Molecular nitrogen promotes catalytic hydrodeoxygenation

Duan，Haohong1,2,3; Liu，Jin Cheng4; Xu，Ming5; Zhao，Yufei2,6; Ma，Xue Lu4; Dong，Juncai7; Zheng，Xusheng8; Zheng，Jianwei2; Allen，Christopher S.9,10; Danaie，Mohsen9,10; Peng，Yung Kang11; Issariyakul，Titipong12; Chen，Dongliang7; Kirkland，Angus I.9,10; Buffet，Jean Charles1; Li，Jun4,13; Tsang，Shik Chi Edman2; O’Hare，Dermot1

2019-12-01

10.1038/s41929-019-0368-6

Nature Catalysis   影响因子和分区

25201158

2520-1158

Although molecular dinitrogen (N) is widely used as a carrier or inert gas for many catalytic reactions, it is rarely considered as a catalytic promoter. Here, we report that N could be used to reduce the activation energy for catalytic hydrodeoxygenation over ruthenium-based catalysts. Specifically, we report a 4.3-fold activity increase in the catalytic hydrodeoxygenation of p-cresol to toluene over a titanium oxide supported ruthenium catalyst (Ru/TiO) by simply introducing 6 bar N under batch conditions at 160 °C and 1 bar hydrogen. Detailed investigations indicate that N can be adsorbed and activated on the metallic ruthenium surface to form hydrogenated nitrogen species, which offer protic hydrogen to lower the activation energy of direct carbon–oxygen bond scission and the hydrogenation of hydroxy groups. Thus, by employing different ruthenium catalysts, including Ru/TiO, Ru/AlO, Ru/ZrO and Ru/C, we demonstrate that N promotion of hydrodeoxygenation can be regarded as a general strategy.

SCI ; EI

英语

其他

Youth Innovation Promotion Association of the Chinese Academy of Sciences[21590792] ; National Natural Science Foundation of China[21878008] ; Fundamental Research Funds for the Central Universities[21902182]

Chemistry

Chemistry, Physical

WOS:000502586500008

Nature Research

20194607667003

Activation energy ; Catalysis ; Hydrogenation ; Inert gases ; Nitrogen ; Ruthenium ; Titanium oxides

Precious Metals:547.1 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2

2-s2.0-85074669225

Scopus

1.Chemistry Research Laboratory,Department of Chemistry,University of Oxford,Oxford,United Kingdom
2.The Wolfson Catalysis Centre,Department of Chemistry,University of Oxford,Oxford,United Kingdom
3.Department of Chemistry,Tsinghua University,Beijing Shi,China
4.Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education,Tsinghua University,Beijing,China
5.Beijing National Laboratory for Molecular Engineering,College of Chemistry and Molecular Engineering and College of Engineering,BIC-ESAT,Peking University,Beijing,China
6.State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing,China
7.Beijing Synchrotron Radiation Facility,Institute of High Energy Physics,Chinese Academy of Sciences,Beijing,China
8.National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei,China
9.Department of Materials,University of Oxford,Oxford,United Kingdom
10.Electron Physical Sciences Imaging Centre (ePSIC),Diamond Light Source,Oxford,United Kingdom
11.Department of Chemistry,City University of Hong Kong,Yeung Kin Man Academic Building,Hong Kong,China
12.Product & Technology Development Center,SCG Packaging Public Company Limited,ThaPha BanPong Ratchaburi,BanPong,Thailand
13.Department of Chemistry,Southern University of Science and Technology,Shenzhen,China

Duan，Haohong,Liu，Jin Cheng,Xu，Ming,et al. Molecular nitrogen promotes catalytic hydrodeoxygenation[J]. Nature Catalysis,2019,2(12):1078-1087.

Duan，Haohong.,Liu，Jin Cheng.,Xu，Ming.,Zhao，Yufei.,Ma，Xue Lu.,...&O’Hare，Dermot.(2019).Molecular nitrogen promotes catalytic hydrodeoxygenation.Nature Catalysis,2(12),1078-1087.

Duan，Haohong,et al."Molecular nitrogen promotes catalytic hydrodeoxygenation".Nature Catalysis 2.12(2019):1078-1087.