石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO

doi:10.15541/jim20230229

无机材料学报 ›› 2024, Vol. 39 ›› Issue (1): 81-89.DOI: 10.15541/jim20230229 CSTR: 32189.14.10.15541/jim20230229

所属专题：【能源环境】化工催化(202506)

石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO

王艳莉(), 钱心怡, 沈春银, 詹亮

华东理工大学化工学院, 化学工程联合国家重点实验室, 上海 200237

收稿日期:2023-05-11 修回日期:2023-08-02 出版日期:2024-01-20 网络出版日期:2023-10-15
作者简介:王艳莉(1975-), 女, 博士, 副教授. E-mail: ylwang@ecust.edu.cn
基金资助:
国家自然科学基金(51472086);国家自然科学基金(51002051);国家自然科学基金(22075081);国家自然科学基金(20806024);上海市自然科学基金(12ZR1407200)

Graphene Based Mesoporous Manganese-Cerium Oxides Catalysts: Preparation and Low-temperature Catalytic Reduction of NO

WANG Yanli(), QIAN Xinyi, SHEN Chunyin, ZHAN Liang

State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2023-05-11 Revised:2023-08-02 Published:2024-01-20 Online:2023-10-15
About author:WANG Yanli (1975-), female, PhD, associate professor. E-mail: ylwang@ecust.edu.cn
Supported by:
National Natural Science Foundation of China(51472086);National Natural Science Foundation of China(51002051);National Natural Science Foundation of China(22075081);National Natural Science Foundation of China(20806024);Natural Science Foundation of Shanghai(12ZR1407200)

摘要/Abstract

摘要：

锰铈氧化物由于较强的氧化还原活性、优良的低温脱硝性能, 已被广泛用于选择性催化还原(SCR)脱硝反应, 但是锰铈氧化物存在活性组分易团聚、比表面积较低等问题, 限制其催化剂活性的提高。本研究以介孔结构的石墨烯基SiO₂(G@SiO₂)纳米材料为模板, 采用水热法制备了系列石墨烯基介孔锰铈氧化物(G@MnO_x-CeO₂)催化剂, 并考察了该催化剂在低温下(100~300 ℃)的SCR脱硝性能。结果表明, 与石墨烯基铈氧化物(G@CeO₂)相比, G@MnO_x-CeO₂催化剂具有较高脱硝活性。当Mn、Ce与模板G@SiO₂质量比分别为0.35、0.90时, G@Mn(0.35)Ce(0.9)催化剂的脱硝活性最佳, 220 ℃下NO转化率达到最高(80%)。添加适量MnO_x, 提高了G@MnO_x-CeO₂催化剂的比表面积、孔容, 降低了催化剂的结晶度; 并且MnO_x-CeO₂以纳米尺度(2~3 nm)较为均匀地分散于石墨烯片层表面。此外, 由于MnO_x与CeO₂之间存在协同作用, Mn原子可以部分替代Ce原子掺杂于CeO₂的晶体结构中形成MnO_x-CeO₂固溶体, 使G@Mn(0.35)Ce(0.9)催化剂表面存在较高含量的高价态Mn³⁺和Mn⁴⁺、Ce⁴⁺以及较高的化学吸附氧浓度, 从而展现出较高的脱硝性能。该工作为MnO_x-CeO₂基催化剂在低温NH₃-SCR中的实际应用提供了基础数据。

关键词: 石墨烯, 铈氧化物, 锰氧化物, NO, 选择性催化还原

Abstract:

