Irreversible catalytic methylcyclohexane dehydrogenation by surface protonics at low temperatureElectronic supplementary information (ESI) available. See DOI: 10.1039/c9ra00407f

• Main Authors: Takise, Kent, Sato, Ayaka, Murakami, Kota, Ogo, Shuhei, Seo, Jeong Gil, Imagawa, Ken-ichi, Kado, Shigeru, Sekine, Yasushi
• Format: Article
• Language: English
• ISSN: 2046-2069
• DOI: 10.1039/c9ra00407f

Liquid organic hydrides are regarded as promising for use as hydrogen carriers via the methylcyclohexane (MCH)-toluene-hydrogen cycle. Because of the endothermic nature of MCH dehydrogenation, the reaction is usually conducted at temperatures higher than 623 K. In this work, low-temperature catalytic MCH dehydrogenation was demonstrated over 3 wt% Pt/CeO 2 catalyst by application of electric field across a fixed-bed flow reactor. Results show that a high conversion of MCH beyond thermodynamic equilibrium was achieved even at 423 K. Kinetic analyses exhibited a positive correlation of hydrogen to the reaction rates and an "inverse" kinetic isotope effect (KIE), suggesting that accelerated proton hopping with the H atoms of MCH promotes the reaction. Operando analyses and DFT calculation proved that the reverse reaction ( i.e. toluene hydrogenation) was suppressed by the facilitation of toluene desorption in the electric field. The electric field promoted MCH dehydrogenation by surface proton hopping, even at low temperatures with an irreversible pathway. Surface protonics by applying electric field promotes low temperature methylcyclohexane dehydrogenation for effective hydrogen production.