堇青石/硼酸铝晶须/Co0.8FexCe0.2-xCr2O4催化剂的制备及其碳烟过滤-催化燃烧性能

doi:10.15541/jim20250250

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 509-518.DOI: 10.15541/jim20250250 CSTR: 32189.14.10.15541/jim20250250

堇青石/硼酸铝晶须/Co_0.8Fe_xCe_0.2-_xCr₂O₄催化剂的制备及其碳烟过滤-催化燃烧性能

张梦婕¹(), 李智博¹^,², 黄瑞楠¹, 吕向菲¹, 王伟¹()

¹ 长安大学地下水文与生态效应教育部重点实验室, 西安 710054
² 中国汽车技术研究中心有限公司移动源污染排放控制技术国家工程实验室, 天津 300300

收稿日期:2025-06-13 修回日期:2025-10-10 出版日期:2026-04-20 网络出版日期:2025-10-17
通讯作者: 王伟, 教授. E-mail: wwchem@chd.edu.cn
作者简介:张梦婕(2000-), 女, 硕士研究生. E-mail: zhangmengjie0120@163.com
基金资助:
国家自然科学基金(51678059);陕西省重点研发计划(2025SF-YBXM-534)

Cordierite/Aluminum Borate Whiskers/Co_0.8Fe_xCe_0.2-_xCr₂O₄ Catalysts: Preparation and Filtration Catalytic Performance for Carbon Soot

ZHANG Mengjie¹(), LI Zhibo¹^,², HUANG Ruinan¹, LÜ Xiangfei¹, WANG Wei¹()

¹ Key Laboratory of Subsurface Hydrology and Ecology in Arid Areas, Ministry of Education, Chang’an University, Xi’an 710054, China
² National Engineering Laboratory for Mobile Source Emission Control Technology, China Automotive Technology & Research Center Co., Ltd., Tianjin 300300, China

Received:2025-06-13 Revised:2025-10-10 Published:2026-04-20 Online:2025-10-17
Contact: WANG Wei, professor. E-mail: wwchem@chd.edu.cn
About author:ZHANG Mengjie (2000-), female, Master candidate. E-mail: zhangmengjie0120@163.com
Supported by:
National Natural Science Foundation of China(51678059);Key R&D Program of Shaanxi Province(2025SF-YBXM-534)

摘要/Abstract

摘要：

随着尾气排放法规的日益严格, 对柴油机尾气颗粒物过滤器(DPF)的过滤精度提出了更高的要求, 传统DPF难以满足尾气中纳米颗粒精密过滤的需求。本研究以堇青石蜂窝陶瓷为基体, 采用十六烷基二甲基溴化铵(CTAB)辅助共沉淀法在硼酸铝晶须上负载Co_0.8Fe_xCe_0.2-_xCr₂O₄系列尖晶石型催化剂。独特的“纤毛状晶须增强过滤-双金属掺杂催化氧化”分级结构设计实现了高效过滤性能和低温催化性能的结合, 可在较低的温度下催化氧化碳烟颗粒, Fe与Ce共掺杂产生了显著的协同效应, 提高了催化剂表面氧物种(氧空位)、Co³⁺、Cr⁶⁺的浓度, 增强了反应活性。负载C_0.8F_0.15C_0.05C₂催化剂(Z/C_0.8F_0.15C_0.05C₂-CT)使碳烟颗粒转化率达到50%对应的温度(T₅₀=446 ℃)显著优于原始堇青石(T₅₀=567 ℃)。5次循环测试表明该催化剂具有良好的稳定性和CO₂选择性(86%~94%)。这种独特的分级结构有效实现了高效颗粒过滤与低温催化燃烧性能的统一, 在DPF领域具有潜在的应用前景。

关键词: 碳烟颗粒, 堇青石, 硼酸铝晶须, 催化氧化, 过滤

Abstract:

