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

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

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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

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