低钼锡比催化剂中钼的价态对甲醇氧化制甲缩醛反应性能的影响

王佳; 高秀娟; 宋法恩; 张俊峰; 王晓星; 张涛; 谭猗生; 韩怡卓; 张清德

doi:10.1016/S1872-5813(23)60370-6

低钼锡比催化剂中钼的价态对甲醇氧化制甲缩醛反应性能的影响

doi: 10.1016/S1872-5813(23)60370-6

王佳^{1, 2,},
高秀娟^{1, 2,},
宋法恩^1, ,,
张俊峰^1,,
王晓星^1,,
张涛^1,,
谭猗生^1,,
韩怡卓^1,,
张清德^{1, 3, ,}

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
中国科学院洁净能源创新研究院, 辽宁大连 116023

基金项目: 国家自然科学基金（22172187），山西省中央引导地方科技发展资金项目（YDZJSX2022A072），中国科学院洁净能源创新研究院合作基金（DNL 201903）和中国科学院青年创新促进会人才项目（2014155）资助

详细信息

通讯作者:
Tel: 0351-4044388, E-mail: songfe@sxicc.ac.cn

qdzhang@sxicc.ac.cn

中图分类号: O643
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出版历程
- 收稿日期: 2023-04-04
- 修回日期: 2023-04-26
- 录用日期: 2023-04-27
- 网络出版日期: 2023-05-24

Effect of molybdenum valence in low Mo/Sn ratio catalystsfor the oxidation of methanol to dimethoxymethane

WANG Jia^{1, 2
,},
GAO Xiujuan^{1, 2
,},
SONG Faen^{1
, ,},
ZHANG Junfeng^1
,,
WANG Xiaoxing^1
,,
ZHANG Tao^1
,,
TAN Yisheng^1
,,
HAN Yizhuo^1
,,
ZHANG Qingde^{1, 3
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Dalian National Laboratory for Clean Energy, Dalian 116023, China

Funds: The project was supported by the National Natural Science Foundation of China (22172187)，the Central Guidance on Local Science and Technology Development Fund of Shanxi Province (YDZJSX2022A072)，the Dalian National Laboratory For Clean Energy (DNL) Cooperation Fund，CAS (DNL 201903)，and the Youth Innovation Promotion Association CAS (2014155)

摘要

摘要: 采用两步水热合成法制备了一系列低Mo/Sn比（1∶20，物质的量比）催化剂，并考察了锡前驱体焙烧温度对甲醇氧化制甲缩醛反应性能的影响。通过XRD、Raman、FT-IR、XPS、NH₃-TPD及H₂-TPR等表征手段对催化剂的晶体结构、表面性质、氧化还原性及钼物种价态等进行了分析。结果表明，在Mo1Sn20-600 ℃Sn催化剂上，反应温度为140 ℃时，甲醇转化率及甲缩醛选择性分别达30.0%及90.0%。锡前驱体焙烧温度的变化主要影响了Mo1Sn20催化剂的结构、钼物种的价态及存在状态，进而影响其催化活性；高温焙烧的锡前驱体更有利于Mo1Sn20催化剂中甲醇活化的活性位点Mo^{6 +}物种的生成。
- 甲醇 /
- 低温氧化 /
- 甲缩醛 /
- Mo1Sn20催化剂 /
- Mo^{6 +} 物种
Abstract: A series of Mo/Sn (1:20, molar ratio) catalysts were prepared by two-step hydrothermal synthesis method, and the effect of calcination temperature of tin precursors on the reaction performance of methanol oxidation to dimethoxymethane (DMM) was investigated. The crystal structure, surface properties, redox property and valence change of molybdenum species of the catalyst were characterized by XRD, Raman, FT-IR, XPS, NH₃-TPD and H₂-TPR. The results showed that Mo1Sn20-600 ℃Sn catalyst exhibited better performance than other catalysts, achieving DMM selectivity of 90% with methanol conversion of 30 % at 140 ℃. From the characterization results, the surface properties of the tin precursors affected the structure of catalyst, the degree of molybdenum oxide dispersion and valence of molybdenum species, and further influenced the performance of the catalysts. The high temperature calcination of tin precursors is more favorable for the generation of Mo⁶⁺ in the Mo1Sn20 catalyst.
- methanol /
- low temperature oxidation /
- dimethoxymethane /
- Mo1Sn20 catalyst /
- Mo^{6 +} species

HTML全文

图 1 不同锡前驱体制备的Mo1Sn20催化剂的XRD谱图

Figure 1 The XRD patterns of the Mo1Sn20 catalysts withdifferent Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-200 ℃Sn; c-Mo1Sn20-300 ℃Sn; d-Mo1Sn20-400 ℃Sn; e-Mo1Sn20-500 ℃Sn; f-Mo1Sn20-600 ℃Sn.

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图 2 不同锡前驱体的N₂吸附-脱附曲线和孔径分布

Figure 2 The N₂ dsorption desorption isotherms and pore size distributionsof the different Sn precursors

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图 3 不同锡前驱体制备的Mo1Sn20催化剂的N₂吸附-脱附曲线和孔径分布

Figure 3 The N₂ adsorption desorption is otherms andpore size distributions of the Mo1Sn20 catalysts with different Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-200 ℃Sn; c-Mo1Sn20-300 ℃Sn; d-Mo1Sn20-400 ℃Sn; e-Mo1Sn20-500 ℃Sn; f-Mo1Sn20-600 ℃Sn.

