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Title: Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst

Abstract

Electrochemical and chemical studies reveal that the amido complex (PNHxP)Fe(CO)(H)(X) (FeN 1, x = 0, X = 0; Fe(H)(NH) 2, x = 1, X = H; PNHP = bis[2-(diisopropylphosphino)ethyl]amine) is active for the electrocatalytic oxidation of isopropanol. At room temperature, the amido FeN 1 dehydrogenates isopropanol to form acetone. The resulting amino hydride complex Fe(H)(NH) 2 is subsequently oxidized by one electron at a low potential (–0.74 V versus ferrocene/ferrocenium, Fco/+) in tetrahydrofuran. In the presence of strong base (phosphazene base P2-Et, Et-N = P2(dma)5, P2), this oxidation process becomes a two-electron, two-proton process that regenerates FeN 1. FeN 1 is active for the electrooxidation of isopropanol in the presence of strong base (i.e., P2) with an onset potential near –1 V versus Fco/+. By cyclic voltammetry, fast turnover frequencies of 1.7 s–1 for isopropanol oxidation are achieved with FeN 1. Lastly, controlled potential electrolysis studies confirm that the product of isopropanol electrooxidation is acetone, generated with high Faradaic efficiency (~100%).

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Stanford Univ., CA (United States)
  2. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1594172
Alternate Identifier(s):
OSTI ID: 1605284
Grant/Contract Number:  
SC0018168; CHE-1213403; AC02-76SF00515; 2017-4-Waymouth
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 59; Journal Issue: 2; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Alcohols; Anions; Catalysts; Tetrahydrofurans; Oxidation

Citation Formats

McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, and Waymouth, Robert M.. Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.inorgchem.9b03230.
McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, & Waymouth, Robert M.. Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst. United States. https://doi.org/10.1021/acs.inorgchem.9b03230
McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, and Waymouth, Robert M.. Mon . "Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst". United States. https://doi.org/10.1021/acs.inorgchem.9b03230. https://www.osti.gov/servlets/purl/1594172.
@article{osti_1594172,
title = {Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst},
author = {McLoughlin, Elizabeth A. and Matson, Benjamin D. and Sarangi, Ritimukta and Waymouth, Robert M.},
abstractNote = {Electrochemical and chemical studies reveal that the amido complex (PNHxP)Fe(CO)(H)(X) (FeN 1, x = 0, X = 0; Fe(H)(NH) 2, x = 1, X = H; PNHP = bis[2-(diisopropylphosphino)ethyl]amine) is active for the electrocatalytic oxidation of isopropanol. At room temperature, the amido FeN 1 dehydrogenates isopropanol to form acetone. The resulting amino hydride complex Fe(H)(NH) 2 is subsequently oxidized by one electron at a low potential (–0.74 V versus ferrocene/ferrocenium, Fco/+) in tetrahydrofuran. In the presence of strong base (phosphazene base P2-Et, Et-N = P2(dma)5, P2), this oxidation process becomes a two-electron, two-proton process that regenerates FeN 1. FeN 1 is active for the electrooxidation of isopropanol in the presence of strong base (i.e., P2) with an onset potential near –1 V versus Fco/+. By cyclic voltammetry, fast turnover frequencies of 1.7 s–1 for isopropanol oxidation are achieved with FeN 1. Lastly, controlled potential electrolysis studies confirm that the product of isopropanol electrooxidation is acetone, generated with high Faradaic efficiency (~100%).},
doi = {10.1021/acs.inorgchem.9b03230},
journal = {Inorganic Chemistry},
number = 2,
volume = 59,
place = {United States},
year = {2019},
month = {12}
}

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