Pt-MOx/CeO2水相重整催化剂上氧化物助剂对于水气变换反应的促进作用研究

ZHANG Wei-jie; TIAN Zhi-peng; HUANG Jia-hao; WANG Jun-yao; LUO Xiang-long; WANG Chao; SHU Ri-yang; LIU Jian-ping; CHEN Ying

doi:10.1016/S1872-5813(23)60363-9

Pt-MO_x/CeO₂水相重整催化剂上氧化物助剂对于水气变换反应的促进作用研究

doi: 10.1016/S1872-5813(23)60363-9

张伟杰^{1, 2,},
田志鹏^{1, 2, 3, ,},
黄嘉豪^{1, 2,},
王珺瑶^{1, 2,},
罗向龙^1,,
王超^1,,
舒日洋^1,,
刘建平^2,,
陈颖^1,

1.
广东工业大学材料与能源学院广东省功能软凝聚态重点实验室, 广东广州510006
2.
广东工业大学材料与能源学院智慧能源研究中心, 广东广州510006
3.
广东省新能源与可再生能源研究与开发重点实验室, 广东广州510640

详细信息

中图分类号: TK91
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出版历程
- 收稿日期: 2023-01-15
- 修回日期: 2023-03-14
- 录用日期: 2023-03-21
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-12-05

Investigation of the promotion effect of metal oxides on the water-gas shift reaction activity over Pt-MO_x/CeO₂ catalysts for aqueous phase reforming

ZHANG Wei-jie^{1, 2
,},
TIAN Zhi-peng^{1, 2, 3
, ,},
HUANG Jia-hao^{1, 2
,},
WANG Jun-yao^{1, 2
,},
LUO Xiang-long^1
,,
WANG Chao^1
,,
SHU Ri-yang^1
,,
LIU Jian-ping^2
,,
CHEN Ying^1
,

1.
Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
2.
Smart Energy Research Center, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
3.
Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Funds: The project was supported by the Natural Science Foundation of China (52106234), Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development (E239kf1301) and Science and Technology Planning Project of Guangdong Province (2021A0505030065).

More Information

Corresponding author: Tel: + 86 20 39322572, E-mail: tianzhipeng@gdut.edu.cn

摘要

摘要: 甲醇水相重整是一种在相对温和条件下的有效产氢路径。采用分步浸渍法制备Pt/CeO₂和Pt-MO_x/CeO₂ (M = Fe、Cr、Mg、Mn)系列催化剂，并对其反应性能进行了研究。采用XPS、XRD、TEM、CO-TPD、NH₃-TPD、CO₂-TPD等表征手段对催化剂的金属价态、氧空位数量、金属粒子分布、CO吸附性能和催化剂的酸/碱性等性质进行表征和分析。通过关联结果表明，MO_x的加入削弱了Pt-CeO₂间的相互作用，促进了价态较低的Pt^{δ +}的生成，这有助于C–H键的裂解，促进甲醇的转化。Pt-MgO/CeO₂上的产氢量最高(164.78 mmol)，CO和CH₄选择性相对较低，而Pt-CrO_x/CeO₂上的CH₄选择性最高(2.21%)。对于Pt/CeO₂和Pt-MO_x/CeO₂ (M = Fe、Cr、Mg、Mn)催化剂的产物选择性而言，CO₂/CH₄比与催化剂碱度相关性较好，说明碱度促进了水分子的解离吸附和水气变换反应活性，降低了甲烷化活性。
- WGS反应 /
- 碱度 /
- 液相重整 /
- 金属–载体相互作用
Abstract: Aqueous phase reforming (APR) of methanol is a potential pathway for the effective hydrogen production under relatively mild conditions. The Pt/CeO₂ and a series of Pt-MO_x/CeO₂ (M = Fe, Cr, Mg, Mn) catalysts were prepared by sequential impregnation method and their APR reaction performances were studied. The catalyst properties including valence state of the promoters, the amount of oxygen vacancies, the metal distributions, the adsorption properties of CO and the acidity/basicity of catalysts were characterized and analyzed by XPS, XRD, TEM, CO-TPD, NH₃-TPD, CO₂-TPD, etc. It was found that the addition of MO_x weakened the Pt-CeO₂ interaction and promoted the generation of Pt^{δ +} species with lower valence state, which contribute to the C−H bond cleavage and facilitate methanol conversion. The highest hydrogen production (164.78 mmol) and relatively low CO and CH₄ selectivities were obtained over the Pt-MgO/CeO₂, while the highest CH₄ selectivity was obtained over the Pt-CrO_x/CeO₂ (2.21%). Over the Pt/CeO₂ and Pt-MO_x/CeO₂ (M = Fe, Cr, Mg, Mn) catalysts, CO₂/CH₄ ratio correlated well with the catalyst basicity, indicating that the basicity promotes the dissociation adsorption of H₂O as well as the water-gas shift (WGS) reaction activity and decreases the methanation activity.
- WGS reaction /
- basicity /
- aqueous phase reforming /
- metal-support interaction

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FIG. 2806. FIG. 2806.

