MnOx/Co3O4片状复合物催化净化碳烟性能研究

张念陈; 王晨; 韩梦宇; 邱健强; 王金果

doi:10.12299/jsues.24-0127

MnO_x/Co₃O₄片状复合物催化净化碳烟性能研究

doi: 10.12299/jsues.24-0127

上海工程技术大学化学化工学院, 上海 201620

基金项目: 国家自然科学基金面上项目（22076117），上海市曙光计划项目（21SG52）

详细信息

作者简介:
张念陈（1996 − ），女，硕士，研究方向为催化剂设计与制备。E-mail：znc8llow@163.com

通讯作者:
王金果（1982 − ），男，教授，博士，研究方向为环境污染控制。E-mail：Jinguowang1982@sues.edu.cn

中图分类号: O643.32
计量
- 文章访问数: 10
- HTML全文浏览量: 8
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-04
- 网络出版日期: 2025-12-22
- 刊出日期: 2025-09-30

Performance research of MnO_x/Co₃O₄ composites within nanosheets for catalytic soot combustion

School of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China

摘要

摘要: 催化燃烧是治理柴油机尾气排放碳烟的有效方法，但关键是如何构筑高效催化剂。通过水热结合等体积浸渍法合成系列MnO_x/Co₃O₄片状复合物，并采用碳烟催化净化反应评价了其催化净化性能。结果显示，Mn/Co物质的量比为20%时，20MnCo片状复合物催化净化碳烟的性能最优，其CO₂选择性为100%、T_m值为354 ℃，这主要源于三方面原因：1)片状复合物具有丰富孔结构和较高比表面积，增大了碳烟与复合物的接触面积，同时降低了气体反应物的传质阻力；2) 负载MnO_x提高了复合物表面Co³⁺和Mn³⁺数量，促进了氧物种吸附活化形成更多活性氧物种参与催化净化碳烟；3) 负载MnO_x提高了复合物氧化还原能力，增强了NO氧化生成NO₂进而提升催化净化碳烟性能。同时，20MnCo片状复合物显示了优异的循环稳定性，说明其具有良好应用前景。
- 碳烟颗粒 /
- 催化燃烧 /
- MnO_x/Co₃O₄复合物 /
- 多孔纳米片 /
- 柴油机尾气
Abstract: Catalytic combustion is presently considered as one of the most effective methods to control soot particles from diesel exhaust, while its key issue is how to construct efficient catalysts. Herein, a series of MnO_x/Co₃O₄ composites within nanosheets were prepared using the hydrothermal integrating with wet-impregnation approach, chiefly aiming to catalyze soot purification. Experimental results indicate that, 20MnCo nanosheet composites with Mn/Co molar ratio of 20% show the optimal soot purification performance with T_m of 354 ℃ and 100% CO₂ selectivity, mainly attributing to the three aspects: 1) porous nanosheets with high surface area and rich pores not merely improved the contact area of composites and soot, but also benefited the decreased mass transfer resistance of gas reactants; 2) loading MnO_x led to the increased ratio of Mn³⁺ and Co³⁺ on composite’s surface, which favored the activating the adsorbed oxygen species on composite’s surface to generate more reactive oxygen species; 3) loading MnO_x resulted in the improved redox ability that facilitated NO oxidation to produce NO₂. Meanwhile, 20MnCo nanosheet composites demonstrated the good recycling stability, showing a good application prospect.
- soot particles /
- catalytic combustion /
- MnO_x/Co₃O₄ composites /
- porous nanosheets /
- diesel exhaust

HTML全文

图 1 所制备复合物的XRD图

Figure 1. XRD patterns of prepared composites

下载: 全尺寸图片幻灯片

图 2 所制备复合物的FESEM图

Figure 2. FESEM images of prepared composites

下载: 全尺寸图片幻灯片

图 3 所制备复合物的N₂吸脱附曲线和孔径分布图

Figure 3. N₂ sorption isotherms and pore size distributions of prepared composites

