焙烧温度对Pt-FeOx/γ-Al2O3催化剂催化甲醛氧化性能的影响

崔维怡; 王希越; 谭乃迪

焙烧温度对Pt-FeO_x/γ-Al₂O₃催化剂催化甲醛氧化性能的影响

崔维怡^{1, 2},
王希越²,
谭乃迪^2, ,

1.
吉林化工学院化工清洁生产技术吉林省高校重点实验室, 吉林吉林 132022
2.
吉林化工学院化学与制药工程学院, 吉林吉林 132022

基金项目:

国家自然科学基金 51805207

吉林省教育厅‘十三五’科学技术研究规划项目 JJKA20180559KJ

吉林市科技创新发展计划项目 201750211

详细信息

中图分类号: TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2019-03-28
- 修回日期: 2019-05-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-08-10

Effect of calcination temperature on catalytic performance of Pt-FeO_x/γ-Al₂O₃ catalysts for HCHO oxidation

CUI Wei-yi^{1, 2},
WANG Xi-yue²,
TAN Nai-di^{2
, ,}

1.
The Key Laboratory of Chemical Cleaner Production Technology of Jilin Province, Jilin Institute of Chemical Technology, Jilin 132022, China;
2.
College of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China

Funds:

the National Science Foundation of China 51805207

13th Five-Year Science and Technology Research and Planning Project of Education Department of Jilin province JJKA20180559KJ

Science and Technology Innovation Development Plan Project of Jilin 201750211

More Information

Corresponding author: TAN Nai-di, E-mail: tannd0119@163.com

摘要

摘要: 采用胶体沉积法制备了Pt-FeO_x/γ-Al₂O₃催化剂，通过XRD、TEM、BET、XPS、H₂-TPR和FT-IR等技术对催化剂进行了表征，考察了焙烧温度对Pt-FeO_x/γ-Al₂O₃催化剂表面结构及其催化甲醛氧化性能的影响。结果表明，焙烧温度对Pt-FeO_x/γ-Al₂O₃催化剂的氧化还原性能、Pt物种的化学状态以及表面羟基的数量有较大的影响。在室温下，所有Pt-FeO_x/γ-Al₂O₃催化剂均表现出催化氧化活性，其中，200℃焙烧的Pt-FeO_x/γ-Al₂O₃催化剂表现出最好的催化性能，可以将甲醛100%转化为CO₂和H₂O。较低温度焙烧的Pt-FeO_x/γ-Al₂O₃催化剂表面Pt物种具有较好的价态分布以及更多的界面活性位，如Pt-O-Fe物种，因而在温和条件下对甲醛的催化氧化活性较高。
- 甲醛 /
- 催化氧化 /
- 活性 /
- 焙烧温度 /
- 铂纳米粒子
Abstract: A series of Pt-FeO_x/γ-Al₂O₃ catalysts were prepared by colloid-deposition method and characterized by XRD, TEM, BET, XPS, H₂-TPR and FT-IR to investigate the effects of calcination temperature on the surface structure of Pt-FeO_x/γ-Al₂O₃ catalyst and its catalytic performance in catalytic HCHO oxidation. The characterization results showed that the applied calcination temperature greatly influenced the redox properties and chemical states of the Pt species, as well as the amount of surface hydroxyl groups. All resultant Pt-FeO_x/γ-Al₂O₃ catalysts demonstrated activity in HCHO oxidation. The sample with calcination at 200 ℃ exhibited the best performance, which afforded 100% conversion of HCHO into CO₂ and H₂O at room temperature. The catalysts with lower calcination temperature should be beneficial to have a better valence distribution of Pt species and produce more accessible interface active sites like Pt-O-Fe species, thus endowing Pt-FeO_x/γ-Al₂O₃ catalyst with relatively high activity for the oxidation of formaldehyde under mild conditions.
- formaldehyde /
- catalytic oxidation /
- reactivity /
- calcination temperature /
- Pt nanoparticles

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图 1 催化剂性能评价流程示意图

Figure 1 Schematic flow diagram of the catalytic performance testing

1: H₂; 2: N₂; 3: O₂; 4, 6: flowmeter; 5: HCHO; 7: three way valve; 8: reactor; 9: chromatography; 10: exhaust; 11: carrier gas; 12: offgas

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图 2 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的XRD谱图

Figure 2 XRD patterns of the Pt/γ-Al₂O₃-200, Pt-FeO_x/ Al₂O₃-t catalysts and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400

