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

Martin Joe Taylor, Li Jiang, Joachim Reichert, Anthoula C. Papageorgiou, Simon K. Beaumont, Karen Wilson, Adam F. Lee, Johannes V. Barth, Georgios Kyriakou

Research output: Contribution to journalArticlepeer-review

Abstract

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.
Original languageEnglish
Pages (from-to)8490–8497
JournalJournal of Physical Chemistry: Part C
Volume121
Issue number15
Early online date28 Mar 2017
DOIs
Publication statusPublished - 20 Apr 2017

Bibliographical note

© 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.

Fingerprint Dive into the research topics of 'Catalytic hydrogenation and hydrodeoxygenation of furfural over Pt(111); a model system for the rational design and operation of practical biomass conversion catalysts'. Together they form a unique fingerprint.

Cite this