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Highly Selective Electrocatalytic Oxidation of Amines to Nitriles Assisted by Water Oxidation on Metal-Doped α-Ni(OH)₂

Sun, Yuxia and Shin, Hyeyoung and Wang, Fangyuan and Tian, Bailin and Chiang, Chen-Wei and Liu, Shengtang and Li, Xiaoshan and Wang, Yiqi and Tang, Lingyu and Goddard, William A., III and Ding, Mengning (2022) Highly Selective Electrocatalytic Oxidation of Amines to Nitriles Assisted by Water Oxidation on Metal-Doped α-Ni(OH)₂. Journal of the American Chemical Society . ISSN 0002-7863. doi:10.1021/jacs.2c05403. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20220811-457444000

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Abstract

Selective oxidation to synthesize nitriles is critical for feedstock manufacturing in the chemical industry. Current strategies typically involve substitutions of alkyl halides with toxic cyanides or the use of strong oxidation reagents (oxygen or peroxide) under ammoxidation/oxidation conditions, setting considerable challenges in energy efficiency, sustainability, and production safety. Herein, we demonstrate a facile, green, and safe electrocatalytic route for selective oxidation of amines to nitriles under ambient conditions, assisted by the anodic water oxidation on metal-doped α-Ni(OH)₂ (a typical oxygen evolution reaction catalyst). By controlling the balance between co-adsorption of the amine molecule and hydroxyls on the catalyst surface, we demonstrate that Mn doping significantly promotes the subsequent chemical oxidation of amines, resulting in Faradaic efficiencies of 96% for nitriles under ≥99% conversion. This anodic oxidation is further coupled with cathodic hydrogen evolution for overall atomic economy and additional green energy production.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.2c05403DOIArticle
ORCID:
AuthorORCID
Shin, Hyeyoung0000-0001-6694-7895
Goddard, William A., III0000-0003-0097-5716
Ding, Mengning0000-0001-6581-3385
Additional Information:© 2022 American Chemical Society. Received 21 May 2022. Published online 10 August 2022. M.D. acknowledges the support from the Natural Science Foundation of China (22172075 and 92156024), the Fundamental Research Funds for the Central Universities in China (14380273), the Natural Science Foundation of Jiangsu Province (BK20220069), Beijing National Laboratory for Molecular Sciences (BNLMS202107), and the Thousand Talents Plan of Jiangxi Province (jxsq2019102002). WAG was funded by the Liquid Sunlight Alliance (LiSA), supported by the US DOE, Office of Science, Office of Basic Energy Sciences, and Fuels from Sunlight Hub under Award DE-SC0021266. H.S. was supported by the National Research Foundation of Korea (NRF) grant (2020R1C1C1008458, 2021R1A5A1084921). Y.S., H.S., and F.W. contributed equally. The authors declare no competing financial interest.
Group:Liquid Sunlight Alliance
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China22172075
National Natural Science Foundation of China92156024
Central University Basic Research Fund of China14380273
Natural Science Foundation of Jiangsu ProviceBK20220069
Beijing National Laboratory for Molecular SciencesBNLMS202107
Thousand Talents Plan of Jiangxi Provincejxsq2019102002
Department of Energy (DOE)DE-SC0021266
National Research Foundation of Korea2020R1C1C1008458
National Research Foundation of KoreaNRF-2021R1A5A1084921
Subject Keywords:Amines, Nitrogen compounds, Oxidation, Radiology, Transition metals
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1528
DOI:10.1021/jacs.2c05403
Record Number:CaltechAUTHORS:20220811-457444000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220811-457444000
Official Citation:Highly Selective Electrocatalytic Oxidation of Amines to Nitriles Assisted by Water Oxidation on Metal-Doped α-Ni(OH)₂ Yuxia Sun, Hyeyoung Shin, Fangyuan Wang, Bailin Tian, Chen-Wei Chiang, Shengtang Liu, Xiaoshan Li, Yiqi Wang, Lingyu Tang, William A. Goddard III, and Mengning Ding Journal of the American Chemical Society Article ASAP DOI: 10.1021/jacs.2c05403
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:116238
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Aug 2022 23:10
Last Modified:15 Aug 2022 00:04

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