Publication Date

7-1-2019

Department

Ames Laboratory; Chemical and Biological Engineering

Campus Units

Ames Laboratory, Chemical and Biological Engineering

OSTI ID+

1556105

Report Number

IS-J 9987

DOI

10.1002/celc.201900482

Journal Title

ChemElectroChem

Volume Number

6

Issue Number

13

First Page

3387

Last Page

3392

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. 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.

DOE Contract Number(s)

AC02-07CH11358

Language

en

Department of Energy Subject Categories

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Publisher

Iowa State University Digital Repository, Ames IA (United States)

Available for download on Sunday, May 31, 2020

Included in

Chemistry Commons

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