With increasingly strict regulations on exhaust emissions, the higher requirements have been built for filtration of diesel particulate filter (DPF) because traditional DPF cannot meet the demand for precise filtration of nanoparticles in exhaust. In this study, a series of Co_0.8Fe_xCe_0.2-_xCr₂O₄ spinel-type catalysts were loaded on aluminum borate whiskers by hexadecyl dimethyl ammonium bromide (CTAB)-assisted co-precipitation method. The unique hierarchical microstructure design of “whisker enhanced filter-bimetallic doping catalytic oxidation” achieves a combination of efficient filtration performance and low-temperature catalytic performance, enabling catalytic oxidation of carbon soot particles at lower temperatures. Fe and Ce co-doping produces significant synergistic effects, increasing concentrations of oxygen species (oxygen vacancies), Co³⁺ and Cr⁶⁺ on the catalyst surface and enhancing reaction activity. Temperature of carbon soot particles at 50% conversion (T₅₀=446 ℃) is significantly lower than that of the blank cordierite sample (T₅₀=567 ℃). Five cyclic stability tests show that the catalysts have good stability and CO₂ selectivity (86%-94%). In conclusion, this unique hierarchical microstructure exhibits a unity of efficient particle filtration and low temperature catalytic combustion performance, with potential application in the field of DPF.

Key words: soot particle, cordierite, aluminum borate whisker, catalytic oxidation, filtration

中图分类号:

TQ174

张梦婕, 李智博, 黄瑞楠, 吕向菲, 王伟. 堇青石/硼酸铝晶须/Co_0.8Fe_xCe_0.2-_xCr₂O₄催化剂的制备及其碳烟过滤-催化燃烧性能[J]. 无机材料学报, 2026, 41(4): 509-518.

ZHANG Mengjie, LI Zhibo, HUANG Ruinan, LÜ Xiangfei, WANG Wei. Cordierite/Aluminum Borate Whiskers/Co_0.8Fe_xCe_0.2-_xCr₂O₄ Catalysts: Preparation and Filtration Catalytic Performance for Carbon Soot[J]. Journal of Inorganic Materials, 2026, 41(4): 509-518.

图/表 23

表1 不同加热温度和保温时间下制备的样品

Table 1 Samples preparation with different heating temperatures and holding time

Sample	Calcination temperature/℃	Holding time/h
A900-3	900	3
A1000-3	1000	3
A1050-3	1050	3
A1100-3	1100	3
A1200-3	1200	3
A1050-1	1050	1
A1050-2	1050	2
A1050-4	1050	4

图1 样品的SEM照片

Fig. 1 SEM images of samples (a) Cordierite honeycomb ceramics; (b) A900-3; (c) A1000-3; (d) A1050-3; (e) A1100-3; (f) A1200-3; (g) A1050-1; (h) A1050-2; (i) A1050-4

图2 整体式催化剂的SEM照片

Fig. 2 SEM images of integral catalysts (a) Z/CoCr2O4-CT; (b) Z/C0.8F0.2C0C2-CT; (c) Z/C0.8F0.15C0.05C2-CT; (d) Z/C0.8F0.1C0.1C2-CT; (e) Z/C0.8F0.05C0.15C2-CT; (f) Z/C0.8F0C0.2C2-CT

图3 Z/C0.8F0.15C0.05C2-CT的元素分布图和EDS图谱

Fig. 3 Element mappings and EDS spectrum of Z/C0.8F0.15C0.05C2- CT

图4 催化剂的XRD图谱

Fig. 4 XRD patterns of catalysts (a) Powder catalysts; (b) Monolithic catalysts

图5 催化剂的FT-IR图谱

Fig. 5 FT-IR spectra of catalysts (a) Powder catalysts; (b) Monolithic catalysts

图6 整体式催化剂的XPS图谱

Fig. 6 XPS spectra of monolithic catalysts (a) Full spectra; (b) O1s; (c) Co2p3/2; (d) Ce3d5/2; (e) Fe2p3/2; (f) Cr2p3/2

图7 Z/C0.8FxC0.2-xC2-CT的Soot-TPR曲线

Fig. 7 Soot-TPR profiles of Z/C0.8FxC0.2-xC2-CT

图8 (a) Z/C0.8FxC0.2-xC2-CT的碳烟催化燃烧活性; (b)尖晶石催化剂在紧密和松散接触条件下的催化性能

Fig. 8 (a) Soot catalytic combustion activity of Z/C0.8FxC0.2-xC2-CT; (b) Catalytic performance of spinel catalysts under tight and loose contact conditions Colorful figures are available on website

