Catalytic Upgrading of Renewable Feedstock (Final Technical Report)

Technical Report · 01 May 2024

DOI:https://doi.org/10.2172/2345186· OSTI ID:2345186

Szymczak, Nathaniel ^[1]; Stephenson, Corey ^[2]

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1. Univ. of Michigan, Ann Arbor, MI (United States); University of Michigan Office of Research and Sponsored Programs
2. Univ. of Michigan, Ann Arbor, MI (United States)

The goal of this DOE-funded project was to investigate the fundamental science related to the development of homogeneous (de)hydrogenation catalysts in order to enable energy-relevant transformations of bio-relevant chemical feedstocks including ethanol. The primary focus was to improve the activity of ethanol upgrading catalysts, specifically informed through mechanistic studies, in order to enable rational design optimization strategies. Following in depth mechanistic studies, targeted reaction optimization approaches included ligand redesign to improve catalyst stability, developing new carbon-carbon bond forming reactions using ethanol as a precursor, and examining photochemically-mediated reactions, ultimately to integrate within other reactor designs such as continuous flow reactors. The high modularity of the catalyst components (ligands) has enabled the preparation and analyses of multiple catalyst precursors. These studies uncovered an unexpectedly beneficial substitution pattern of the ligand structure that led to the development of new catalysts that are the best in class for upgrading ethanol to butanol with a turnover number of 155,890 and a turnover frequency of 12,690 h^–1. In addition to upgrading ethanol to butanol, cascade reaction sequences were developed to form new C-C bonds using ethanol as a bio-relevant feedstock, providing access to platform chemicals from renewable sources. As part of the reaction discovery process, new mechanistic details were uncovered that provided insights into: a) catalyst speciation, b) decomposition pathways, c) carbon monoxide releasing pathways, and d) carbon-carbon and carbon hydrogen bond breaking pathways. Most of these outcomes were previously not known; however, they provide important directions for new catalyst design strategies. Finally, use of high throughput and in situ photochemical reaction analyses enabled detailed studies into changes to the catalyst structure upon irradiation. Irradiation was found to improve hydrogen transfer catalysis, by promoting a ligand dissociation event.

• Research Organization: Univ. of Michigan, Ann Arbor, MI (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• DOE Contract Number: SC0020191
• OSTI ID: 2345186
• Report Number(s): DOE-UMICH--20191-1
• Country of Publication: United States
• Language: English

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