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图 4 不同锡前驱体制备的Mo1Sn20催化剂的Raman谱图

Figure 4 The Raman spectra of the Mo1Sn20 catalysts with different Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-500 ℃Sn; c-Mo1Sn20-600 ℃Sn.

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图 5 不同锡前驱体制备的Mo1Sn20催化剂的FT-IR谱图

Figure 5 The FI-IR spectra of the Mo1Sn20 catalysts withdifferent Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-200 ℃Sn; c-Mo1Sn20-300 ℃Sn; d-Mo1Sn20-400 ℃Sn; e-Mo1Sn20-500 ℃Sn; f-Mo1Sn20-600 ℃Sn.

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图 6 不同锡前驱体制备的Mo1Sn20催化剂的NH₃-TPD谱图

Figure 6 The NH₃-TPD profiles of the Mo1Sn20 catalysts with different Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-200 ℃Sn; c-Mo1Sn20-300 ℃Sn; d-Mo1Sn20-400 ℃Sn; e-Mo1Sn20-500 ℃Sn; f-Mo1Sn20-600 ℃Sn.

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图 7 不同锡前驱体制备的Mo1Sn20催化剂的H₂-TPR谱图

Figure 7 The H₂-TPR of the Mo1Sn20 catalysts withdifferent Sn precursors

a-Mo1Sn20-80 ℃Sn; b-Mo1Sn20-200 ℃Sn; c-Mo1Sn20-300 ℃Sn; d-Mo1Sn20-400 ℃Sn; e-Mo1Sn20-500 ℃Sn; f-Mo1Sn20-600 ℃Sn; g-600 ℃SnO₂.

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图 8 不同锡前驱体制备的Mo1Sn20催化剂的XPS谱图

Figure 8 The XPS of the Mo1Sn20 catalysts with different Sn precursors

a-Sn 3d; b-Mo 3d.

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图 9 钼物种催化甲醇氧化机理

Figure 9 Mechanism of methanol oxidation on Mo species

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表 1 不同锡前驱体制备的Mo1Sn20催化剂上甲醇氧化的反应性能

Table 1 Reaction performance of methanol oxidation over Mo1Sn20 catalysts with different Sn precursors

Catalyst	CH₃OH conversion /%	C-mol selectivity /%					DMM yield /%
Catalyst	CH₃OH conversion /%	MF	DME	FA	DMM	CO_x	DMM yield /%
Mo1Sn20-80 ℃Sn	15.9	8.7	1.3	0	90.0	0	14.3
Mo1Sn20-200 ℃Sn	17.7	9.0	2.1	0	88.9	0	15.7
Mo1Sn20-300 ℃Sn	19.5	6.8	2.0	0	91.2	0	17.8
Mo1Sn20-400 ℃Sn	21.4	5.6	2.1	0	92.3	0	19.8
Mo1Sn20-500 ℃Sn	21.5	7.1	2.3	0	90.6	0	19.5
Mo1Sn20-600 ℃Sn	30.0	5.8	4.2	0	90.0	0	27.0
Reaction conditions: atmospheric pressure, t_R=140 ℃，n(CH₃OH): n(O₂)=1∶9.415, CH₃OH flow rate=0.817 mL/h, GHSV=7200 h⁻¹.

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表 2 不同锡前驱体的织构性能

Table 2 Textural performance of thedifferent Sn precursors

Catalysts	Surface area / (m²·g⁻¹)	Volume of pore / (cm³·g⁻¹)	Pore size / nm
80 ℃Sn	254.65	0.12	1.87
200 ℃Sn	284.28	0.13	1.83
300 ℃Sn	212.76	0.13	2.51
400 ℃Sn	131.87	0.13	4.0
500 ℃Sn	66.75	0.12	7.2
600 ℃Sn	37.41	0.12	13.0

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表 3 不同锡前驱体制备的Mo1Sn20催化剂的织构性能

Table 3 Textural performance of the Mo1Sn20 catalysts with different Sn precursors

Catalyst	Surface area / (m²·g⁻¹)	Volume of pore / (cm³·g⁻¹)	Pore size / nm
Mo1Sn20-80 ℃Sn	112.09	0.12	4.12
Mo1Sn20-200 ℃Sn	112.65	0.10	3.70
Mo1Sn20-300 ℃Sn	128.55	0.11	3.39
Mo1Sn20-400 ℃Sn	85.53	0.10	4.86
Mo1Sn20-500 ℃Sn	51.64	0.11	8.66
Mo1Sn20-600 ℃Sn	21.76	0.10	18.45

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表 4 不同锡前驱体制备的Mo1Sn20催化剂的XPS-Mo 3d拟合

Table 4 The XPS-Mo 3d fitting resultsof the Mo1Sn20 catalysts withdifferent Sn precursors

Catalyst	Mo^{6 +}/%	Mo^{5 +}/%
MoSn20-80 ℃Sn	49.2	50.8
Mo1Sn20-500 ℃Sn	76.0	24.0
Mo1Sn20-600 ℃Sn	79.9	20.1

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