Manganese and cerium oxides are extensively used for selective catalytic reduction (SCR) in denitrification reaction due to their high redox ability and excellent low-temperature SCR activities. However, these catalysts still face problems such as easy aggregation of active components and low specific surface area, which restricts the enhancement of catalytic activity. Here, graphene based SiO₂ nanocomposites (G@SiO₂) with mesoporous structure was used as the template to prepare series of graphene based mesoporous manganese-cerium oxides (G@MnO_x-CeO₂) catalysts by hydrothermal method. The obtained catalysts were investigated for selective catalytic reduction (SCR) of NO at low temperature (100-300 ℃). The results indicate that G@MnO_x-CeO₂catalyst exhibits better SCR activity than graphene based cerium oxides (G@CeO₂). With the mass ratio of Mn and Ce to G@SiO₂of 0.35 and 0.90, respectively, the G@Mn(0.35)Ce(0.9) catalyst shows the best NO removal activity with the maximum conversion of 80% at 220 ℃. It is found that the addition of appropriate amount of MnO_x increases specific surface area and pore volume but decreases crystallinity of the catalyst G@MnO_x-CeO₂. Furthermore, MnO_xand CeO₂are uniformly distributed on the surface of graphene sheets in the form of nanoparticles. In addition, partial replaced Ce atoms is actually doped with Mn atoms into the structure of CeO₂to form MnO_x-CeO₂ solid solution, resulting in higher percentage of Mn³⁺and Mn⁴⁺ with higher valance states and Ce⁴⁺, and higher concentration of surface chemisorbed oxygen on the surface. These results contribute to higher SCR activity of the G@Mn(0.35)Ce(0.9) catalyst. This work provides promising basic data for the practical application of MnO_x-CeO₂based catalysts in low temperature NH₃-SCR.

Key words: graphene, cerium oxide, manganese oxide, NO, selective catalytic reduction

中图分类号:

TQ426

王艳莉, 钱心怡, 沈春银, 詹亮. 石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO[J]. 无机材料学报, 2024, 39(1): 81-89.

WANG Yanli, QIAN Xinyi, SHEN Chunyin, ZHAN Liang. Graphene Based Mesoporous Manganese-Cerium Oxides Catalysts: Preparation and Low-temperature Catalytic Reduction of NO[J]. Journal of Inorganic Materials, 2024, 39(1): 81-89.

图/表 14

图1 G@MnOx-CeO2催化剂的制备流程图

Fig. 1 Preparation of G@MnOx-CeO2 catalyst

图2 不同催化剂在不同反应温度的脱硝活性

Fig. 2 NO conversions at different reaction temperatures over various catalysts

图3 不同金属担载量时G@MnOx-CeO2催化剂的脱硝活性

Fig. 3 NO conversions over G@MnOx-CeO2 catalysts with different metal loadings

图4 G@SiO2介孔模板的(a) N2吸附-脱附等温线和(b)孔径分布曲线

Fig. 4 (a) Nitrogen adsorption/desorption isotherm and (b) corresponding pore size distribution curve of G@SiO2 template

图5 不同金属担载量时G@MnOx-CeO2催化剂的(a)N2吸附-脱附等温线和(b)孔径分布曲线

Fig. 5 (a) Nitrogen adsorption/desorption isotherms and (b) corresponding pore size distribution curves of G@MnOx-CeO2 catalysts with different metal loadings

表1 不同催化剂的孔结构参数

Table 1 Pore parameters of various catalysts

Sample	S_BET/ (m²·g^-1)	V_total/ (cm³·g^-1)	Average pore size/nm
G@Ce(0.9)	65.0	0.125	7.67
G@Mn(0.18)Ce(0.45)	241.2	0.230	3.81
G@Mn(0.35)Ce(0.9)	197.5	0.287	5.82
G@Mn(1)Ce(2.7)	126.6	0.199	6.29

图6 G@Mn(0.35)Ce(0.9)催化剂的SEM照片

Fig. 6 SEM images of G@Mn(0.35)Ce(0.9) catalyst

图7 G@Mn(0.35)Ce(0.9)催化剂的(a-d)TEM照片, (e-i)选定区域TEM照片及其对应的C、Mn、Ce、O元素分布图

Fig. 7 (a-d) TEM images, (e-i) TEM image and corresponding C, Mn, Ce, O element mappings for selected area of G@Mn(0.35)Ce(0.9) catalyst

图8 不同样品的XRD谱图

Fig. 8 XRD patterns of different samples

图9 G@Ce(0.9)和G@Mn(0.35)Ce(0.9)催化剂的Raman谱图

Fig. 9 Raman spectra of G@Ce(0.9) and G@Mn(0.35)Ce(0.9) catalysts

图10 G@Mn(0.35)Ce(0.9)催化剂的XPS谱图

Fig. 10 XPS spectra of G@Mn(0.35)Ce(0.9) catalyst (a) Total survey; (b) C1s; (c) O1s; (d) Mn2p; (e) Ce3d

