泡沫镍负载CeO2改性CuO催化剂的碳烟燃烧性能研究

doi:10.11949/0438-1157.20230677

摘要/Abstract

摘要：

通过在泡沫镍基底上预沉积CeO₂晶核，采用水热法成功合成出泡沫镍负载CeO₂改性CuO催化剂（xCeO₂-CuO/NF），同未加入CeO₂的催化剂（CuO/NF）相比，其碳烟氧化活性显著提高。随着催化剂中CeO₂含量的增加，Ce/Cu质量比不断增大直至趋于平稳，催化剂的催化活性随之提高直至基本不变。其中，6.5CeO₂-CuO/NF的催化活性最好，T₅₀（383℃）最低，比CuO/NF催化剂低32℃。研究结果表明，预沉积CeO₂晶核一方面可促进CuO微纳结构的生长，提高碳烟颗粒与催化剂活性位点的接触效率；另一方面，xCeO₂-CuO/NF中形成的Cu _x Ce_1-_x O固溶体增强了铜铈之间的相互作用，通过Ce³⁺/Ce⁴⁺和Cu²⁺/Cu⁺之间氧化还原耦合循环促使活性氧物种的生成，并提升了其本征活性，从而极大地提高了其催化碳烟氧化的能力。

关键词: 催化剂, 固溶体, 纳米结构, 多相反应, 活性氧物种

Abstract:

CeO₂-modified CuO catalyst (xCeO₂-CuO/NF) was successfully synthesized by hydrothermal method through pre-deposition of CeO₂ crystal nuclei on nickel foam substrate. The soot oxidation activity of xCeO₂-CuO/NF was significantly higher than that of the catalyst without addition of CeO₂ (CuO/NF). With the increase of CeO₂ content, the Ce/Cu mass ratio and the intrinsic catalytic activity of the catalyst gradually increased, and finally both of them reached stable. Among them, the catalytic activity of 6.5CeO₂-CuO/NF was the best with the lowest T₅₀ (383℃), which was 32℃ lower than that of the CuO/NF catalyst. The results indicate that the pre-deposition of CeO₂ crystal nuclei can promote the growth of CuO into a nanostructure, which improves the contact efficiency between soot particles and active sites of the catalyst, on the other hand, the formation of Cu _x Ce_1-_x O solid solution on xCeO₂-CuO/NF enhances the interaction between Ce and Cu cations. The interaction generates a redox coupling cycle between Ce³⁺/Ce⁴⁺ and Cu²⁺/Cu⁺, prompting the generation and intrinsic activity of active oxygen species. All of these merits greatly improve the catalytic performance of soot oxidation over our as-synthesized catalysts.

Key words: catalyst, solid solution, nanostructure, multiphase reaction, active oxygen species

中图分类号:

TQ 131.2

张家琳, 徐大为, 高越, 李新刚. 泡沫镍负载CeO₂改性CuO催化剂的碳烟燃烧性能研究[J]. 化工学报, 2024, 75(1): 312-321.

Jialin ZHANG, Dawei XU, Yue GAO, Xingang LI. Performance of soot combustion over CeO₂ modified CuO catalysts supported on nickel foams[J]. CIESC Journal, 2024, 75(1): 312-321.

图/表 14

图1 催化剂CuO/NF和xCeO2-CuO/NF的制备过程

Fig.1 Preparation process of the CuO/NF and xCeO2-CuO/NF monolithic catalysts

图2 催化剂在不同反应气氛下的催化碳烟燃烧的活性结果

Fig.2 Catalytic soot oxidation activities of the catalysts in different atmospheres

表1 催化剂在10%（体积分数） O2/N2和600 μl·L-1 NO/10%（体积分数）O2/N2反应气氛下碳烟燃烧反应中的T10、T50、T90和CO2选择性

Table 1 T10， T50， T90 and CO2 selectivity of the as-prepared catalysts during soot combustion in 10% （vol） O2/N2 and 600 μl·L-1 NO/10% （vol） O2/N2

催化剂	T₁₀/℃		T₅₀/℃		T₉₀/℃		S $_{C O_{2}}$ /%
催化剂	O₂	NO+O₂	O₂	NO+O₂	O₂	NO+O₂	O₂	NO+O₂
blank	471	466	545	541	588	583	51	56
NF	460	418	527	464	494	573	约100	约100
CuO/NF	423	380	482	416	447	519	约100	约100
3.5CeO₂-CuO/NF	389	361	453	404	433	485	约100	约100
6.3CeO₂-CuO/NF	370	343	429	387	418	470	约100	约100
6.5CeO₂-CuO/NF	362	335	423	383	416	469	约100	约100

表1 催化剂在10%（体积分数） O2/N2和600 μl·L-1 NO/10%（体积分数）O2/N2反应气氛下碳烟燃烧反应中的T10、T50、T90和CO2选择性

