Active site isolation in bismuth-poisoned Pd/SiO2 catalysts for selective hydrogenation of furfural

Nikolay Cherkasov (Corresponding author), Antonio José Expósito, Moom Sinn Aw, Javier Fernández-García, Steven Huband, Jeremy Sloan, Larysa Paniwnyk, Evgeny V. Rebrov (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

31 Citations (Scopus)

Abstract

Active site isolation in furfural (FA) hydrogenation was studied by poisoning a Pd catalyst with bismuth. A solution of FA in water was hydrogenated over a 5 wt% Pd/SiO2 catalyst in a batch reactor at various reaction temperatures and pressures. Furfuryl alcohol (FAL) was an intermediate product which was further hydrogenated into tetrahydrofurfuryl alcohol (TFAL) or cyclopentanone (CPA) and cyclopentanol (CPOL). While application of hydrogen pressure above 30 bar had little effect on the hydrogenation kinetics, a reaction temperature affected product distribution and the main product changed from TFAL (at 50 °C) to FAL (100 and 150 °C). Poisoning the catalyst with Bi decreased the number of available active sites but had little effect on the turn-over frequencies, most likely because of the absence of electronic effects of Bi on Pd nanoparticles. The main reaction product over the Bi-poisoned catalyst was FAL with no FA oligomerisation products. At a reaction temperature of 150 °C, CPA was formed with a 57% yield. Considering that Bi preferentially poisons step sites of Pd, the comparison of the product distribution between the Pd and Pd-Bi catalyst as well as the literature data for the alloy Pd-Cu catalysts indicates that the active site isolation observed in the Pd-Bi catalysts is responsible for the increasing FAL and CPA selectivities and elimination of oligomer by-products.

Original languageEnglish
Pages (from-to)183-191
Number of pages9
JournalApplied Catalysis. A, General
Volume570
DOIs
Publication statusPublished - 25 Jan 2019

Bibliographical note

Publisher Copyright:
© 2018 Elsevier B.V.

Funding

We acknowledge the support of the European Research Council Proof of Concept grant (project Micarf 693739). JS is indebted to support from EPSRC grants EP/M010643/1 and EP/R019428/1. The authors are grateful to Jonathan Strong for the ICP and TEM analyses and to Dr Aruni Fonseka for assistance with the elemental mapping on the ARM200F instrument. We acknowledge the support of the European Research Council Proof of Concept grant (project Micarf 693739). JS is indebted to support from EPSRC grants EP/M010643/1 and EP/R019428/1 . The authors are grateful to Jonathan Strong for the ICP and TEM analyses and to Dr Aruni Fonseka for assistance with the elemental mapping on the ARM200F instrument.

FundersFunder number
H2020 European Research Council693739
Engineering and Physical Sciences Research CouncilEP/R019428/1, EP/M010643/1
H2020 European Research Council

    Keywords

    • Active site
    • Bismuth
    • Hydrogenation
    • Palladium
    • Poison

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