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

Cherkasov, N; Expósito, AJ; Aw, MS; Fernández-García, J; Huband, S; Sloan, J; Paniwnyk, L; (2019) Active site isolation in bismuth-poisoned Pd/SiO₂ catalysts for selective hydrogenation of furfural. Applied Catalysis A: General , 570 pp. 183-191. 10.1016/j.apcata.2018.11.016. Green open access

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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.

Type: Article
Title: Active site isolation in bismuth-poisoned Pd/SiO₂ catalysts for selective hydrogenation of furfural
Open access status: An open access version is available from UCL Discovery
DOI: 10.1016/j.apcata.2018.11.016
Publisher version: https://doi.org/10.1016/j.apcata.2018.11.016
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher's terms and conditions.
Keywords: Hydrogenation, Active site, Palladium, BismuthPoison
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering
URI: https://discovery.ucl.ac.uk/id/eprint/10113180
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