Table 1 T10， T50， T90 and CO2 selectivity of the as-prepared catalysts during soot combustion in 10% （vol） O2/N2 and 600 μl·L-1 NO/10% （vol） O2/N2

催化剂	T₁₀/℃		T₅₀/℃		T₉₀/℃		S $_{C O_{2}}$ /%
催化剂	O₂	NO+O₂	O₂	NO+O₂	O₂	NO+O₂	O₂	NO+O₂
blank	471	466	545	541	588	583	51	56
NF	460	418	527	464	494	573	约100	约100
CuO/NF	423	380	482	416	447	519	约100	约100
3.5CeO₂-CuO/NF	389	361	453	404	433	485	约100	约100
6.3CeO₂-CuO/NF	370	343	429	387	418	470	约100	约100
6.5CeO₂-CuO/NF	362	335	423	383	416	469	约100	约100

图3 催化剂的XRD谱图

Fig.3 XRD patterns of catalysts

图4 催化剂的Raman谱图

Fig.4 Raman spectra of the catalysts

图5 催化剂的扫描电镜图

Fig.5 SEM images of the catalysts

图6 催化剂的透射电镜图和高分辨透射电镜图

Fig.6 TEM and HRTEM images of the catalysts

图7 催化剂的H2-TPR曲线

Fig.7 H2-TPR profiles of the catalysts

图8 催化剂的soot-TPR图

Fig.8 soot-TPR profiles of catalysts

图9 催化剂的NO-TPO图

Fig.9 NO-TPO profiles of the catalysts

图10 催化剂的O 1s (a)和Cu 2p (b)的XPS谱图、Cu LMM谱图(c)及Ce 3d的XPS谱图(d)

Fig.10 XPS O 1s (a) and Cu 2p (b) spectra, XPS Cu LMM spectra (c) and XPS Ce 3d spectra (d) of catalysts

表2 XPS和ICP测定的O、Cu和Ce元素的表面化学价态和含量

Table 2 Surface chemical state and content of the O， Cu and Ce elements determined by XPS and ICP

催化剂	O_ads/(O_lat+O_ads)^①	Cu²⁺/(Cu²⁺+Cu⁺)^①	Ce³⁺/(Ce³⁺+Ce⁴⁺)^①	Ce/Cu^①	Ce/Cu^②
CuO/NF	0.32	>99.5%	—	—	—
3.5CeO₂-CuO/NF	0.39	0.93	0.34	5.3	3.5
6.3CeO₂-CuO/NF	0.42	0.85	0.42	10.1	5.9
6.5CeO₂-CuO/NF	0.43	0.84	0.43	10.2	6.2

图11 催化剂的重复性测试结果

Fig.11 Results of repeatability tests

表3 催化剂的反应速率（r）、活性氧数量（N）数量和TOF值

Table 3 Reaction rate （r）， active oxygen amount（N）， and TOF of the catalysts

催化剂	r/ (10^-7 mol·s^-1·g^-1)	N/ (10^-4 mol·g^-1)	TOF/ (10^-3 s^-1)
CuO/NF	5.2	3.6	1.4
3.5CeO₂-CuO/NF	6.0	3.8	1.7
6.3CeO₂-CuO/NF	8.6	4.9	1.8
6.5CeO₂-CuO/NF	8.8	5.0	1.8

