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Title: Oxidation by Reduction: Efficient and Selective Oxidation of Alcohols by the Electrocatalytic Reduction of Peroxydisulfate
Award ID(s):
2002158
NSF-PAR ID:
10379406
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
144
Issue:
46
ISSN:
0002-7863
Page Range / eLocation ID:
p. 21103-21115
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Microdroplets show unique chemistry, especially in their intrinsic redox properties, and to this we here add a case of simultaneous and spontaneous oxidation and reduction. We report the concurrent conversions of several phosphonates to phosphonic acids by reduction (R−P → H−P) and to pentavalent phosphoric acids by oxidation. The experimental results suggest that the active reagent is the water radical cation/anion pair. The water radical cation is observed directly as the ionized water dimer while the water radical anion is only seen indirectly though the spontaneous reduction of carbon dioxide to formate. The coexistence of oxidative and reductive species in turn supports the proposal of a double‐layer structure at the microdroplet surface, where the water radical cation and radical anion are separated and accumulated.

     
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  2. Abstract

    Microdroplets show unique chemistry, especially in their intrinsic redox properties, and to this we here add a case of simultaneous and spontaneous oxidation and reduction. We report the concurrent conversions of several phosphonates to phosphonic acids by reduction (R−P → H−P) and to pentavalent phosphoric acids by oxidation. The experimental results suggest that the active reagent is the water radical cation/anion pair. The water radical cation is observed directly as the ionized water dimer while the water radical anion is only seen indirectly though the spontaneous reduction of carbon dioxide to formate. The coexistence of oxidative and reductive species in turn supports the proposal of a double‐layer structure at the microdroplet surface, where the water radical cation and radical anion are separated and accumulated.

     
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