Catalytic hydrogenation and hydrodeoxygenation of furfural over Pt(111); a model system for the rational design and operation of practical biomass conversion catalysts


Furfural is a key bio-derived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature programmed reaction spectrometry (TPRS) 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 co-adsorbed hydrogen. Pre-adsorbed 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 to 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.

Publication DOI:
Dataset DOI:
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
College of Engineering & Physical Sciences
Additional Information: © 2017 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Funding: Aston University (PhD studentship); EPSRC (EP/K014676/1; EP/K014749/1; and EP/M005186/2); China Scholarship Council (CSC); European Research Council Advanced Grant MolArt (No. 247299); Durham and the Leverhulme Trust's Early Career Fellowship scheme; University Addison Wheeler scheme; and Royal Society.
Publication ISSN: 1932-7455
Last Modified: 01 Apr 2024 07:18
Date Deposited: 04 Apr 2017 08:40
PURE Output Type: Article
Published Date: 2017-04-20
Published Online Date: 2017-03-28
Accepted Date: 2017-03-28
Authors: Taylor, Martin Joe
Jiang, Li
Reichert, Joachim
Papageorgiou, Anthoula C.
Beaumont, Simon K.
Wilson, Karen (ORCID Profile 0000-0003-4873-708X)
Lee, Adam F.
Barth, Johannes V.
Kyriakou, Georgios



Version: Published Version

License: Creative Commons Attribution

| Preview


Version: Accepted Version

Access Restriction: Restricted to Repository staff only

Export / Share Citation


Additional statistics for this record