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Anatase TiO2 Activated by Gold Nanoparticles for Selective Hydrodeoxygenation of Guaiacol to Phenolics

发表时间:2019-03-12
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论文类型:
期刊论文
第一作者:
Mao, Jingbo
通讯作者:
Zhang, ZC (reprint author), Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China.
合写作者:
Zhang, Z. Conrad,Zhou, Jinxia,Xia, Zhi,Wang, Zhiguang,Xu, Zhanwei,Xu, Wenjuan,Yan, Peifang,Liu, Kairui,Guo, Xinwen
发表时间:
2017-01-01
发表刊物:
ACS CATALYSIS
收录刊物:
SCIE、EI、Scopus
文献类型:
J
卷号:
7
期号:
1
页面范围:
695-705
ISSN号:
2155-5435
关键字:
guaiacol hydrogenation; phenol; gold catalyst; anatase; lignin
摘要:
Gold nanoparticles on a number of supporting materials, including anatase TiO2 (TiO2-A, in 40 nm and 45 pm), rutile TiO2 (TiO2-R), ZrO2, Al2O3, SiO2, and activated carbon, were evaluated for hydrodeoxygenation of guaiacol in 6.5 MPa initial H-2 pressure at 300 degrees C. The presence of gold nanoparticles on the supports did not show distinguishable performance compared to that of the supports alone in the conversion level and in the product distribution, except for that on a TiO2-A-40 nm. The lack of marked catalytic activity on supports other than TiO2-A-40 nm suggests that Au nanoparticles are not catalytically active on these supports. Most strikingly, the gold nanoparticles on the least-active TiO2-A-40 nm support stood out as the best catalyst exhibiting high activity with excellent stability and remarkable selectivity to phenolics from guaiacol hydrodeoxygenation. The conversion of guaiacol (similar to 43.1%) over gold on the TiO2-A-40 nm was about 33 times that (1.3%) over the TiO2-A-40 nm alone. The selectivity of phenolics was 87.1%. The products are mainly phenolic compounds with no aromatics and saturated hydrocarbons such as cyclohexane. The gold particle size ranging from 2.7 to 41 nm and water content were found to significantly affect the Au/TiO2-A-40 nm catalyst activity but not the product selectivity. The reaction rates of 0.26 and 0.91 (min(-1) g-cat(-1) cm(3)) were determined for guaiacol hydrogenation and catechol hydrogenation, respectively. Bimolecular methylation was established as the dominant mechanism for methyl group transfer among the phenolics. Two major pathways of guaiacol hydrogenation to phenolics over the 0.4Au-19 nm/TiO2-A-40 nm are proposed: (1) direct hydrogenation of guaiacol to form phenol and methanol, (2) hydrodehydroxylation of catechol intermediate from the transmethylation between guaiacol and phenol.
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