下载: 全尺寸图片幻灯片

图 4 所制备复合物的拉曼光谱图

Figure 4. Raman spectra of prepared composites

下载: 全尺寸图片幻灯片

图 5 所制备复合物的XPS图

Figure 5. XPS spectra of prepared composites

下载: 全尺寸图片幻灯片

图 6 所制备复合物的H₂-TPR图

Figure 6. H₂-TPR profiles of prepared composites

下载: 全尺寸图片幻灯片

图 7 所制备复合物的活性曲线和柱状图

Figure 7. Activity curve and histogram of prepared composites

下载: 全尺寸图片幻灯片

图 8 反应气氛对20MnCo的活性曲线和柱状图

Figure 8. Reaction gases effecting on activity curve and histogram of 20MnCo

下载: 全尺寸图片幻灯片

图 9 20MnCo的循环测试活性曲线和柱状图

Figure 9. Recycling test curve and histogram of 20MnCo

下载: 全尺寸图片幻灯片

表 1 所制备复合物的物理结构参数

Table 1. Physical parameters of the prepared composites

Catalyst	Mn/Co molar ratio determined by XRF/%	S_BET (m²↔g⁻¹)	V_P (cm³↔g⁻¹)	D_P /nm	Crystallite size/nm
Co₃O₄	0	20	0.09	24	29
2MnCo	1.95	33	0.12	14	17
12MnCo	11.98	35	0.13	13	13
20MnCo	19.96	38	0.15	12	13
30MnCo	29.92	31	0.11	14	12
40MnCo	39.43	15	0.07	13	11

下载: 导出CSV

表 2 所制备复合物的元素组成和价态参数

Table 2. Elemental composition and chemical valence states of prepared composites

Catalyst	Mn2p			Co2p			O1s
Catalyst	Mn³⁺/%	Mn⁴⁺/%	n(Mn³⁺)/n(Mn⁴⁺)	Co³⁺/%	Co²⁺/%	n(Co³⁺)/n(Co²⁺)	O_ads /%	O_latt /%	n(O_ads)/n(O_latt)
Co₃O₄	—	—	—	53	47	1.13	21	79	0.27
2MnCo	62	38	1.63	57	43	1.33	23	77	0.30
12MnCo	63	37	1.70	58	42	1.38	30	70	0.43
20MnCo	64	36	1.78	60	40	1.50	32	68	0.47
30MnCo	62	38	1.38	57	43	1.33	34	66	0.52
40MnCo	60	40	1.50	56	44	1.27	39	61	0.64

下载: 导出CSV

参考文献(21)

