Sarkar, C;
Paul, R;
Shit, SC;
Quang, TT;
Koley, P;
Rao, BS;
Beale, AM;
... Mondal, J; + view all
(2021)
Navigating Copper-Atom-Pair Structural Effect inside a Porous Organic Polymer Cavity for Selective Hydrogenation of Biomass-Derived 5-Hydroxymethylfurfural.
ACS Sustainable Chemistry and Engineering
, 9
(5)
pp. 2136-2151.
10.1021/acssuschemeng.0c07594.
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Abstract
In recent times, selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (5-HMF) to produce the novel difuranic polyol scaffold 2,5-dihydroxymethylfuran (DHMF) has attracted the interest of the many researchers due to its peculiar symmetrical structure and its widespread application as a monomer for the preparation of cross-linked polyesters and polyurethane. Copper-based catalysts have been explored for selective catalytic hydrogenation; however, hurdles are still associated with the strongly reducing H2 atmosphere and oxidizing C–O bond that make the Cu0 and Cux+ surface active species unstable, limiting the rational design of highly efficient integrated catalyst systems. To address this, herein, we built catalytic systems for 5-HMF hydrogenation with stable and balanced Cu0 and Cux+ active surface species inside the nanocage of a catechol-based porous organic polymer (POP) endowed with large surface areas, impressive stabilities, and spatial restriction inhibiting nanoparticle aggregation. Batch reactor screening identified that a superior catalytic performance (DHMF selectivity of 98%) has been achieved with our newly designed Cu@C-POP at 150 °C temperature and 20 bar H2 pressure, which was also higher than that of other reported copper catalysts. Comprehensive characterization understanding with H2-TPR and X-ray photoelectron spectroscopy (XPS) study revealed that substantially boosted activity is induced by the presence of the bulk CuOx phase and atomically dispersed Cu species incorporating isolated Cu ions, which are further confirmed through the positive binding energy shift of Cu 2p3/2 XPS spectra (∼0.4 eV). The Cu environment in our catalytic systems comprises a predominantly square planar geometry (probably Jahn–Teller distorted OH), which we gleaned from the extended X-ray absorption for fine structure (EXAFS) analysis featuring two adjacent copper atoms with the valence state in between of 0 and +2, as validated by XANES absorption edge positions. EXAFS studies further revealed a lowering of the Cu coordination number for the most active Cu@C-POP-B catalyst, suggesting the presence of metal vacancies. Density functional theory calculations showed that the presence of Cu metal vacancies stabilized the reaction intermediates formed during 5-HMF hydrogenation and decreased the hydrogenation barriers, resulting in an enhanced catalytic activity of the Cu@C-POP-B catalyst.
| Type: | Article |
|---|---|
| Title: | Navigating Copper-Atom-Pair Structural Effect inside a Porous Organic Polymer Cavity for Selective Hydrogenation of Biomass-Derived 5-Hydroxymethylfurfural |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acssuschemeng.0c07594 |
| Publisher version: | https://doi.org/10.1021/acssuschemeng.0c07594 |
| 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: | Porous organic polymer (POP) biomass 5-hydroxymethylfurfural (HMF) Cu-cooperative effect Cu0−Cux+ dual atom pair species |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10124111 |
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