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Title: Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural

Abstract

Motivated by replacing the kinetically unfavorable oxygen evolution reaction (OER) and producing value-added products in photoelectrochemical cells (PECs), we report that bismuth vanadate (BiVO4) photoelectrodes modified with a cobalt phosphate (CoPi) overlayer facilitate 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated selective oxidation of 5-hydroxymethylfurfural (HMF). CoPi layers with sufficient thickness were found to reduce the potential required for TEMPO oxidation by 0.5 V, as well as increase charge injection efficiency sevenfold compared to BiVO4 without CoPi. Furthermore, the undesired OER was completely suppressed when using the heterostructured photoanodes. Transient photocurrent measurements suggested that CoPi alleviates recombination losses resulting from the back reduction of oxidized TEMPO. The PECs with BiVO4/CoPi bilayer achieved 88 % yield to 2,5-furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO4. In conclusion, these findings suggest that suppression of the back reduction process substantially improves the efficiency of the oxidation, giving a potential route to more efficient solar fuel/chemical production.

Authors:
 [1];  [1];  [1];  [1];  [2]
  1. Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1556105
Alternate Identifier(s):
OSTI ID: 1532790
Report Number(s):
IS-J-9987
Journal ID: ISSN 2196-0216
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 6; Journal Issue: 13; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alcohol oxidation; TEMPO; photoelectrocatalysis; bismuth vanadate; biomass

Citation Formats

Chadderdon, David J., Wu, Li‐Pin, McGraw, Zachary A., Panthani, Matthew, and Li, Wenzhen. Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural. United States: N. p., 2019. Web. doi:10.1002/celc.201900482.
Chadderdon, David J., Wu, Li‐Pin, McGraw, Zachary A., Panthani, Matthew, & Li, Wenzhen. Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural. United States. doi:10.1002/celc.201900482.
Chadderdon, David J., Wu, Li‐Pin, McGraw, Zachary A., Panthani, Matthew, and Li, Wenzhen. Fri . "Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural". United States. doi:10.1002/celc.201900482. https://www.osti.gov/servlets/purl/1556105.
@article{osti_1556105,
title = {Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural},
author = {Chadderdon, David J. and Wu, Li‐Pin and McGraw, Zachary A. and Panthani, Matthew and Li, Wenzhen},
abstractNote = {Motivated by replacing the kinetically unfavorable oxygen evolution reaction (OER) and producing value-added products in photoelectrochemical cells (PECs), we report that bismuth vanadate (BiVO4) photoelectrodes modified with a cobalt phosphate (CoPi) overlayer facilitate 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated selective oxidation of 5-hydroxymethylfurfural (HMF). CoPi layers with sufficient thickness were found to reduce the potential required for TEMPO oxidation by 0.5 V, as well as increase charge injection efficiency sevenfold compared to BiVO4 without CoPi. Furthermore, the undesired OER was completely suppressed when using the heterostructured photoanodes. Transient photocurrent measurements suggested that CoPi alleviates recombination losses resulting from the back reduction of oxidized TEMPO. The PECs with BiVO4/CoPi bilayer achieved 88 % yield to 2,5-furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO4. In conclusion, these findings suggest that suppression of the back reduction process substantially improves the efficiency of the oxidation, giving a potential route to more efficient solar fuel/chemical production.},
doi = {10.1002/celc.201900482},
journal = {ChemElectroChem},
number = 13,
volume = 6,
place = {United States},
year = {2019},
month = {5}
}

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