参考文献 42

1	Lin X T, Li S J, He H, et al. Evolution of oxygen vacancies in MnO _x -CeO₂ mixed oxides for soot oxidation[J]. Applied Catalysis B: Environmental, 2018, 223: 91-102.
2	Soltani S, Andersson R, Andersson B. The effect of exhaust gas composition on the kinetics of soot oxidation and diesel particulate filter regeneration[J]. Fuel, 2018, 220: 453-463.
3	Wang M, Zhang Y, Yu Y B, et al. Cesium as a dual function promoter in Co/Ce-Sn catalyst for soot oxidation[J]. Applied Catalysis B: Environmental, 2021, 285: 119850.
4	邓湘玲, 叶松寿, 曹志凯, 等. Ag/Ce_0.75Zr_0.25O₂催化剂中Ag的负载量对碳烟燃烧活性的影响[J]. 化工学报, 2017, 68(8): 3064-3070.
	Deng X L, Ye S S, Cao Z K, et al. Effect of Ag loading on soot oxidation for Ag/ Ce_0.75Zr_0.25O₂catalysts[J]. CIESC Journal, 2017, 68(8): 3064-3070.
5	Andana T, Piumetti M, Bensaid S, et al. CuO nanoparticles supported by ceria for NO _x -assisted soot oxidation: insight into catalytic activity and sintering[J]. Applied Catalysis B: Environmental, 2017, 216: 41-58.
6	刘晓刚, 魏波, 史芸菲, 等. La_1- _x Li _x MnO₃钙钛矿催化剂同时消除NO和碳烟催化性能[J]. 化工学报, 2020, 71(3): 1053-1059.
	Liu X G, Wei B, Shi Y F, et al. Simultaneous removal of NO and soot over La_1- _x Li _x MnO₃ perovskite catalysts[J]. CIESC Journal, 2020, 71(3): 1053-1059.
7	梁红, 叶代启, 林维明, 等. Sn催化剂对柴油车排气颗粒去除效果[J]. 化工学报, 2004, 55(11): 1869-1873.
	Liang H, Ye D Q, Lin W M, et al. Sn containing catalyst for particulate removal from diesel exhaust gases[J]. Journal of Chemical Industry and Engineering (China), 2004, 55(11): 1869-1873.
8	李艳, 曹进辉, 刘原一, 等. 生物质固定床热解碳烟结构特征及反应活性[J]. 化工学报, 2022, 73(12): 5564-5571.
	Li Y, Cao J H, Liu Y Y, et al. Characterization and reactivity of soot from biomass pyrolysis in a fixed bed reactor[J]. CIESC Journal, 2022, 73(12): 5564-5571.
9	Cao C M, Li X G, Zha Y Q, et al. Crossed ferric oxide nanosheets supported cobalt oxide on 3-dimensional macroporous Ni foam substrate used for diesel soot elimination under self-capture contact mode[J]. Nanoscale, 2016, 8(11): 5857-5864.
10	Raj S, Hattori M, Ozawa M. Ag-doped ZrO₂ nanoparticles prepared by hydrothermal method for efficient diesel soot oxidation[J]. Materials Letters, 2019, 234: 205-207.
11	Xia Y, Lao J Z, Ye J R, et al. Role of two-electron defects on the CeO₂ surface in CO preferential oxidation over CuO/CeO₂ catalysts[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(22): 18421-18433.
12	Xiong J, Wei Y C, Zhang Y L, et al. Facile synthesis of 3D ordered macro-mesoporous Ce_1- _x Zr _x O₂ catalysts with enhanced catalytic activity for soot oxidation[J]. Catalysis Today, 2020, 355: 587-595.
13	Cui B, Li Y, Li S R, et al. Bi-doped ceria as a highly efficient catalyst for soot combustion: improved mobility of lattice oxygen in Ce _x Bi_1- _x O _y catalysts[J]. Energy & Fuels, 2020, 34(8): 9932-9939.
14	Haneda M, Towata A. Catalytic performance of supported Ag nano-particles prepared by liquid phase chemical reduction for soot oxidation[J]. Catalysis Today, 2015, 242: 351-356.
15	Mane R, Kim H, Han K, et al. Pivotal role of MnO _x physicochemical structure in soot oxidation activity[J]. Fuel, 2023, 346: 128287.
16	Hinot K, Burtscher H, Weber A P, et al. The effect of the contact between platinum and soot particles on the catalytic oxidation of soot deposits on a diesel particle filter[J]. Applied Catalysis B: Environmental, 2007, 71(3/4): 271-278.
17	Lee K, Kosaka H, Sato S, et al. Effects of Cu loading and zeolite topology on the selective catalytic reduction with C₃H₆ over Cu/zeolite catalysts[J]. Journal of Industrial and Engineering Chemistry, 2019, 72: 73-86.
18	Zhang J Y, Liang J, Peng H G, et al. Cost-effective fast-synthesis of chabazite zeolites for the reduction of NO _x [J]. Applied Catalysis B: Environmental, 2021, 292: 120163.
19	Smeets P J, Groothaert M H, van Teeffelen R M, et al. Direct NO and N₂O decomposition and NO-assisted N₂O decomposition over Cu-zeolites: elucidating the influence of the Cu-Cu distance on oxygen migration[J]. Journal of Catalysis, 2007, 245(2): 358-368.
20	Shin K, Zhang L, An H, et al. Interface engineering for a rational design of poison-free bimetallic CO oxidation catalysts[J]. Nanoscale, 2017, 9(16): 5244-5253.
21	Qi C X, Zheng Y H, Lin H, et al. CO oxidation over gold catalysts supported on CuO/Cu₂O both in O₂-rich and H₂-rich streams: necessity of copper oxide[J]. Applied Catalysis B: Environmental, 2019, 253: 160-169.