图9 Z/C0.8F0.15C0.05C2-CT的TG-DTG曲线

Fig. 9 TG-DTG curves of Z/C0.8F015C0.05C2-CT

图10 Z/C0.8FxC0.2-xC2-CT催化碳烟燃烧生成的CO和CO2积分曲线

Fig. 10 Integral curves of CO and CO2 generated from combustion of soot catalyzed by Z/C0.8FxC0.2-xC2-CT (a) Z/CoCrO4-CT; (b) Z/C0.8F0.2C0C2-CT; (c) Z/C0.8F0.15C0.05C2-CT; (d) Z/C0.8F0.1C0.1C2-CT; (e) Z/C0.8F0.05C0.15C2-CT; (f) Z/C0.8F0C0.2C2-CT

图11 Z/C0.8F0.15C0.05C2-CT的循环稳定性能

Fig. 11 Cyclic stability performance of Z/C0.8F0.15C0.05C2-CT (a) Soot conversion rate; (b) T10, T50 and T90. Colorful figures are available on website

表S1 硼酸铝晶须的各种参数

Table S1 Various parameters of aluminum borate whiskers

Sample	L_mean/μm	D_mean/μm	L_mean/D_mean
A900-3	8.69	0.66	13.17
A1000-3	37.86	1.93	19.62
A1050-3	48.42	0.71	68.20
A1100-3	42.79	1.64	26.09
A1050-1	15.70	0.62	25.32
A1050-2	36.33	1.36	26.71
A1050-4	53.49	2.07	25.84

表S2 Z/C0.8F0.15C0.05C2-CT的表面元素含量

Table S2 Surface element contents of Z/C0.8F0.15C0.05C2-CT

Element	O	Na	Mg	Al	Si	Co	Ce	Fe	Cr
Atomic/%	54.01	11.22	1.67	27.90	3.03	0.52	0.07	0.23	1.35

表S3 催化剂的晶格参数

Table S3 Crystal parameters of catalysts

Sample	2θ/(°)	FWHM/(°)	D/nm	d/nm	a
P-CoCr₂O₄-CT	35.7881	0.8329	9.9079	0.2506	0.8312
P-C_0.8F_0.2C₀C₂-CT	35.7934	1.0052	8.2100	0.2506	0.8310
P-C_0.8F_0.15C_0.05C₂-CT	35.8655	1.2531	6.5869	0.2500	0.8294
P-C_0.8F_0.1C_0.1C₂-CT	35.8792	1.4346	5.7536	0.2500	0.8291
P-C_0.8F_0.05C_0.15C₂-CT	35.8928	1.4480	5.7009	0.2499	0.8288
P-C_0.8F₀C_0.2C₂-CT	35.9450	1.2704	6.4985	0.2496	0.8277

表S4 表面物种的相对原子比

Table S4 Relative atomic ratios of surface species

Sample	Relative atomic ratio
Sample	O_sur/O	Co³⁺/Co	Fe³⁺/Fe	Ce⁴⁺/Ce	Cr⁶⁺/Cr
Z/CoCr₂O₄-CT	0.78	0.53	/	/	0.41
Z/C_0.8F_0.2C₀C₂-CT	0.81	0.55	0.36	0.75	0.50
Z/C_0.8F_0.15C_0.05C₂-CT	0.82	0.56	0.36	0.77	0.50
Z/C_0.8F_0.1C_0.1C₂-CT	0.80	0.54	0.33	0.73	0.49
Z/C_0.8F_0.05C_0.15C₂-CT	0.81	0.55	0.35	0.74	0.49
Z/C_0.8F₀C_0.2C₂-CT	0.79	0.53	0.34	0.72	0.44

表S5 Soot-TPR曲线的定量结果

Table S5 Quantitative results of Soot-TPR profiles

Sample	Amount of carbon dioxide formed/(a.u.)
Z/CoCr₂O₄-CT	85.312
Z/C_0.8F_0.2C₀C₂-CT	141.973
Z/C_0.8F_0.15C_0.05C₂-CT	145.109
Z/C_0.8F_0.1C_0.1C₂-CT	137.191
Z/C_0.8F_0.05C_0.15C₂-CT	138.278
Z/C_0.8F₀C_0.2C₂-CT	107.788