表2 G@Mn(0.35)Ce(0.9)催化剂的表面元素浓度

Table 2 Surface atomic concentrations of G@Mn(0.35)Ce(0.9) catalyst

Sample	Surface atomic concentration/%				Relative atomic ratio/%
Sample	C	O	Mn	Ce	O_β/O	(Mn³⁺+Mn⁴⁺)/Mn
G@Mn(0.35)Ce(0.9)	18.10	65.72	8.26	7.92	45.2	80.1

图S1 G@Mn(0.35)Ce(0.9)催化剂的循环脱硝活性

Fig. S1 Cyclic NO removal activity of G@Mn(0.35)Ce(0.9) catalyst

图S2 G@SiO2介孔模板的SEM照片

Fig. S2 SEM images of G@SiO2 mesoporous template

参考文献 36

[1]	QI G, YANG R T. Low-temperature selective catalytic reduction of NO with NH₃ over iron and manganese oxides supported on titania. Applied Catalysis B: Environmental, 2003, 44(3):217. DOI URL
[2]	KOMPIO P G, BRUCKNER A, HIPLER F, et al. A new view on the relations between tungsten and vanadium in V₂O₅-WO₃/TiO₂catalysts for the selective reduction of NO with NH₃. Journal of Catalysis, 2012, 286(1):237. DOI URL
[3]	LEE I Y, KIM D W, LEE J B, et al. A practical scale evaluation of sulfated V₂O₅/TiO₂ catalyst from metatitanic acid for selective catalytic reduction of NO by NH₃. Chemical Engineering Journal, 2002, 90(3):267. DOI URL
[4]	KANG M, PARK E D, KIM J M, et al. Manganese oxide catalysts for NO_x reduction with NH₃ at low temperatures. Applied Catalysis A: General, 2007, 327(2):261. DOI URL
[5]	QI G, YANG R T. Performance and kinetics study for low- temperature SCR of NO with NH₃ over MnO_x-CeO₂ catalyst. Journal of Catalysis, 2003, 217(2):434. DOI URL
[6]	WU Z B, JIN R B, LIU Y, et al. Ceria modified MnO_x/TiO₂ as a superior catalyst for NO reduction with NH₃ at low-temperature. Catalysis Communications, 2008, 9(13): 2217. DOI URL
[7]	LIU Z M, YANG Y, ZHANG S X, et al. Selective catalytic reduction of NO_x with NH₃ over Mn-Ce mixed oxide catalyst at low temperatures. Catalysis Today, 2013, 216: 76.
[8]	LI Yi, LI Y P, WANG P F, et al. Low-temperature selective catalytic reduction of NO_x with NH₃ over MnFeO_x nanorods. Chemical Engineering Journal, 2017, 330: 213.
[9]	DENG S S, LI Y H, A R T, et al. Low-temperature selective catalytic reduction of NO with NH₃ over manganese and tin oxides supported on titania. Chemical Industry and Engineering Progress, 2013, 32(10):2403.
[10]	CHANG H Z, LI J H, CHEN X Y, et al. Effect of Sn on MnO_x-CeO₂ catalyst for SCR of NO_x by ammonia: Enhancement of activity and remarkable resistance to SO₂. Catalysis Communications, 2012, 27: 54.
[11]	YAO X J, CHEN L, CAO J, et al. Enhancing the deNO_x performance of MnO_x/CeO₂-ZrO₂ nanorod catalyst for low- temperature NH₃-SCR by TiO₂ modification. Chemical Engineering Journal, 2019, 369: 46.
[12]	TANG X L, WANG C Z, GAO F Y, et al. Effect of hierarchical element doping on the low-temperature activity of manganese- based catalysts for NH₃-SCR. Journal of Environmental Chemical Engineering, 2020, 8(5):104399. DOI URL
[13]	WANG Y L, LI X X, ZHAN L, et al. Effect of SO₂ on activated carbon honeycomb supported CeO₂-MnO_x catalyst for NO removal at low temperature. Industrial & Engineering Chemistry Research, 2015, 54(8):2274. DOI URL
[14]	SHEN B X, LIU T. Deactivation of MnO_x-CeO_x/ACF catalysts for low-temperature NH₃-SCR in the presence of SO₂. Acta Physico-Chimica Sinica, 2010, 26(11):3009. DOI URL
[15]	ZHANG D S, ZHANG L, SHI L Y, et al. In situ supported MnO_x-CeO_x on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH₃. Nanoscale, 2013, 5(3):1127. DOI URL
[16]	JIAO J Z, LI S H, HUANG B C. Preparation of manganese oxides supported on graphene catalysts and their activity in low-temperature NH₃-SCR. Acta Physico-Chimica Sinica, 2015, 31(7):1383. DOI URL
[17]	XU H M, QU Z, ZONG C X, et al. MnO_x/graphene for the catalytic oxidation and adsorption of elemental mercury. Environmental Science and Technology, 2015, 49(11): 6823.
