Recycling of CO2 via hydrogenation of carbonate derivatives to methanol: tuning copper-oxide promotion effects in supported catalysts.
Journal: 2020/February - ChemSusChem
ISSN: 1864-564X
Abstract:
The hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO2 with renewable H2 mediated by condensed CO2 surrogates. Oxide-supported copper nanoparticles (NPs) are promising solid catalysts for this selective hydrogenation. However, essential for their optimization is to rationalize the prominent impact of the oxide support on performance. Herein, the role of Lewis acid centers, exposed on the oxide support at the periphery of the Cu NPs is systematically assessed. For the hydrogenation of propylene carbonate, as a model cyclic carbonate, the conversion rate, the apparent activation energy as well as the selectivity to methanol correlate with the Lewis acidity of the coordinatively unsaturared cationic sites (cus) exposed on the oxide carrier. Lewis sites of markedly low and high electron withdrawing character promote decarbonylation and decarboxylation unselective reaction pathways, respectively. Supports exposing Lewis sites of intermediate acidity maximize the selectivity to methanol while inhibiting secondary, acid-catalyzed reactions of the propanediol product, enabling its recovery in cyclic processes of CO2 hydrogenation mediated by condensed carbonate derivatives. These findings help rationalize metal-support promotion effects which determine the performance of supported metal NPs in this and other selective hydrogenations of significance in the context of sustainable chemistry.
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