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Combined biomass valorization and hydrogen production in a photoelectrochemical cell

Nature Chemistry volume 7, pages 328–333 (2015)Cite this article

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Abstract

In a typical hydrogen-producing photoelectrochemical cell (PEC), water reduction at the cathode (producing hydrogen) is accompanied by water oxidation at the anode (producing oxygen). This anode reaction is, however, not kinetically favourable. Here we investigate the possibility of utilizing solar energy for biomass conversion by performing the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) at the anode of a PEC. HMF is a key intermediate in biomass conversion, and FDCA is an important monomer for the production of numerous polymers. Using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator, we obtained a near-quantitative yield and 100% Faradaic efficiency at ambient conditions without the use of precious-metal catalysts. This reaction is also thermodynamically and kinetically more favourable than water oxidation. Our results suggest that solar-driven biomass conversion can be a viable anode reaction that has the potential to increase both the efficiency and the utility of PECs constructed for solar-fuel production.

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Figure 1: Molecules involved with HMF oxidation.
Figure 2: Electrochemical TEMPO-mediated HMF oxidation.
Figure 3: Photoelectrochemical TEMPO-mediated HMF oxidation.
Figure 4: Schematic comparison of the photoelectrochemical and electrochemical cells.
Figure 5: Electrochemical TEMPO-mediated HMF oxidation using carbon felt.

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Acknowledgements

This work was supported by the University of Wisconsin-Madison, the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry and the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US Department of Energy through Grant DE-SC0008707. The authors thank L. M. Smith and Q. Li for the use of the HPLC.

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  1. Department of Chemistry, University of Wisconsin-Madison, Madison, 53706, Wisconsin, USA

    Hyun Gil Cha & Kyoung-Shin Choi

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  1. Hyun Gil Cha
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Contributions

K-S.C. supervised the project. H.G.C. carried out all the experiments. H.G.C. and K-S.C. analysed the results and prepared the manuscript.

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Correspondence to Kyoung-Shin Choi.

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Cha, H., Choi, KS. Combined biomass valorization and hydrogen production in a photoelectrochemical cell. Nature Chem 7, 328–333 (2015). https://doi.org/10.1038/nchem.2194

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