[18]	LU X N, SONG C Y, JIA S H, et al. Low-temperature selective catalytic reduction of NO_x with NH₃ over cerium and manganese oxides supported on TiO₂-graphene. Chemical Engineering Journal, 2015, 260(12):776. DOI URL
[19]	XIAO X, SHENG Z Y, YANG L, et al. Low-temperature selective catalytic reduction of NO_x with NH₃ over a manganese and cerium oxide/graphene composite prepared by a hydrothermal method. Catalysis Science & Technology, 2016, 6(5):1507.
[20]	YAO W Q, WU S B, ZHAN L, et al. Two-dimensional porous carbon-coated sandwich-like mesoporous SnO₂/graphene/mesoporous SnO₂ nanosheets towards high-rate and long cycle life lithium-ion batteries. Chemical Engineering Journal, 2019, 361: 329.
[21]	YANG S B, ZHAN L, XU X Y, et al. Graphene-based porous silica sheets impregnated with polyethyleneimine for superior CO₂ capture. Advanced Materials, 2013, 25(15): 2130. DOI URL
[22]	YAO W Q, CUI Y S, ZHAN L, et al. Two-dimensional sandwich-like Ag coated silicon-graphene-silicon nanostructures for superior lithium storage. Applied Surface Science, 2017, 425(1):614. DOI URL
[23]	LV L, SHEN Y Q. Selective catalytic reduction with NH₃ at low temperature. Journal of Combustion Science and Technology, 2011, 17(2):103.
[24]	LIU Chang, GAO G, SHI J W, et al. MnO_x-CeO₂ shell-in-shell microspheres for NH₃-SCR de-NO_x at low temperature. Catalysis Communications, 2016, 86: 36.
[25]	KONG Z K, LI Y, WANG Y L, et al. Monodispersed MnO_x-CeO₂ solid solution as superior electrocatalyst for Li₂S precipitation and conversion. Chemical Engineering Journal, 2020, 392: 123697.
[26]	DENG D Y, CHEN N, XIAO X C, et al. Electrochemical performance of CeO₂ nanoparticle-decorated graphene oxide as an electrode material for supercapacitor. Ionics, 2017, 23(1):121. DOI URL
[27]	YAO W Y, LIU Y, WU Z B. The promoting effect of CeO₂@Ce-O-P multi-core@shell structure on SO₂ tolerance for selective catalytic reduction of NO with NH₃ at low temperature. Applied Surface Science, 2018, 442: 156.
[28]	MACHIDA M, UTO M, KUROGI D, et al. Solid-gas interaction of nitrogen oxide adsorbed on MnO_x-CeO₂: a DRIFTS study. Journal of Materials Chemistry, 2001, 11(3):900. DOI URL
[29]	ZHANG X M, DENG Y Q, TIAN P, et al. Dynamic active sites over binary oxide catalysts: In situ/operando spectroscopic study of low-temperature CO oxidation over MnO_x-CeO₂ catalysts. Applied Catalysis B: Environmental, 2016, 191: 179.
[30]	YOU X C, SHENG Z Y, YU D Q, et al. Influence of Mn/Ce ratio on the physicochemical properties and catalytic performance of graphene supported MnO_x-CeO₂ oxides for NH₃-SCR at low temperature. Applied Surface Science, 2017, 423: 845.
[31]	WU Y Z, LIU S Q, WANG H Y, et al. A novel solvothermal synthesis of Mn₃O₄/graphene composites for supercapacitors. Electrochimica Acta, 2013, 90: 210.
[32]	WANG Y L, KANG Y, GE M, et al. Cerium and tin oxides anchored onto reduced graphene oxide for selective catalytic reduction of NO with NH₃ at low temperatures. RSC Advances, 2018, 8(63):36383. DOI URL
[33]	LU X N, SONG C Y, CHANG C C, et al. Manganese oxides supported on TiO₂-graphene nanocomposite catalysts for selective catalytic reduction of NO_x with NH₃ at low temperature. Industrial & Engineering Chemistry Research, 2014, 53(29):11601. DOI URL
[34]	WANG X, ZHENG Y Y, XU Z, et al. Low-temperature NO reduction with NH₃ over Mn-CeO_x/CNT catalysts prepared by a liquid-phase method. Catalysis Science & Technology, 2014, 4(6):1738.
[35]	FAN Z Y, SHI J W, GAO C, et al. Rationally designed porous MnO_x-FeO_x nanoneedles for low-temperature selective catalytic reduction of NO_x by NH₃. ACS Applied Materials & Interfaces, 2017, 9(19):16117.
[36]	SUN M T, HUANG B C, MA J W, et al. Morphological effects of manganese dioxide on catalytic reactions for low-temperature NH₃-SCR. Acta Physico-Chimica Sinica, 2016, 32(6):1501. DOI URL