22	Zhang Z H, Fan L P, Liao W Q, et al. Structure sensitivity of CuO in CO oxidation over CeO₂-CuO/Cu₂O catalysts [J]. Journal of Catalysis, 2022, 405: 333-345.
23	Venkataswamy P, Jampaiah D, Mukherjee D, et al. CuO/Zn-CeO₂ nanocomposite as an efficient catalyst for enhanced diesel soot oxidation[J]. Emission Control Science and Technology, 2019, 5(4): 328-341.
24	Shen J T, Rao C, Fu Z Y, et al. The influence on the structural and redox property of CuO by using different precursors and precipitants for catalytic soot combustion[J]. Applied Surface Science, 2018, 453: 204-213.
25	Yu Y F, Meng M, Dai F F. The monolithic lawn-like CuO-based nanorods array used for diesel soot combustion under gravitational contact mode[J]. Nanoscale, 2013, 5(3): 904-909.
26	Deng C S, Huang Q Q, Zhu X Y, et al. The influence of Mn-doped CeO₂ on the activity of CuO/CeO₂ in CO oxidation and NO+CO model reaction[J]. Applied Surface Science, 2016, 389: 1033-1049.
27	Zhang R B, Lu K, Zong L J, et al. Control synthesis of CeO₂ nanomaterials supported gold for catalytic oxidation of carbon monoxide[J]. Molecular Catalysis, 2017, 442: 173-180.
28	Yang J X, Ding H H, Zhu Z, et al. Surface modification of CeO₂ nanoflakes by low temperature plasma treatment to enhance imine yield: influences of different plasma atmospheres[J]. Applied Surface Science, 2018, 454: 173-180.
29	Huang C Q, Li H X, Yang J M, et al. Ce_0.6Zr_0.3Y_0.1O₂ solid solutions-supported NiCo bimetal nanocatalysts for NH₃ decomposition[J]. Applied Surface Science, 2019, 478: 708-716.
30	Rao K N, Venkataswamy P, Reddy B M. Structural characterization and catalytic evaluation of supported copper-ceria catalysts for soot oxidation[J]. Industrial & Engineering Chemistry Research, 2011, 50(21): 11960-11969.
31	Sudarsanam P, Hillary B, Mallesham B, et al. Designing CuO _x nanoparticle-decorated CeO₂ nanocubes for catalytic soot oxidation: role of the nanointerface in the catalytic performance of heterostructured nanomaterials[J]. Langmuir, 2016, 32(9): 2208-2215.
32	Sudarsanam P, Hillary B, Amin M H, et al. Heterostructured copper-ceria and iron-ceria nanorods: role of morphology, redox, and acid properties in catalytic diesel soot combustion[J]. Langmuir, 2018, 34(8): 2663-2673.
33	Aneggi E, Wiater D, de Leitenburg C, et al. Shape-dependent activity of ceria in soot combustion[J]. ACS Catalysis, 2014, 4(1): 172-181.
34	Goldstein H F, Kim D S, Yu P Y, et al. Raman study of CuO single crystals[J]. Physical Review B, 1990, 41(10): 7192-7194.
35	Khan M A, Nayan N, Shadiullah, et al. Surface study of CuO nanopetals by advanced nanocharacterization techniques with enhanced optical and catalytic properties[J]. Nanomaterials, 2020, 10(7): 1298.
36	Syrrokostas G, Govatsi K, Yannopoulos S N. High-quality, reproducible ZnO nanowire arrays obtained by a multiparameter optimization of chemical bath deposition growth[J]. Crystal Growth & Design, 2016, 16(4): 2140-2150.
37	Sun H C, Wang H, Qu Z P. Construction of CuO/CeO₂ catalysts via the ceria shape effect for selective catalytic oxidation of ammonia[J]. ACS Catalysis, 2023, 13(2): 1077-1088.
38	Guo X, Meng M, Dai F, et al. NO _x -assisted soot combustion over dually substituted perovskite catalysts La_1- _x K _x Co_1- _y Pd _y O_3- _δ [J]. Applied Catalysis B: Environmental, 2013, 142/143: 278-289.
39	Ren J L, Yu Y F, Dai F F, et al. Domain-confined catalytic soot combustion over Co₃O₄anchored on a TiO₂ nanotube array catalyst prepared by mercaptoacetic acid induced surface-grafting[J]. Nanoscale, 2013, 5(24): 12144-12149.
40	Cao C M, Xing L L, Yang Y X, et al. Diesel soot elimination over potassium-promoted Co₃O₄nanowires monolithic catalysts under gravitation contact mode[J]. Applied Catalysis B: Environmental, 2017, 218: 32-45.
41	Xiong J, Wu Q Q, Mei X L, et al. Fabrication of spinel-type Pd _x Co_3- _x O₄ 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.
42	Zheng Y F, Su Y, Pang C H, et al. Interface-enhanced oxygen vacancies of CoCuO _x catalysts in situ grown on monolithic Cu foam for VOC catalytic oxidation[J]. Environmental Science & Technology, 2022, 56(3): 1905-1916.

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泡沫镍负载CeO₂改性CuO催化剂的碳烟燃烧性能研究

Performance of soot combustion over CeO₂ modified CuO catalysts supported on nickel foams

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