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  Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction

Neumann, C. N., Payn, M. T., Rozeveld, S. J., Wu, Z., Zhang, G., Comito, R. J., et al. (2021). Structural Evolution of MOF-Derived RuCo, A General Catalyst for the Guerbet Reaction. ACS Applied Materials and Interfaces, 13(44), 52113-52124. doi:10.1021/acsami.1c09873.

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Neumann, Constanze N.1, Author           
Payn, Michael T.1, Author
Rozeveld, Steven J.2, Author
Wu, Zhenwei3, Author
Zhang, Guanghui3, Author
Comito, Robert J.1, Author
Miller, Jeffrey T.3, Author
Dincă, Mircea1, Author
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States, ou_persistent22              
2Core R&D, The Dow Chemical Company, Midland, Michigan 48674, United States, ou_persistent22              
3Davidson School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, Indiana 47907, United States, ou_persistent22              


Free keywords: Guerbet reaction; RuCo; 2-ethylhexanol; MOF-derived catalyst; alcohol upgrading
 Abstract: Guerbet alcohols, a class of β-branched terminal alcohols, find widespread application because of their low melting points and excellent fluidity. Because of the limitations in the activity and selectivity of existing Guerbet catalysts, Guerbet alcohols are not currently produced via the Guerbet reaction but via hydroformylation of oil-derived alkenes followed by aldol condensation. In pursuit of a one-step synthesis of Guerbet alcohols from simple linear alcohol precursors, we show that MOF-derived RuCo alloys achieve over a million turnovers in the Guerbet reaction of 1-propanol, 1-butanol, and 1-pentanol. The active catalyst is formed in situ from ruthenium-impregnated metal–organic framework MFU-1. XPS and XAS studies indicate that the precatalyst is composed of Ru precursor trapped inside the MOF pores with no change in the oxidation state or coordination environment of Ru upon MOF incorporation. The significantly higher reactivity of Ru-impregnated MOF versus a physical mixture of Ru precursor and MOF suggests that the MOF plays an important role in templating the formation of the active catalyst and/or its stabilization. XPS reveals partial reduction of both ruthenium and MOF-derived cobalt under the Guerbet reaction conditions, and TEM/EDX imaging shows that Ru is decorated on the edges of dense nanoparticles, as well as thin nanoplates of CoOx. The use of ethanol rather than higher alcohols as a substrate results in lower turnover frequencies, and RuCo recovered from ethanol upgrading lacks nanostructures with plate-like morphology and does not exhibit Ru-enrichment on the surface and edge sites. Notably, 1H and 31P NMR studies show that through use of K3PO4 as a base promoter in the RuCo-catalyzed alcohol upgrading, the formation of carboxylate salts, a common side product in the Guerbet reaction, was effectively eliminated.


Language(s): eng - English
 Dates: 2021-05-282021-08-052021-08-182021-11-10
 Publication Status: Issued
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acsami.1c09873
 Degree: -



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Title: ACS Applied Materials and Interfaces
  Abbreviation : ACS Appl. Mater. Interfaces
Source Genre: Journal
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 13 (44) Sequence Number: - Start / End Page: 52113 - 52124 Identifier: ISSN: 1944-8244
CoNE: https://pure.mpg.de/cone/journals/resource/1944-8244