State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences
University of Chinese Academy of Sciences
Dalian National Laboratory for Clean Energy

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。

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.

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

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. 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[J]. 燃料化学学报（中英文）, 2024, 52(1): 38-46.

WANG Jia, GAO Xiujuan, SONG Faen, ZHANG Junfeng, WANG Xiaoxing, ZHANG Tao, TAN Yisheng, HAN Yizhuo, ZHANG Qingde. Effect of molybdenum valence in low Mo/Sn ratio catalysts for the oxidation of methanol to dimethoxymethane[J]. Journal of Fuel Chemistry and Technology, 2024, 52(1): 38-46.