Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

Liu, Yuan1,2,5; Liu, Jin-Cheng1,2; Li, Teng-Hao3; Duan, Zeng-Hui1,2; Zhang, Tian-Yu4; Yan, Ming3; Li, Wan-Lu1,2; Xiao, Hai1,2; Wang, Yang-Gang5; Chang, Chun-Ran3; Li, Jun1,2,5

2020-08-20

10.1002/anie.202003908

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe-1 (c) SiC2), followed by C-C coupling and hydrogen transfer to produce the main product (ethylene) via a key -CH-CH(2)intermediate. We find a quasi Mars-van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe-1 (c) SiO(2)and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.

computational simulations methane reaction mechanisms single-atom catalysis

SCI ; EI

英语

NI期刊 ; NI论文

通讯

National Natural Science Foundation of China[91645203][21603170][21590792] ; China Postdoctoral Science Foundation[2018T111034][2018M630139] ; Fundamental Research Funds for the Central Universities[xtr0218016][cxtd2017004] ; Rising Star Program in Science and Technology of Shaanxi Province[2020KJXX-079] ; Shaanxi Creative Talents Promotion Plan-Technological Innovation Team[2019TD-039] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000561037600001

WILEY-V C H VERLAG GMBH

20203409085539

Carbon ; Phase interfaces ; Silicon ; Surface reactions ; Catalysis ; Atoms ; Ethylene ; Gases ; Iron compounds ; Catalysts ; Iron ; Silica

Iron:545.1 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
2.Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
3.Xi An Jiao Tong Univ, Sch Chem Engn & Technol, Shaanxi Key Lab Energy Chem Proc Intensificat, Xian 710049, Peoples R China
4.Southern Illinois Univ, Dept Chem & Biochem, Carbondale, IL 62901 USA
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Liu, Yuan,Liu, Jin-Cheng,Li, Teng-Hao,et al. Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2020,59:18586-18590.

Liu, Yuan.,Liu, Jin-Cheng.,Li, Teng-Hao.,Duan, Zeng-Hui.,Zhang, Tian-Yu.,...&Li, Jun.(2020).Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,59,18586-18590.

Liu, Yuan,et al."Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59(2020):18586-18590.