Ce/Co比对Ag/CeO2-Co3O4催化剂低温氧化降解甲醛性能的影响

唐彤; 卫广程; 王慧敏; 刘墨; 张秋林; 宁平

Ce/Co比对Ag/CeO₂-Co₃O₄催化剂低温氧化降解甲醛性能的影响

昆明理工大学环境科学与工程学院, 云南昆明 650500

基金项目:

国家重点研发计划 2018YFC0213400

详细信息

通讯作者:
张秋林, E-mail:qiulinzhang_kmust@163.com

中图分类号: X701.7
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- 被引次数: 0
出版历程
- 收稿日期: 2019-01-17
- 修回日期: 2019-03-02
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-05-10

Effect of Ce/Co ratio on the catalytic performance of Ag/CeO₂-Co₃O₄ in the low-temperature oxidation of formaldehyde

Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China

Funds:

The project was supported by the National Key Research and Development Program 2018YFC0213400

摘要

摘要: 采用共沉淀法制备了一系列具有不同Ce/Co比的Ag/CeO₂-Co₃O₄催化剂，对其在甲醛低温氧化降解中的催化性能进行了研究。结果发现，Ag/CeO₂-Co₃O₄催化剂具有较好的甲醛低温降解活性，而Ce/Co比是影响其催化性能的一个重要因素。XRD、氮吸附-脱附、Raman光谱、H₂-TPR和in-situ DRIFTS等表征结果表明，随着Co含量的增加，Ag/CeO₂-Co₃O₄催化剂的孔体积随之增大，而比表面积减小。CeO₂有利于Ag/CeO₂-Co₃O₄催化剂的氧化还原性能提高，促进氧空位增加，提升Co²⁺的含量，从而有利于氧分子的活化，促进甲醛降解。同时，in-situ DRIFTS结果表明，甲酸盐物种的分解是甲醛在Ag/CeO₂-Co₃O₄催化剂表面催化氧化降解的速控步骤。
- 共沉淀法 /
- CeO₂-Co₃O₄ /
- 甲醛催化氧化 /
- 氧空位 /
- 甲酸盐
Abstract: A series of Ag/CeO₂-Co₃O₄ catalysts with various Ce/Co ratios were prepared by co-precipitation method and employed in the low-temperature oxidation of formaldehyde. The results demonstrate that the Ag/CeO₂-Co₃O₄ catalysts exhibit excellent performance in the oxidation of formaldehyde and the Ce/Co ratio has a significant impact on the catalytic performance. The XRD, nitrogen adsorption-desorption, Raman spectroscopy, H₂-TPR and in-situ DRIFTS results illustrate that with the increase of Co content in Ag/CeO₂-Co₃O₄, the pore volume increases whereas the surface area decreases. The presence of CeO₂ is beneficial to enhancing the redox ability and increasing the oxygen vacancies and Co²⁺ species, which can promote the activation of oxygen species and then the degradation of formaldehyde. According to the in-situ DRIFTS results, the decomposition of formates on the catalyst surface is probably the rate-determining step for the degradation of formaldehyde at low temperature.
- co-precipitation /
- CeO₂-Co₃O₄ /
- formaldehyde oxidation /
- oxygen vacancy /
- formate

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图 1 不同Ce/Co物质的量比对催化剂甲醛催化性能的影响

Figure 1 Influence of Ce/Co molar ratio on the catalytic performance of CeO₂-Co₃O₄ (a) and Ag/CeO₂-Co₃O₄ (b) in formaldehyde degradation; (c) long term test for the Ag/Ce1Co19 catalyst

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图 2 催化剂的XRD谱图

a: Ag/Co；b: Ag/Ce1Co19；c: Ag/Ce5Co15；d: Ag/Ce10Co10；e: Ag/Ce15Co5；f: Ag/Ce19Co1

Figure 2 XRD patterns of various catalysts

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图 3 不同催化剂的N₂吸附-脱附曲线

Figure 3 N₂ adsorption-desorption isotherms of various Ag/CeO₂-Co₃O₄ catalysts

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图 4 不同催化剂的拉曼光谱谱图

Figure 4 Raman spectra of various Ag/CeO₂-Co₃O₄ catalysts

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图 5 催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of various Ag/CeO₂-Co₃O₄ catalysts

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图 6 70 ℃下HCHO吸附(a)随后通氧反应(b)期间在Ag/Ce5Co15上及HCHO吸附(c)随后通氧反应(d)期间在Ag/Ce1Co19上获得的原位漫反射傅里叶红外光谱谱图

Figure 6 In situ DRIFTS spectra obtained during HCHO adsorption (a) and then HCHO oxidation (b) on Ag/Ce5Co15 catalyst, and those during HCHO adsorption (c) and then HCHO oxidation (d) on Ag/Ce1Co19 catalyst under 70 ℃

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表 1 不同催化剂的孔结构参数

Table 1 Textural properties of various Ag/CeO₂-Co₃O₄ catalysts

Sample	A_BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore size d/nm
Ag/Co	33.63	0.206	17.1
Ag/Ce1Co19	35.88	0.148	16.7
Ag/Ce5Co15	40.05	0.123	12.0
Ag/Ce10Co10	53.67	0.117	8.4
Ag/Ce15Co5	73.94	0.116	6.9
Ag/Ce19Co1	99.78	0.109	5.9

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