphy H,et al. Oxidative functionalization of carbon nanotubes in atmospheric pressure filamentary dielectric barrier discharge (APDBD)[J]. Carbon,2005,43:2951-2959.

[7] Zhang X W,Lei L C,Xia B,et al. Oxidization of carbon nanotubes through hydroxyl radical induced by pulsed O₂ plasma and its application for O₂ reduction in eletro fenton[J]. Electrochimica Acta,2009,54:2810-2817.

[8] Xu T,Yang J H,Liu J W,et al. Surface modification of multi-walled carbon nanotubes by O₂ plasma[J]. Applied Surface Science,2007,253:8945-8951.

[9] Zhu Y W,Cheong F C,Yu T,et al. Effects of CF₄ plasma on the field emission properties of aligned multi-wall carbon nanotubes films [J]. Carbon,2005,43:395-400.

[10] Luca V,Jelena M,Ilaria A,et a1. Modification of fluorinated single-walled carbon nanotubes with aminosilane molecules[J]. Carbon,2006,44:2196-2201.

[11] Lin Y C,Lin C Y,Chiu P W. Controllable graphene N-doping with ammonia plasma[J]. Applied Physics Letters,2010,96:133100(1)- 133100(3).

[12] Ruelle B,Peeterbroeck S,Gouttebaron R,et al. Functionalization of carbon nanotubes by atomic nitrogen formed in a microwaveplasma Ar + N₂ and subsequent poly(ε-caprolactone) grafting[J]. Journal of Materials Chemistry,2007,17:157-159.

[13] Huang M C,Teng H S. Nitrogen-containing carbons from phenol-formaldehyde resins and their catalytic activity in NO reduction with NH₃[J]. Carbon,2003,41:951-957.

[14] Grzegorz S Szymánski,Teresa G,Helmut P. Influence of nitrogen surface functionalities on the catalytic activity of activated carbon in low temperature SCR of NO_x with NH₃[J]. Catalysis Today,2004,90:51-59.

[15] Muñiz J,Marbán G,Fuertes A B. Low temperature selective catalytic reduction of NO over modified activated carbon fibres[J]. Applied Catalysis B:Environmental,2000,27:27-36.

[16] Grzybek T,Klinik J,Samojeden B,et al. Nitrogen-promoted active carbons as DeNO_x catalysts 1. The influence of modification parameters on the structure and catalytic properties[J]. Catalysis Today,2008,137:228-234.

[17] Grzybek T,Klinik J,Samojeden B,et al. Nitrogen-promoted active carbons as DeNO_x catalysts 2. The influence of Mn promotion on the structure and catalytic properties in SCR [J]. Catalysis Today,2008,137:235-241.

[18] Wang W H,Huang B C,Wang L S. Oxidative treatment of multi-wall carbon nanotubes with oxygen dielectric barrier discharge plasma[J]. Surface & Coatings Technology,2011,205:4896-4901.

[19] 周红军. 催化裂化原料油加氢脱金属催化剂研究[D]. 青岛:中国石油大学化学工程与技术学院,2011.

[20] Shang Z J,Huang S M,Xu X J,et al. Mo/MgO from avalanche-like reduction of MgMoO₄ for high efficient growth of multi-walled carbon nanotubes by chemical vapor deposition[J]. Mater. Chem. Phys.,2009,114:173-178.

[21] Masoud V N,Abbas A K,Yadollah M,et al. Fast and clean functionalization of carbon nanotubes by dielectric barrier discharge plasma in air compared to acid treatment[J]. Carbon,2010,48:1369-1379.

[22] Yang S X,Li X,Zhu W P,et al. Catalytic activity,stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol[J]. Carbon,2008,46:445-452.

[23] Qu L T,Liu Y. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells[J]. Acsnano,2010,4:1321-1326.

[24] Yang,Z,Xia Y,Mokaya R. Aligned N-doped carbon nanotube bundles prepared via CVD using zeolite substrates[J]. Chem. Mater.,2005,17:4502-4508.

[25] Kim S Y,Lee J,Na C W,et al. N-doped double-walled carbon nanotubes synthesized by chemical vapor deposition[J]. Chem. Phys. Lett.,2005,413:300-305.

[26] Maldonado S,Stevenson K J. Direct preparation of carbon nanofiber electrodes via pyrolysis of iron(II)Phthalo cyanine:Electro catalytic aspects for oxygen reduction[J]. Phys. Chem. B,2004,108:11375-11383.

[27] Ayala P,Gruneis A,Gemming T,et al. Tailoring N-doped single and double wall carbon nanotubes from a nondiluted carbon nitrogen feedstock.[J]. Phys. Chem. C,2007,111:2879-2884.

[28] Khaled P,Yang S B,Yenuy H,et al. Nitrogen-doped graphene and its iron-based composite as efficient electro catalysts for oxygen reduction reaction[J]. ACS Nano,2012,6:9541-9550.

[29] Chen Z,Higgins D,Tao H,et al. Highly active nitrogen-doped carbon nanotubes for oxygen reduction reaction in fuel cell application[J]. Phys. Chem. C,2009,113:21008-21013.

[30] 王丽珊. M_xO_y/MWCNTs催化剂的低温SCR性能与反应机理的研究[D]. 广州:华南理工大学能源与环境学院,2012.

[31] Macleod N,Cropley R,Lambert R M. Efficient reduction of NO_x by H₂ under oxygen-rich conditions over Pd/TiO₂catalysts:An in situ DRIFTS study[J]. Catal. Lett.,2003,86:69-74.

[32] Richter M,Trunschke A,Bentrup U,et al. Selective catalytic reduction of nitric oxide by ammonia over egg-shell MnO_x/NaY composite catalysts[J]. J. Catal.,2002,206(1):98-113.

[33] Marbán G,Valdés S T,Fuertes A B. Mechanism of low temperature selective catalytic reduction of NO with NH₃ over carbon-supported Mn₃O₄[J]. Chem. Phys.,2004,6(2):453-464.

[34] Kijlstra W S,Brands D S,Smit H I,et al. Mechanism of the selective catalytic reduction of NO by NH₃ over MnO_x/Al₂O₃. 2.Reactivity of adsorbed NH₃ and NO complexes[J]. Journal of Catalysis,1997,171(1):219-230.

NH₃等离子体优化MnO_x/MWCNTs催化剂低温选择性催化还原性能

Optimization of the performance of MnO_x/MWCNTs catalyst by NH₃ plasma for low temperature SCR

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[3]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[4]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[5]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[6]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[7]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.
[8]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[9]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[10]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[11]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[12]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[13]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[14]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[15]	白亚迪, 邓帅, 赵睿恺, 赵力, 杨英霞. 变温吸附碳捕集机组标准化测试方案探讨及性能实验[J]. 化工进展, 2023, 42(7): 3834-3846.