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图 3 t/γ-Al₂O₃-200和Pt-FeO_x/γ-Al₂O₃-t催化剂的HRTEM电镜照片((a)-(d), (f))，Pt-FeO_x/γ-Al₂O₃-200催化剂的HAADF-STEM电镜照片(e)和EDX元素能量分布图(g)

Figure 3 HRTEM ((a)-(d), (f)) of the Pt/γ-Al₂O₃-200 and Pt-FeO_x/γ-Al₂O₃ -t catalyst, HAADF-STEM(e) and EDX mapping images(g) of the Pt-FeO_x/γ-Al₂O₃-200 catalyst

(a): Pt/γ-Al₂O₃-200; (b): Pt-FeO_x/γ-Al₂O₃-200; (c): Pt-FeO_x/γ-Al₂O₃-300; (d): Pt-FeO_x/γ-Al₂O₃-400 (e): Pt-FeO_x/γ-Al₂O₃-200; (f): Pt-FeO_x/γ-Al₂O₃-200; (g): Pt-FeO_x/γ-Al₂O₃-200

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图 4 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的甲醛催化氧化活性

Figure 4 HCHO catalytic oxidation activities of the Pt/γ- Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400 (reaction conditions: HCHO 375 mg/m³, φ_O₂=20%, N₂ balance, RH = 30%, GHSV: 60000 cm³/(g·h))

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图 5 Pt/γ-Al₂O₃-200、Pt-FeO_x/Al₂O₃-t催化剂的Pt 4f的XPS谱图

Figure 5 Pt 4f XPS spectra of the Pt/γ-Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts

(a): Pt/γ-Al₂O₃-200; (b): Pt-FeO_x/γ-Al₂O₃-200; (c): Pt-FeO_x/γ-Al₂O₃-300; (d): Pt-FeO_x/γ-Al₂O₃-400

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图 6 Pt-FeO_x/γ-Al₂O₃-t催化剂的Fe 2p XPS谱图

Figure 6 Fe 2p XPS spectra of the Pt-FeO_x/γ-Al₂O₃ catalysts calcined at various temperatures

a: Pt-FeO_x/γ-Al₂O₃-200; b: Pt-FeO_x/γ-Al₂O₃-300; c: Pt-FeO_x/γ-Al₂O₃-400

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图 7 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的Al 2p的XPS谱图

Figure 7 Al 2p XPS spectra of Pt/γ-Al₂O₃-200, Pt-FeO_x/γ-Al₂O₃-t catalyst and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400

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图 8 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的O 1s的XPS谱图

Figure 8 O 1s XPS spectra of the Pt/γ-Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400

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图 9 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的FT-IR谱图

Figure 9 FT-IR spectra of the Pt/γ-Al₂O₃-200, Pt-FeO_x/ Al₂O₃-t catalysts and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400

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图 10 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的H₂-TPR谱图

Figure 10 H₂ -TPR profiles of the Pt/γ-Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts and γ-Al₂O₃ support

a: γ-Al₂O₃; b: Pt/γ-Al₂O₃-200; c: Pt-FeO_x/γ-Al₂O₃-200; d: Pt-FeO_x/γ-Al₂O₃-300; e: Pt-FeO_x/γ-Al₂O₃-400

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表 1 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂和γ-Al₂O₃载体的物化性能

Table 1 Physical properties of the Pt/γ-Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts and γ-Al₂O₃ support

Catalyst	A_BET/(m²·g^-1)	Pore volume v/(m³·g^-1)	Pore size d/nm
γ-Al₂O₃	162	0.23	6.0
Pt/γ-Al₂O₃-200	119	0.17	6.5
Pt-FeO_x/γ-Al₂O₃-200	113	0.17	6.6
Pt-FeO_x/γ-Al₂O₃-300	104	0.16	6.7
Pt-FeO_x/γ-Al₂O₃-400	98	0.14	6.9

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表 2 Pt/γ-Al₂O₃-200、Pt-FeO_x/γ-Al₂O₃-t催化剂以及γ-Al₂O₃载体的Pt 4d和O 1s XPS拟合

Table 2 Pt 4d and O 1s XPS curve fitting results of Pt/γ- Al₂O₃-200, Pt-FeO_x/Al₂O₃-t catalysts and γ-Al₂O₃ support

Catalyst	Pt²⁺/Pt ⁰	O_II/(O_I+ O_II)
γ-Al₂O₃		0.37
Pt/γ-Al₂O₃-200	0.36	0.31
Pt-FeO_x/γ-Al₂O₃-200	0.39	0.31
Pt-FeO_x/γ-Al₂O₃-300	0.58	0.23
Pt-FeO_x/γ-Al₂O₃-400	1.33	0.18

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