Application of thiolate self-assembled monolayers in selective alcohol oxidation for suppression of Pd catalyst deactivation

Hao, Pengxiao; Pylypenko, Svitlana; Schwartz, Daniel K.; Medlin, J. Will

doi:10.1016/j.jcat.2016.08.023

Application of thiolate self-assembled monolayers in selective alcohol oxidation for suppression of Pd catalyst deactivation

Journal Article · Mon Sep 19 00:00:00 EDT 2016 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2016.08.023· OSTI ID:1533926

Hao, Pengxiao ^[1]; Pylypenko, Svitlana ^[2]; Schwartz, Daniel K. ^[3]; Medlin, J. Will ^[3]

University of Colorado, Boulder, CO (United States); DOE/OSTI
Colorado School of Mines, Golden, CO (United States)
University of Colorado, Boulder, CO (United States)

Rapid deactivation often reduces the effectiveness of Pt-group catalysts in the low-temperature aerobic oxidation of alcohols. We report the use of thiolate self-assembled monolayers (SAMs) as activity promoters in the liquid-phase oxidation of trans-2-hexen-1-ol (HOL) under low air pressure; the oxidation rate was significantly improved, particularly at high conversion, in contrast to the frequently observed activity decrease induced by SAM modification in hydrogenation reactions. Reaction studies indicated that in the regime of low air pressure, catalyst deactivation was mainly caused by the carbonaceous poisons generated from the reaction product 2-hexenal (HAL). Infrared spectroscopy revealed that HAL produced surface residues on Pd that poisoned the catalyst, hypothetically through decarbonylation and dimerization. This poisoning can be suppressed by the SAM modifiers, in a manner that was controllable by varying thiolate surface coverage through use of either 1-adamantanethiol (AT) or 1-octadecanethiol (C18) SAMs.

View Accepted Manuscript (DOE)

Research Organization:: University of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0005239

OSTI ID:: 1533926

Alternate ID(s):: OSTI ID: 1411079

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 344; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
alcohol oxidation
alkanethiol
deactivation
heterogeneous catalysis
palladium
self-assembled monolayers
surface modification

Application of thiolate self-assembled monolayers in selective alcohol oxidation for suppression of Pd catalyst deactivation

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