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
计量
- 文章访问数: 282
- HTML全文浏览量: 81
- PDF下载量: 43
- 被引次数: 0
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
- 刊出日期: 2024-01-09

Effect of molybdenum valence in low Mo/Sn ratio catalysts for 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Mo⁶⁺物种的生成。
- 甲醇 /
- 低温氧化 /
- 甲缩醛 /
- Mo1Sn20催化剂 /
- Mo⁶⁺ 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 /
- Mo⁶⁺ species

HTML全文

FIG. 2878. FIG. 2878.

下载: 全尺寸图片幻灯片

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 with different Sn precursors

下载: 全尺寸图片幻灯片

图 2 不同锡前驱体的N₂吸附-脱附曲线（a）和孔径分布（b）

Figure 2 The N₂ dsorption desorption isotherms (a) and pore size distributions (b) of the different Sn precursors

下载: 全尺寸图片幻灯片

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

Figure 3 The N₂ adsorption desorption isotherms (a) and pore size distributions (b) of the Mo1Sn20 catalysts with different Sn precursors

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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 with different Sn precursors

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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 with different Sn precursors

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

图 9 钼物种催化甲醇氧化机理

Figure 9 Mechanism of methanol oxidation on Mo species

下载: 全尺寸图片幻灯片

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.

下载: 导出CSV

表 2 不同锡前驱体的织构性能

Table 2 Textural performance of the different Sn precursors

Catalyst	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

下载: 导出CSV

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

下载: 导出CSV

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 results of the Mo1Sn20 catalysts with different Sn precursors

Catalyst	Mo⁶⁺/%	Mo⁵⁺/%
MoSn20-80℃Sn	49.2	50.8
Mo1Sn20-500℃Sn	76.0	24.0
Mo1Sn20-600℃Sn	79.9	20.1

下载: 导出CSV

参考文献(37)

