English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Recycling of CO2 by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper-Oxide Promotion Effects in Supported Catalysts

MPS-Authors
/persons/resource/persons228159

Kim,  Jonglack
Research Group Prieto, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons21955

Pfänder,  Norbert
Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons141739

Prieto,  Gonzalo
Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Research Group Prieto, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Resource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Kim, J., Pfänder, N., & Prieto, G. (2020). Recycling of CO2 by Hydrogenation of Carbonate Derivatives to Methanol: Tuning Copper-Oxide Promotion Effects in Supported Catalysts. ChemSusChem, 13(8), 2043-2052. doi:10.1002/cssc.202000166.


Cite as: http://hdl.handle.net/21.11116/0000-0007-B3BE-9
Abstract
The selective hydrogenation of organic carbonates to methanol is a relevant transformation to realize flexible processes for the recycling of waste CO2 with renewable H-2 mediated by condensed carbon dioxide surrogates. Oxide-supported copper nanoparticles 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 nanoparticles, was systematically assessed. For the hydrogenation of propylene carbonate, as a model cyclic carbonate, the conversion rate, the apparent activation energy, and the selectivity to methanol correlate with the Lewis acidity of the coordinatively unsaturated cationic sites exposed on the oxide support. Lewis sites of markedly low and high electron-withdrawing character promote unselective decarbonylation and decarboxylation reaction pathways, respectively. Supports exposing Lewis sites of intermediate acidity maximize the selectivity to methanol while inhibiting acid-catalyzed secondary reactions of the propanediol product, and thus enable its recovery in cyclic processes of CO2 hydrogenation mediated by condensed carbonate derivatives. These findings help rationalize metal-support promotion effects that determine the performance of supported metal nanoparticles in this and other selective hydrogenation reactions of significance in the context of sustainable chemistry.