Campisi, Sebastiano, Chan-Thaw, Carine E., Chinchilla, Lidia E. , Chutia, Arunabhiram, Botton, Gianluigi A., Mohammed, Khaled. M. H., Dimitratos, Nikolaos, Wells, Peter P. and Villa, Alberto (2020) Dual-Site Mediated Hydrogenation Catalysis on Pd/NiO: Selective Biomass Transformation and Maintaining Catalytic Activity at Low Pd Loading. ACS Catalysis . ISSN 2155-5435
Full content URL: https://doi.org/10.1021/acscatal.0c00414
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2020_ACSCat_JustAccepted.pdf - Whole Document Available under License Creative Commons Attribution-NonCommercial 4.0 International. 605kB |
Item Type: | Article |
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Item Status: | Live Archive |
Abstract
Creating a new chemical ecosystem based on platform chemicals derived from waste biomass has significant
challenges; catalysts need to be able to convert these highly functionalised molecules to specific target chemicals,
economical – not relying on large quantities of precious metals - and maintain activity over many cycles. Herein, we
demonstrate how Pd/NiO is able to direct the selectivity of furfural hydrogenation and maintain performance at low Pd
loading by a unique dual-site mechanism. Sol-immobilization was used to prepare 1 wt% Pd nanoparticles supported on
NiO and TiO2, with the Pd/NiO catalyst showing enhanced activity with a significantly different selectivity profile; Pd/NiO
favours tetrahydrofurfuryl alcohol (72%), whereas Pd/TiO2 produces furfuryl alcohol as the major product (68%). Density
functional theory studies evidenced significant differences on the adsorption of furfural on both NiO and Pd surfaces. Based on this observation we hypothesised that the role of Pd was to dissociate hydrogen, with the NiO surface adsorbing furfural. This dual-site hydrogenation mechanism was supported by comparing the performance of 0.1 wt% Pd/NiO and 0.1 wt% Pd/TiO2. In this study, the 0.1 and 1 wt% Pd/NiO catalysts had a comparable activity, whereas there was a 10-fold reduction in performance for 0.1 wt% Pd/TiO2. When using TiO2 as the support the Pd nanoparticles are responsible for both hydrogen dissociation and furfural adsorption, and the activity is strongly correlated with the effective metal surface area. This work has significant implications for the upgrading of bio-derived feedstocks, suggesting alternative ways for promoting selective transformations and reducing the reliance on precious metals.
Keywords: | DFT, biomass, Pd nanoparticles, Pd/NiO |
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Subjects: | F Physical Sciences > F100 Chemistry |
Divisions: | College of Science > School of Chemistry |
ID Code: | 40620 |
Deposited On: | 16 Apr 2020 09:38 |
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