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

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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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