石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO

Graphene Based Mesoporous Manganese-Cerium Oxides Catalysts: Preparation and Low-temperature Catalytic Reduction of NO

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨茗凯, 黄泽皑, 周芸霄, 刘彤, 张魁魁, 谭浩, 刘梦颖, 詹俊杰, 陈国星, 周莹. 基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究[J]. 无机材料学报, 2025, 40(5): 473-480.
[2]	高晨光, 孙晓亮, 陈君, 李达鑫, 陈庆庆, 贾德昌, 周玉. 基于湿法纺丝技术的SiBCN-rGO陶瓷纤维的组织结构、力学和吸波性能[J]. 无机材料学报, 2025, 40(3): 290-296.
[3]	王悦, 王欣, 于显利. 室温铁磁性还原氧化石墨烯基全碳膜[J]. 无机材料学报, 2025, 40(3): 305-313.
[4]	李家琪, 李小松, 李煊赫, 朱晓兵, 朱爱民. 暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂[J]. 无机材料学报, 2024, 39(7): 835-844.
[5]	李红兰, 张俊苗, 宋二红, 杨兴林. Mo/S共掺杂的石墨烯用于合成氨: 密度泛函理论研究[J]. 无机材料学报, 2024, 39(5): 561-568.
[6]	孙川, 何鹏飞, 胡振峰, 王荣, 邢悦, 张志彬, 李竞龙, 万春磊, 梁秀兵. 含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能[J]. 无机材料学报, 2024, 39(3): 267-273.
[7]	杨平军, 李铁虎, 李昊, 党阿磊. 石墨烯对环氧树脂泡沫炭石墨化、电导率和力学性能的影响[J]. 无机材料学报, 2024, 39(1): 107-112.
[8]	董怡曼, 谭占鳌. 宽带隙钙钛矿基二端叠层太阳电池复合层的研究进展[J]. 无机材料学报, 2023, 38(9): 1031-1043.
[9]	陈赛赛, 庞雅莉, 王娇娜, 龚䶮, 王锐, 栾筱婉, 李昕. 绿-黄可逆电热致变色织物的制备及其性能[J]. 无机材料学报, 2022, 37(9): 954-960.
[10]	孙铭, 邵溥真, 孙凯, 黄建华, 张强, 修子扬, 肖海英, 武高辉. RGO/Al复合材料界面性质第一性原理研究[J]. 无机材料学报, 2022, 37(6): 651-659.
[11]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.
[12]	王虹力, 王男, 王丽莹, 宋二红, 赵占奎. 功能化石墨烯担载型AuPd纳米催化剂增强甲酸制氢反应[J]. 无机材料学报, 2022, 37(5): 547-553.
[13]	董淑蕊, 赵笛, 赵静, 金万勤. 离子化氨基酸对氧化石墨烯膜渗透汽化过程中水选择性渗透的影响[J]. 无机材料学报, 2022, 37(4): 387-394.
[14]	蒋丽丽, 徐帅帅, 夏宝凯, 陈胜, 朱俊武. 缺陷调控石墨烯复合催化剂在氧还原反应中的作用[J]. 无机材料学报, 2022, 37(2): 215-222.
[15]	吴静, 余立兵, 刘帅帅, 黄秋艳, 姜姗姗, ANTON Matveev, 王连莉, 宋二红, 肖蓓蓓. NiN₄/Cr修饰的石墨烯电化学固氮电极[J]. 无机材料学报, 2022, 37(10): 1141-1148.