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Dual-site mediated hydrogenation catalysis on Pd/NiO: selective biomass transformation and maintaining catalytic activity at low Pd loading

DOI: 10.1021/acscatal.0c00414 DOI Help

Authors: Sebastiano Campisi (Università degli Studi di Milano) , Carine E. Chan-thaw (Università degli Studi di Milano) , Lidia E. Chinchilla (McMaster University) , Arunabhiram Chutia (University of Lincoln) , Gianluigi A. Botton (McMaster University) , Khaled M. H. Mohammed (University of Southampton; Sohag University) , Nikolaos Dimitratos (University of Bologna) , Peter Wells (University of Southampton; UK Catalysis Hub, Research Complex at Harwell; Diamond Light Source) , Alberto Villa (Università degli Studi di Milano)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acs Catalysis

State: Published (Approved)
Published: April 2020
Diamond Proposal Number(s): 10306

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.

Journal Keywords: Furfural hydrogenation; Pd; NiO; heterogeneous catalysis; hydrogen spillover

Subject Areas: Chemistry, Biology and Bio-materials

Instruments: B18-Core EXAFS

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