Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural
Abstract
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 (BiVO 4 ) 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 BiVO 4 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 BiVO 4 /CoPi bilayer achieved 88 % yield to 2,5‐furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO 4 . 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:
-
- Iowa State Univ., Ames, IA (United States)
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), 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. https://doi.org/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. https://doi.org/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 = {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 (BiVO 4 ) 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 BiVO 4 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 BiVO 4 /CoPi bilayer achieved 88 % yield to 2,5‐furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO 4 . 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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