Taylor, Martin J. and Jiang, Li and Reichert, Joachim and Papageorgiou, Anthoula C. and Beaumont, Simon K. and Wilson, Karen and Lee, Adam F. and Barth, Johannes V. and Kyriakou, Georgios (2017) 'Catalytic hydrogenation and hydrodeoxygenation of furfural over Pt(111) : a model system for the rational design and operation of practical biomass conversion catalysts.', Journal of physical chemistry C., 121 (15). pp. 8490-8497.
Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.
|Full text:||(AM) Accepted Manuscript|
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|Publisher Web site:||https://doi.org/10.1021/acs.jpcc.7b01744|
|Publisher statement:||This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.7b01744.|
|Date accepted:||28 March 2017|
|Date deposited:||02 June 2017|
|Date of first online publication:||28 March 2017|
|Date first made open access:||28 March 2018|
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