Citation: WU Jian-bing, SHI Rui-ping, QIN Zhang-feng, LIU Huan, LI Zhi-kai, ZHU Hua-qing, ZHAO Yong-xiang, WANG Jian-guo. Selective oxidation of methanol to methyl formate over bimetallic Au-Pd nanoparticles supported on SiO₂[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(7): 780-790. shu

Selective oxidation of methanol to methyl formate over bimetallic Au-Pd nanoparticles supported on SiO₂

1.
Engineering Research Center of Ministry of Education for Fine Chemicals, Shanxi University, Taiyuan 030006, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: QIN Zhang-feng, qzhf@sxicc.ac.cn WANG Jian-guo, iccjgw@sxicc.ac.cn
Received Date: 2 March 2019
Revised Date: 5 April 2019

Fund Project: the Strategic Program of Coal-based Technology of Shanxi Province MQ2014-10the National Key R & D Program of China 2018YFB0604804the National Natural Science Foundation of China 21703127the Strategic Program of Coal-based Technology of Shanxi Province MQ2014-11The project was supported by the National Key R & D Program of China (2018YFB0604804), the National Natural Science Foundation of China (21603254, 21703127, 21703276), the Strategic Program of Coal-based Technology of Shanxi Province (MQ2014-11, MQ2014-10), the Key Research Program of the Chinese Academy of Sciences (KFZD-SW-410)the Key Research Program of the Chinese Academy of Sciences KFZD-SW-410the National Natural Science Foundation of China 21603254the National Natural Science Foundation of China 21703276

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Selective oxidation of methanol to methyl formate (MF) is one of the most attractive processes to get valuable methanol-downstream products, where the supported Au and Pd catalysts were proved rather effective at low temperature. To search for highly active, regenerable and practical catalysts as well as to reveal the synergy of Au-Pd and reaction mechanism for the methanol oxidation, a series of silica supported Au-Pd nanoparticles (Au-Pd/SiO₂) were prepared and their catalytic performance in the oxidation of methanol to MF with molecular oxygen was investigated in this work. The results indicate that the Au₂-Pd₁/SiO₂ catalyst with an Au+Pd loading of only 0.6% and a Au/Pd mass ratio of 2 exhibits excellent performance in the methanol oxidation with oxygen; the conversion of methanol over Au₂-Pd₁/SiO₂ reaches 57.0% at 130℃, with a selectivity of 72.7% to MF. Various characterization results illustrate that the Au-Pd bimetallic nanoparticles (2-4 nm) are highly dispersed on the silica surface, inclined to take a twinned structure and present the (111) planes, which may contribute to the high activity of Au-Pd/SiO₂ in the oxidation of methanol to MF. A possible reaction mechanism was proposed on the basis of DRIFTS results:methanol was first activated by surface oxygen on the interface of Au-Pd nanoparticles, forming the chemisorbed methoxy species; the methoxy species was then deprotonated to adsorbed formaldehyde species, which reacted with another methoxy species, producing MF by nucleophilic attack and subsequent β-H elimination.
- selective oxidation of methanol,
- methyl formate,
- gold,
- palladium,
- silica,
- bimetallic nanoparticles
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Selective oxidation of methanol to methyl formate over bimetallic Au-Pd nanoparticles supported on SiO2

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通讯作者: 陈斌, bchen63@163.com

Selective oxidation of methanol to methyl formate over bimetallic Au-Pd nanoparticles supported on SiO₂