[1]	WU Q, TU K, ZENG Y, et al. Discussion on the main problems and countermeasures for building an upgrade version of main energy (coal) industry in China[J]. J China Coal Soc,2019,44(6):1625−1636.
[2]	XIE H, WU L, ZHENG D. Prediction on the energy consumption and coal demand of China in 2025[J]. J China Coal Soc,2019,44(7):1949−1960.
[3]	SHIH C F, ZHANG T, LI J H, et al. Powering the future with liquid sunshine[J]. Joule,2018,2(10):1925−1949. doi: 10.1016/j.joule.2018.08.016
[4]	REN J, XIN F, XU Y S. A review on direct synthesis of dimethoxymethane[J]. Chin J Chem Eng,2022,50:43−55. doi: 10.1016/j.cjche.2022.09.008
[5]	SCHMITZ N, BURGER J, HASSE H. Reaction kinetics of the formation of poly(oxymethylene) dimethyl ethers from formaldehyde and methanol in aqueous solutions[J]. Ind Eng Chem Res,2015,54(50):12553−12560. doi: 10.1021/acs.iecr.5b04046
[6]	YUAN M, DONG M R, TIAN Z W, et al. Reaction mechanisms and catalysis in the one-step synthesis of methylal via methanol oxidation[J]. J Energy Inst,2022,103:47−53. doi: 10.1016/j.joei.2022.05.006
[7]	GAO X J, ZHANG J F, SONG F E, et al. Selective oxidation conversion of methanol/dimethyl ether[J]. Chem Commun,2022,58(30):4687−4699. doi: 10.1039/D1CC07276E
[8]	AHMAD W, CHAN F L, SHROTRI A, et al. Dimethoxymethane production via CO₂ hydrogenation in methanol over novel Ru based hierarchical BEA[J]. J Energy Chem,2022,66:181−189. doi: 10.1016/j.jechem.2021.07.026
[9]	YUAN Y Z, LIU H C, IMOTO H, et al. Performance and characterization of a new crystalline SbRe₂O₆ catalyst for selective oxidation of methanol to methylal[J]. J Catal,2000,195(1):51−61. doi: 10.1006/jcat.2000.2990
[10]	LIU H C, IGLESIA E. Effects of support on bifunctional methanol oxidation pathways catalyzed by polyoxometallate Keggin clusters[J]. J Catal,2004,223(1):161−169. doi: 10.1016/j.jcat.2004.01.012
[11]	ZHAO H Y, BENNICI S, SHEN J Y, et al. Nature of surface sites of V₂O₅-TiO₂/ $ {\rm{SO}}_4^{2-} $ catalysts and reactivity in selective oxidation of methanol to dimethoxymethane[J]. J Catal,2010,272(1):176−189. doi: 10.1016/j.jcat.2010.02.028
[12]	GORNAY J, SECORDEL X, TESQUET G, et al. Direct conversion of methanol into 1, 1-dimethoxymethane: remarkably high productivity over an FeMo catalyst placed under unusual conditions[J]. Green Chem,2010,12(10):1722−1725. doi: 10.1039/c0gc00194e
[13]	MENG Y L, WAG T, CHEN S, et al. Selective oxidation of methanol to dimethoxymethane on V₂O₅-MoO₃/gamma-Al₂O₃ catalysts[J]. Appl Catal B: Environ,2014,160:161−172.
[14]	YUAN Y Z, SHIDO T, IWASAWA Y. The new catalytic property of supported rhenium oxides for selective oxidation of methanol to methylal[J]. Chem Commun,2000,(15):1421−1422. doi: 10.1039/b003870i
[15]	GUO H Q, LI D B, CHEN C B, et al. The one-step oxidation of methanol to dimethoxymethane over sulfated vanadia-titania catalysts: influence of calcination temperature[J]. RSC Adv,2015,5(79):64202−64207. doi: 10.1039/C5RA09072E
[16]	THAVORNPRASERT K A, CAPRON M, JALOWIECKI-DUHAMEL L, et al. Highly productive iron molybdate mixed oxides and their relevant catalytic properties for direct synthesis of 1, 1-dimethoxymethane from methanol[J]. Appl Catal B: Environ,2014,145:126−135. doi: 10.1016/j.apcatb.2013.01.043
[17]	ZHANG Z Z, ZHANG Q D, JIA L Y, et al. The effects of the Mo-Sn contact interface on the oxidation reaction of dimethyl ether to methyl formate at a low reaction temperature[J]. Catal Sci Technol,2016,6(15):6109−6117. doi: 10.1039/C6CY00460A
[18]	VALENTE N G, ARRUA L A, CADUS L E. Structure and activity of Sn-Mo-O catalysts: partial oxidation of methanol[J]. Appl Catal A: Gen,2001,205(1-2):201−214. doi: 10.1016/S0926-860X(00)00565-2
[19]	LIU H C, CHEUNG P, IGLESIA E. Structure and support effects on the selective oxidation of dimethyl ether to formaldehyde catalyzed by MoO_x domains[J]. J Catal,2003,217(1):222−232.
[20]	GONCALVES F, MEDEIROS P R S, EON J G, et al. Active sites for ethanol oxidation over SnO₂-supported molybdenum oxides[J]. Appl Catal A: Gen,2000,193(1/2):195−202. doi: 10.1016/S0926-860X(99)00430-5
