Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

Journal Article · Tue Dec 15 00:00:00 EST 2015 · Materials Research Bulletin

DOI:https://doi.org/10.1016/J.MATERRESBULL.2015.07.027· OSTI ID:22584231

Kamiguchi, Satoshi ^[1]; Okumura, Kazu ^[2]; Nagashima, Sayoko; Chihara, Teiji ^[3]

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1. Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan)
2. School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan)
3. Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

• OSTI ID: 22584231
• Journal Information: Materials Research Bulletin, Vol. 72; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0025-5408
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALCOHOLS
ALDEHYDES
BENZOIC ACID
CATALYSIS
COPPER COMPOUNDS
DEHYDROGENATION
HYDROGEN
INORGANIC COMPOUNDS
KETONES
LIGANDS
MOLYBDENUM
MOLYBDENUM SULFIDES
PYRIDINE
SUPERCONDUCTORS
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0400-1000 K