Catalytic Mechanism of Liquid-Metal Indium for Direct Dehydrogenative Conversion of Methane to Higher Hydrocarbons.

Autor: Nishikawa Y; Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo 152-8552, Japan., Ohtsuka Y; Institute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan., Ogihara H; Graduate School of Science and Engineering, Saitama University, Saitama 338-8570, Japan., Rattanawan R; Institute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan., Gao M; Institute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan., Nakayama A; Graduate School of Engineering, Department of Chemical System Engineering, University of Tokyo, Tokyo 113-8656, Japan., Hasegawa JY; Institute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan., Yamanaka I; Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo 152-8552, Japan.
Jazyk: angličtina
Zdroj: ACS omega [ACS Omega] 2020 Oct 22; Vol. 5 (43), pp. 28158-28167. Date of Electronic Publication: 2020 Oct 22 (Print Publication: 2020).
DOI: 10.1021/acsomega.0c03827
Abstrakt: There is a great interest in direct conversion of methane to valuable chemicals. Recently, we reported that silica-supported liquid-metal indium catalysts (In/SiO 2 ) were effective for direct dehydrogenative conversion of methane to higher hydrocarbons. However, the catalytic mechanism of liquid-metal indium has not been clear. Here, we show the catalytic mechanism of the In/SiO 2 catalyst in terms of both experiments and calculations in detail. Kinetic studies clearly show that liquid-metal indium activates a C-H bond of methane and converts methane to ethane. The apparent activation energy of the In/SiO 2 catalyst is 170 kJ mol -1 , which is much lower than that of SiO 2 , 365 kJ mol -1 . Temperature-programmed reactions in CH 4 , C 2 H 6 , and C 2 H 4 and reactivity of C 2 H 6 for the In/SiO 2 catalyst indicate that indium selectively activates methane among hydrocarbons. In addition, density functional theory calculations and first-principles molecular dynamics calculations were performed to evaluate activation free energy for methane activation, its reverse reaction, CH 3 -CH 3 coupling via Langmuir-Hinshelwood (LH) and Eley-Rideal mechanisms, and other side reactions. A qualitative level of interpretation is as follows. CH 3 -In and H-In species form after the activation of methane. The CH 3 -In species wander on liquid-metal indium surfaces and couple each other with ethane via the LH mechanism. The solubility of H species into the bulk phase of In is important to enhance the coupling of CH 3 -In species to C 2 H 6 by decreasing the formation of CH 4 though the coupling of CH 3 -In species and H-In species. Results of isotope experiments by combinations of CD 4 , CH 4 , D 2 , and H 2 corresponded to the LH mechanism.
Competing Interests: The authors declare no competing financial interest.
(© 2020 American Chemical Society.)
Databáze: MEDLINE
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