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Dual-site-mediated hydrogenation catalysis on Pd/NiO: Selective biomass transformation and maintenance of catalytic activity at low Pd loading

Dual-site-mediated hydrogenation catalysis on Pd/NiO: Selective biomass transformation and maintenance of catalytic activity at low Pd loading
Dual-site-mediated hydrogenation catalysis on Pd/NiO: Selective biomass transformation and maintenance of catalytic activity at low Pd loading
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 functionalized molecules to specific target chemicals and they need to be 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 favors 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. On the basis of this observation we hypothesized 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 comparable activities, whereas there was a 10-fold reduction in performance for 0.1 wt % Pd/TiO2. When TiO2 is used 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 bioderived feedstocks, suggesting alternative ways for promoting selective transformations and reducing the reliance on precious metals.
NiO, Pd, furfural hydrogenation, heterogeneous catalysis, hydrogen spillover
2155-5435
5483-5492
Campisi, Sebastiano
b4462871-7c4b-46cb-be36-ca409248ef3d
Chan-Thaw, Carine E.
5482e5d2-1252-4643-8e40-4576c27aaf61
Chinchilla, Lidia E.
8eb5786f-38f4-4dc8-85d1-a4f8f536c64e
Chutia, Arunabhiram
fe207bfe-0a7e-4369-8e62-bfa575399f83
Botton, Gianluigi A.
2827985f-b9cf-4b02-b4af-53092730cb03
Mohammed, Khaled M. H.
1c3c5641-4d0a-4c4d-bb26-fe733b8dbf63
Dimitratos, Nikolaos
a4385576-4a05-478b-8389-460bfb43412b
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Villa, Alberto
d1f6646b-f0d4-420c-8a52-c09663f46e5f
Campisi, Sebastiano
b4462871-7c4b-46cb-be36-ca409248ef3d
Chan-Thaw, Carine E.
5482e5d2-1252-4643-8e40-4576c27aaf61
Chinchilla, Lidia E.
8eb5786f-38f4-4dc8-85d1-a4f8f536c64e
Chutia, Arunabhiram
fe207bfe-0a7e-4369-8e62-bfa575399f83
Botton, Gianluigi A.
2827985f-b9cf-4b02-b4af-53092730cb03
Mohammed, Khaled M. H.
1c3c5641-4d0a-4c4d-bb26-fe733b8dbf63
Dimitratos, Nikolaos
a4385576-4a05-478b-8389-460bfb43412b
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Villa, Alberto
d1f6646b-f0d4-420c-8a52-c09663f46e5f

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 maintenance of catalytic activity at low Pd loading. ACS Catalysis, 10 (10), 5483-5492. (doi:10.1021/acscatal.0c00414).

Record type: Article

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 functionalized molecules to specific target chemicals and they need to be 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 favors 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. On the basis of this observation we hypothesized 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 comparable activities, whereas there was a 10-fold reduction in performance for 0.1 wt % Pd/TiO2. When TiO2 is used 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 bioderived feedstocks, suggesting alternative ways for promoting selective transformations and reducing the reliance on precious metals.

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Accepted/In Press date: 10 April 2020
e-pub ahead of print date: 10 April 2020
Published date: 15 May 2020
Keywords: NiO, Pd, furfural hydrogenation, heterogeneous catalysis, hydrogen spillover

Identifiers

Local EPrints ID: 440926
URI: http://eprints.soton.ac.uk/id/eprint/440926
ISSN: 2155-5435
PURE UUID: aa633fbd-ff24-403b-ac64-6d6843c35b89
ORCID for Khaled M. H. Mohammed: ORCID iD orcid.org/0000-0002-9538-0936
ORCID for Peter P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

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Date deposited: 22 May 2020 16:40
Last modified: 28 Apr 2022 04:54

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Contributors

Author: Sebastiano Campisi
Author: Carine E. Chan-Thaw
Author: Lidia E. Chinchilla
Author: Arunabhiram Chutia
Author: Gianluigi A. Botton
Author: Nikolaos Dimitratos
Author: Peter P. Wells ORCID iD
Author: Alberto Villa

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