[21]	熊盼, 高秀娟, 王文秀, 等. 焙烧温度对钼锡催化剂结构和二甲醚氧化性能的影响[J]. 燃料化学学报,2022,50(1):63−71. XIONG Pan, GAO Xiu-juan, WANG Wen-xiu, et al. Effect of calcination temperature on the structure and performance of molybdenum-tin catalyst for DME oxidation[J]. J Fuel Chem Technol,2022,50(1):63−71.
[22]	王文秀. 钼基催化剂上甲醇低温氧化研究[D]. 北京: 中国科学院大学, 2021. WANG Wen-xiu. Study on low temperature oxidation of methanol over molybdenum-based catalyst[D]. Beijing: University of Chinese Academy of Sciences, 2021.
[23]	YAN L N, ZHANG J F, GAO X J, et al. Oxidative coupling of methane over Mo-Sn catalysts[J]. Chem Commun,2021,57(98):13297−13300. doi: 10.1039/D1CC04821J
[24]	CHIORINO A, GHIOTTI G, PRINETTO F, et al. Preparation and characterization of SnO₂ and MoO_x-SnO₂ nanosized powders for thick film gas sensors[J]. Sens Actuators B: Chem,1999,58(1/3):338−349. doi: 10.1016/S0925-4005(99)00094-5
[25]	MAKEEVA E A, RUMYANTSEVA M N, GAS'KOV A M. Synthesis, microstructure, and gas-sensing properties of SnO₂/MoO₃ nanocomposites[J]. Inorg Mater,2005,41(4):370−377. doi: 10.1007/s10789-005-0139-4
[26]	SHAKIR I, SHAHID M, CHEREVKO S, et al. Ultrahigh-energy and stable supercapacitors based on intertwined porous MoO₃-MWCNT nanocomposites[J]. Electrochim Acta,2011,58:76−80. doi: 10.1016/j.electacta.2011.08.076
[27]	ZHANG Z Z, ZHANG Q D, JIA L Y, et al. Effects of tetrahedral molybdenum oxide species and MoO_x domains on the selective oxidation of dimethyl ether under mild conditions[J]. Catal Sci Technol,2016,6(9):2975−2983. doi: 10.1039/C5CY01569C
[28]	杨奇, 高秀娟, 冯茹, 等. 水热合成的MoO₃-SnO₂催化剂催化氧化二甲醚的性能研究[J]. 燃料化学学报,2019,47(8):934−941. doi: 10.1016/S1872-5813(19)30038-6 YANG Qi, GAO Xiu-juan, FENG Ru, et al. MoO₃-SnO₂ catalyst prepared by hydrothermal synthesis method for dimethyl ether catalytic oxidation[J]. J Fuel Chem Technol,2019,47(8):934−941. doi: 10.1016/S1872-5813(19)30038-6
[29]	王文秀, 高秀娟, 熊盼, 等. Mo-Sn催化剂上甲醇低温氧化制甲缩醛[J]. 燃料化学学报,2021,49(10):1487−1494. doi: 10.1016/S1872-5813(21)60094-4 WANG Wen-xiu, GAO Xiu-juan, XIONG Pan, et al. Low-temperature oxidation of methanol over Mo-Sn catalyst[J]. J Fuel Chem Technol,2021,49(10):1487−1494. doi: 10.1016/S1872-5813(21)60094-4
[30]	GU Y Y, ZHANG Z Z, WANG W F, et al. Effects of calcination atmosphere on the structure and performance of MoO₃-SnO₂ catalyst for theoxidation of dimethyl ether at low temperature[J]. J Fuel Chem Technol,2017,45(5):572−580.
[31]	YUAN M, TANG R Y, SUN X Y, et al. Effects of the support on bifunctional one-step synthesis of methylal via methanol oxidation catalysed by Fe-Mo-based bifunctional catalysts[J]. Sustainable Energy Fuels,2021,5(1):246−260. doi: 10.1039/D0SE01194K
[32]	ROJAS F, KORNHAUSER I, FELIPE C, et al. Capillary condensation in heterogeneous mesoporous networks consisting of variable connectivity and pore-size correlation[J]. Phys Chem Chem Phys,2002,4(11):2346−2355. doi: 10.1039/b108785a
[33]	熊盼. 二甲醚低温氧化钼基催化剂活性位结构与性能的研究[D]. 北京: 中国科学院大学, 2021. XIONG Pan. Study on the structure and properties of active site of low temperature oxidation of dimethyl ether over molybdenum based catalyst[D]. Beijing: University of Chinese Academy of Sciences, 2021.
[34]	MESTL G, SRINIVASAN T K K. Raman spectroscopy of monolayer-type catalysts: Supported molybdenum oxides[J]. Catal Rev,1998,40(4):451−570. doi: 10.1080/01614949808007114
[35]	YANG J K, ZHAO H L, ZHANG F C. Effects of heat treatment on the chemical states of O 1s and Sn 3d at the surface of SnO_x: F films by APCVD[J]. Mater Lett,2013,90:37−40. doi: 10.1016/j.matlet.2012.07.055
[36]	TAN X J, WANG L Z, CHENG C, et al. Plasmonic MoO_3-x@MoO₃ nanosheets for highly sensitive SERS detection through nanoshell-isolated electromagnetic enhancement[J]. Chem Commun,2016,52(14):2893−2896. doi: 10.1039/C5CC10020H
[37]	YANG J, XIAO X, CHEN P, et al. Creating oxygen-vacancies in MoO_3-x nanobelts toward high volumetric energy-density asymmetric supercapacitors with long lifespan[J]. Nano Energy,2019,58(1):455−465.