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Photocatalytic Selective Ring Hydrogenation of Phenol to Cyclohexanone over a Palladium‐Loaded Titanium(IV) Oxide under Hydrogen‐Free Conditions
Author(s) -
Kinoshita Atsufumi,
Nakanishi Kousuke,
Tanaka Atsuhiro,
Hashimoto Keiji,
Kominami Hiroshi
Publication year - 2019
Publication title -
chemphotochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.13
H-Index - 18
ISSN - 2367-0932
DOI - 10.1002/cptc.201900069
Subject(s) - cyclohexanone , chemistry , phenol , cyclohexanol , palladium , cyclohexane , inorganic chemistry , oxalic acid , benzene , catalysis , photochemistry , organic chemistry
Photocatalytic ring hydrogenation of phenol proceeded in an aqueous suspension of palladium‐loaded TiO 2 at room temperature in the presence of oxalic acid as a hole scavenger, and cyclohexanone was produced in a high yield (90 %) without the use of hydrogen gas. Cyclohexanone was formed via keto‐enol tautomerism of cyclohexenol. The effects of hole scavengers and solvents on the hydrogenation of phenol can be explained by the adsorption behaviour of phenol and hole scavengers in the solvents. Over a Pd‐TiO 2 photocatalyst, the apparent activation energy ( E a) in the ring hydrogenation of phenol and the E a value in the hydrogenation of cyclohexanone were estimated to be 25 kJ mol −1 and 36 kJ mol −1 , respectively, as calculated by using the Arrhenius equation. We concluded that the difference in the E a values is attributable to the selective production of cyclohexanone and the decreased production of cyclohexanol in the ring hydrogenation of phenol over a Pd‐TiO 2 photocatalyst.