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Figure 1 XRD patterns of Pt/CeO₂ and Pt-MO_x/CeO₂ catalysts (a): Fresh catalysts; (b): Spent catalysts

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Figure 2 TEM and HRTEM images of the fresh (a) Pt/CeO₂, (b) Pt-FeO_x/CeO₂, (c) Pt-CrO_x/CeO₂, (d) Pt-MgO/CeO₂ and (e) Pt-MnO_x/CeO₂ catalysts

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Figure 3 TEM images of the spent (a′) Pt/CeO₂, (b′) Pt-FeO_x/CeO₂, (c′) Pt-CrO_x/CeO₂, (d′) Pt-MgO/CeO₂ and (e′) Pt-MnO_x/CeO₂ catalysts

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Figure 4 (a) Pt 4f, (b) Mn 2p, Fe 2p, Mg 1s, Cr 2p, (c) Ce 3d and (d) O 1s XPS spectra of the as-synthesized catalysts

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Figure 5 Pt phases on the Pt/CeO₂ and Pt-MO_x/CeO₂ prepared by sequential impregnation method

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Figure 6 CO-TPD profiles of the Pt/CeO₂, Pt-FeO_x/CeO₂, Pt-CrO_x/CeO₂, Pt-MgO/CeO₂ and Pt-MnO_x/CeO₂ catalysts

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Figure 7 (a) CO₂-TPD and (b) NH₃-TPD profiles of the Pt/CeO₂, Pt-FeO_x/CeO₂, Pt-CrO_x/CeO₂, Pt-MgO/CeO₂ and Pt-MnO_x/CeO₂ catalysts

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Figure 8 Relationship between CO₂/CH₄ and catalyst basicity

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Table 1 APR performances over different catalysts

Catalyst	Con. /%	Product selectivity /%				Gas yield /mmol				CO₂/CH₄
Catalyst	Con. /%	H₂	CO₂	CH₄	CO	H₂	CO₂	CH₄	CO	CO₂/CH₄
Pt/CeO₂	80.98	74.28	24.75	0.82	0.15	136.93	45.62	1.51	0.28	30.21
Pt-FeO_x/CeO₂	85.86	72.65	26.01	1.20	0.14	141.99	50.84	2.34	0.28	21.73
Pt-CrO_x/CeO₂	86.98	72.52	25.07	2.21	0.20	143.59	49.65	4.39	0.39	11.31
Pt-MgO/CeO₂	96.77	74.80	24.74	0.38	0.08	164.78	54.51	0.83	0.18	65.67
Pt-MnO_x/CeO₂	76.43	72.31	26.81	0.68	0.19	125.82	46.66	1.19	0.34	39.21

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Table 2 Catalyst properties of the Pt/CeO₂ and Pt-MO_x/CeO₂ catalysts (M = Fe, Cr, Mg, Mn)

Catalyst	Metal contents w/%		Average diameter /nm^a	O_β/(O_α + O_β + O_γ)	Ce^{3 +}/(Ce^{3 +} + Ce^{4 +})
Catalyst	Pt	M	Average diameter /nm^a	O_β/(O_α + O_β + O_γ)	Ce^{3 +}/(Ce^{3 +} + Ce^{4 +})
Pt/CeO₂	1.74	−	9.3	57.14%	22.91%
Pt-FeO_x/CeO₂	1.80	1.07 (Fe)	8.3	27.60%	21.76%
Pt-CrO_x/CeO₂	1.74	1.11 (Cr)	8.0	55.56%	22.42%
Pt-MgO/CeO₂	1.72	0.99 (Mg)	8.5	44.84%	21.99%
Pt-MnO_x/CeO₂	1.77	1.04 (Mn)	8.5	64.52%	39.32%
^a: Calculated by Scherrer equation ^[23]

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Table 3 Desorption amounts (low temperature range/high temperature range) in TPD characterizations of the Pt/CeO₂ and Pt-MO_x/CeO₂ (M = Fe, Cr, Mg, Mn) catalysts

Catalyst	Desorption amount /(mmol·g⁻¹)
Catalyst	CO-TPD	CO₂-TPD	NH₃-TPD
Pt/CeO₂	− /0.54	0.28/ −	1.04/ −
Pt-FeO_x/CeO₂	0.30/0.53	0.19/ −	0.76/ −
Pt-CrO_x/CeO₂	2.50/ −	0.17/ −	1.09/ −
Pt-MgO/CeO₂	− /1.37	0.07/0.51	0.43/ −
Pt-MnO_x/CeO₂	1.99/ −	0.16/ −	0.48/ −

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