[1]	贺泓, 翁端, 资新运. 柴油车尾气排放污染控制技术综述[J] . 环境科学, 2007, 28(6): 1169 − 1177.
[2]	陈卫红, 曹丽敏, 刘跃伟, 等. 空气细颗粒物与呼吸系统的健康损害[J] . 公共卫生与预防医学, 2016, 27(3) : 1 − 4.
[3]	李炳章, 张文军, 张园园, 等. 柴油车尾气净化技术研究进展[J] . 山东化工, 2019, 48(9) : 105 − 106.
[4]	FRANK B, SCHLÖGL R, SU D S. Diesel soot toxification[J] . Environmental Science & Technology, 2013, 47(7) : 3026 − 3027.
[5]	YU X H, WANG L Y, CHEN M Z, et al. Enhanced activity and sulfur resistance for soot combustion on three-dimensionally ordered macroporous-mesoporous Mn_xCe_1-xO_δ/SiO₂ catalysts[J] . Applied Catalysis B: Environmental, 2019, 254: 246 − 259. doi: 10.1016/j.apcatb.2019.04.097
[6]	ZHAI G J, WANG J G, CHEN Z M, et al. Boosting soot combustion efficiency of Co₃O₄ nanocrystals via tailoring crystal facets[J] . Chemical Engineering Journal, 2018, 337: 488 − 498. doi: 10.1016/j.cej.2017.12.141
[7]	CHENG Y, LIU J, ZHAO Z, et al. Highly efficient and simultaneously catalytic removal of PM and NO_x from diesel engines with 3DOM Ce_0.8M_0.1Zr_0.1O₂ (M = Mn, Co, Ni) catalysts[J] . Chemical Engineering Science, 2017, 167: 219 − 228. doi: 10.1016/j.ces.2017.04.023
[8]	REN W, DING T, YANG Y X, et al. Identifying oxygen activation/oxidation sites for efficient soot combustion over silver catalysts interacted with nanoflower-Like hydrotalcite-derived CoAlO metal oxides[J] . ACS Catalysis, 2019, 9(9) : 8772 − 8784. doi: 10.1021/acscatal.9b01897
[9]	WU Q Q, XIONG J, ZHANG Y L, et al. Interaction-induced self-assembly of Au@La₂O₃ core-shell nanoparticles on La₂O₂CO₃ nanorods with enhanced catalytic activity and stability for soot oxidation[J] . ACS Catalysis, 2019, 9(4) : 3700 − 3715. doi: 10.1021/acscatal.9b00107
[10]	XIONG J, WU Q Q, MEI X L, et al. Fabrication of spinel-type Pd_xCo_3-xO₄ binary active sites on 3D ordered meso-macroporous Ce-Zr-O₂ with enhanced activity for catalytic soot oxidation[J] . ACS Catalysis, 2018, 8(9) : 7915 − 7930. doi: 10.1021/acscatal.8b01924
[11]	ZHAI G J, WANG J G, CHEN Z M, et al. Highly enhanced soot oxidation activity over 3DOM Co₃O₄-CeO₂ catalysts by synergistic promoting effect[J] . Journal of Hazardous Materials, 2019, 363: 214 − 226. doi: 10.1016/j.jhazmat.2018.08.065
[12]	WANG J G, YANG S F, SUN H H, et al. Highly improved soot combustion performance over synergetic Mn_xCe_1-xO₂ solid solutions within mesoporous nanosheets[J] . Journal of Colloid and Interface Science, 2020, 577: 355 − 367. doi: 10.1016/j.jcis.2020.05.090
[13]	YANG S F, WANG J G, CHAI W, et al. Enhanced soot oxidation activity over CuO/CeO₂ mesoporous nanosheets[J] . Catalysis Science & Technology, 2019, 9(7) : 1699 − 1709.
[14]	PUSHKIN A N, GULISH O K, KOSHCHEEVA D A, et al. Catalytic activity of Cu-containing oxide systems with K₂CO₃ additives in the oxidation of diesel soot by oxygen[J] . Russian Journal of Physical Chemistry A, 2013, 87(1) : 23 − 27. doi: 10.1134/S0036024413010196
[15]	XU J N, LU G Z, GUO Y, et al. A highly effective catalyst of Co-CeO₂ for the oxidation of diesel soot: the excellent NO oxidation activity and NO_x storage capacity[J] . Applied Catalysis A: General, 2017, 535: 1 − 8. doi: 10.1016/j.apcata.2017.02.005
[16]	WANG J G, CHENG L, AN W, et al. Boosting soot combustion efficiencies over CuO-CeO₂ catalysts with a 3DOM structure[J] . Catalysis Science & Technology, 2016, 6(19) : 7342 − 7350.
[17]	JUNG J, LEE J H, SONG S, et al. Measurement of soot oxidation with NO₂-O₂-H₂O in a flow reactor simulating diesel engine DPF[J] . International Journal of Automotive Technology, 2008, 9(4) : 423 − 428. doi: 10.1007/s12239-008-0051-4
[18]	OI-UCHISAWA J, OBUCHI A, OGATA A, et al. Effect of feed gas composition on the rate of carbon oxidation with Pt/SiO₂ and the oxidation mechanism[J] . Applied Catalysis B: Environmental, 1999, 21(1) : 9 − 17. doi: 10.1016/S0926-3373(99)00002-8
[19]	ZHOU X X, CHEN H R, ZHANG G B, et al. Cu/Mn co-loaded hierarchically porous zeolite beta: a highly efficient synergetic catalyst for soot oxidation[J] . Journal of Materials Chemistry A, 2015, 3(18) : 9745 − 9753. doi: 10.1039/C5TA00094G
[20]	FINO D, RUSSO N, SARACCO G, et al. Catalytic removal of NO_x and diesel soot over nanostructured spinel-type oxides[J] . Journal of Catalysis, 2006, 242(1) : 38 − 47. doi: 10.1016/j.jcat.2006.05.023
[21]	WANG J G, YANG G Y, CHENG L, et al. Three-dimensionally ordered macroporous spinel-type MCr₂O₄ (M = Co, Ni, Zn, Mn) catalysts with highly enhanced catalytic performance for soot combustion[J] . Catalysis Science & Technology, 2015, 5(9) : 4594 − 4601.