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

Journal Article · · ChemElectroChem
 [1];  [1];  [1];  [1];  [2]
  1. Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)

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.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1556105
Alternate ID(s):
OSTI ID: 1532790
Report Number(s):
IS-J--9987
Journal Information:
ChemElectroChem, Journal Name: ChemElectroChem Journal Issue: 13 Vol. 6; ISSN 2196-0216
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic journal December 2019
Paired electrocatalytic hydrogenation and oxidation of 5-(hydroxymethyl)furfural for efficient production of biomass-derived monomers journal January 2019