表S6 在79% N2、21% O2气氛下的碳烟燃烧性能

Table S6 Soot combustion performance in 79% N2 and 21% O2 atmosphere

Sample	T₁₀/℃	T₅₀/℃	T₉₀/℃
Cordierite	505	567	605
Z/CoCr₂O₄-CT	426	462	506
Z/C_0.8F_0.2C₀C₂-CT	418	450	489
Z/C_0.8F_0.15C_0.05C₂-CT	418	446	478
Z/C_0.8F_0.1C_0.1C₂-CT	426	457	494
Z/C_0.8F_0.05C_0.15C₂-CT	426	456	491
Z/C_0.8F₀C_0.2C₂-CT	432	460	486

表S7 整体式催化剂的CO2选择性

Table S7 CO2 selectivity of integral catalysts

Sample	${\displaystyle {\int }_{{T}_{0}}^{T}{C}_{{\text{CO}}_{\text{2}}}\text{d}T}$/mL	${\displaystyle {\int }_{{T}_{0}}^{T}{C}_{\text{CO}}\text{d}T}$/mL	${S}_{{\text{CO}}_{\text{2}}}$
Z/CoCr₂O₄-CT	27.6	3.6	88.5%
Z/C_0.8F_0.2C₀C₂-CT	36.4	2.8	92.9%
Z/C_0.8F_0.15C_0.05C₂-CT	23.4	1.9	92.5%
Z/C_0.8F_0.1C_0.1C₂-CT	33.2	3.9	89.5%
Z/C_0.8F_0.05C_0.15C₂-CT	32.0	3.1	91.2%
Z/C_0.8F₀C_0.2C₂-CT	23.0	2.6	89.8%

表S8 循环样品的CO2选择性

Table S8 CO2 selectivity of circulated samples

Cycle	${\displaystyle {\int }_{{T}_{0}}^{T}{C}_{{\text{CO}}_{\text{2}}}\text{d}T}$/mL	${\displaystyle {\int }_{{T}_{0}}^{T}{C}_{\text{CO}}\text{d}T}$/mL	${S}_{{\text{CO}}_{\text{2}}}$
1st	23.4	1.9	92.5%
2nd	47.3	4.7	91.0%
3rd	31.9	2.2	93.5%
4th	32.0	5.0	86.5%
5th	29.4	4.3	87.2%

表S9 整体式催化剂的过滤性能

Table S9 Filtration performance of monolithic catalysts

Sample	M₀/g	(M₀-∆M)/g	η/%
Cordierite	0.0157	0.0079	50.32
Cordierite/aluminum borate		0.0139	88.54
Z/C_0.8F_0.15C_0.05C₂-CT		0.0141	89.81

表S10 过滤催化性能对比

Table S10 Comparison of filtration catalytic performance of different catalyzers

Catalyzer	Maximum combustion rate temperature/℃	Ref.
Pt/Al₂O₃	464	[S1]
Cu_xZn_1-_xAl₂O₄	630	[S2]
CoAl₂O₄	510	[S3]
CoCr₂O₄	420	[S4]
CuCo₂O₄	574	[S5]
Z/C_0.8F_0.15C_0.05C₂-CT	446	This work

图S1 Z/C0.8F0.15C0.05C2-CT循环催化碳烟燃烧生成的CO和CO2积分曲线

Fig. S1 Integral curves of CO and CO2 generated from cycle catalytic soot combustion by Z/C0.8FxC0.2-xC2-CT (a) Cycle 1; (b) Cycle 2; (c) Cycle 3; (d) Cycle 4; (e) Cycle 5

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堇青石/硼酸铝晶须/Co_0.8Fe_xCe_0.2-_xCr₂O₄催化剂的制备及其碳烟过滤-催化燃烧性能

Cordierite/Aluminum Borate Whiskers/Co_0.8Fe_xCe_0.2-_xCr₂O₄ Catalysts: Preparation and Filtration Catalytic Performance for Carbon Soot

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