Ambient-pressure synthesis of ethylene glycol catalyzed by C ₆₀ -buffered Cu/SiO ₂

Abstract

Bulk chemicals such as ethylene glycol (EG) can be industrially synthesized from either ethylene or syngas, but the latter undergoes a bottleneck reaction and requires high hydrogen pressures. We show that fullerene (exemplified by C 60 ) can act as an electron buffer for a copper-silica catalyst (Cu/SiO 2 ). Hydrogenation of dimethyl oxalate over a C 60 -Cu/SiO 2 catalyst at ambient pressure and temperatures of 180° to 190°C had an EG yield of up to 98 ± 1%. In a kilogram-scale reaction, no deactivation of the catalyst was seen after 1000 hours. This mild route for the final step toward EG can be combined with the already-industrialized ambient reaction from syngas to the intermediate of dimethyl oxalate.

Sorbitol-derived carbon overlayers encapsulated Cu nanoparticles on SiO2: Stable and efficient for the continuous hydrogenation of ethylene carbonate

“…The hydrogenation of EC starts with the nucleophilic attack of adsorbed H atoms to the electron-deficient carbon of the ester group. Furthermore, the promotion of H 2 activation on the Cu surface by graphitized carbon can facilitate the activation of EC ( Zheng et al., 2022 ), which is beneficial to the selectivity toward MeOH.…”

“…The stabilization of Cu nanoparticles by graphitized carbon overlayers, in this case, is very similar to the case of the C 60 -buffered Cu/SiO 2 catalyst. With the d-π interaction between Cu and C 60 , the C 60 -buffered Cu/SiO 2 catalyst had a stable Cu 0 /Cu + ratio to realize the hydrogenation of diethyl oxalate at ambient pressure with higher selectivity to ethyl glycol and longer lifetime ( Zheng et al., 2022 ).…”

Implementation of the β-hydroxyaspartate cycle increases growth performance of Pseudomonas putida on the PET monomer ethylene glycol

“…Notably, EG is not only a key building block of PET, as well as other polyester resins and fibers (Yue et al, 2012), but also finds applications as antifreeze agent or solvent worldwide (Dobson, 2000). Furthermore, EG can be electrochemically generated from syngas in a two-step process, thus gaining increasing attention as a key component for a carbon neutral bio-economy (Zheng et al, 2022). Therefore, efforts to develop microbial strains with improved conversion capacities for EG is not only important for microbial PET upcycling, but also in the broader context of establishing circular economic routes for the biotechnological use of this abundant chemical.…”

Palladium-catalyzed decarboxylative [2 + 3] cyclocarbonylation reactions of [60]fullerene: selective synthesis of [60]fullerene-fused 3-vinylcyclopentan-4-ones and cyclopentane-4-carbaldehydes

“…The unique structures and electronic properties of fullerenes endow them with wide applications in materials science, 1 photovoltaic cells, 2 biomedicine, 3 supramolecular chemistry, 4 and catalysis. 5 Therefore, the preparation and functionalization of fullerenes have been an important scientific research area. 6,7 Among various prepared functionalized fullerenes, [60]fullerene-fused carbonyl derivatives are a class of valuable nanostructures and have been demonstrated to serve as acceptor materials for the construction of [60]fullerene-based donor–acceptor dyad systems, 8 as electron transport materials for perovskite solar cells, 9 and as intermediates for the preparation of other functionalized fullerenes.…”