Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Schichtl, Zebulon G.; Conlin, Samuel K.; Mehrabi, Hamed; Nielander, Adam C.; Coridan, Robert H.

doi:10.1021/acsaem.2c00377

Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Journal Article · Fri Mar 18 00:00:00 EDT 2022 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.2c00377· OSTI ID:2951724

^[1]; Conlin, Samuel K. ^[1]; Mehrabi, Hamed ^[1]; ^[2]; ^[1]

University of Arkansas, Fayetteville, AR (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Unassisted solar-driven water electrolysis as a sustainable source for H₂ is limited by the high overpotential necessary to drive the oxygen evolution reaction (OER). Crude glycerol is an extremely alkaline byproduct of biodiesel synthesis that can be valorized or refined to produce more desirable chemicals. Glycerol can also be directly oxidized on an anode, replacing water oxidation, to reduce the applied cell potential requirements of electrolytic H₂ production or CO₂ reduction. An advantage of oxidizing glycerol in its crude form is the opportunity to valorize it without initial refinement. We describe an approach to replace the OER half-reaction with the sacrificial crude glycerol electrooxidation on a layered Au–Pt–Bi electrocatalyst on a Ni substrate. Compared to compositions with fewer components, the AuPtBi–Ni electrocatalyst improved the duration of performance and reduced the overall cell potential for glycerol electrooxidation in the extreme alkaline solutions representative of crude glycerol. These enhancements facilitated extended, unassisted hydrogen evolution from crude glycerol electrolysis, even under the power of a single-junction silicon solar cell at less than 1 sun illumination. We characterized the oxidation products of crude glycerol electrolysis and the subsequent products formed spontaneously in the electrolyte in the highly alkaline solution. This analysis helps to both identify the stoichiometric limits of glycerol oxidation at the low cell potentials of interest here and to understand the chemical control imparted by electrocatalysis on the ultimate compounds formed in the crude solution. Furthermore, the results for the AuPtBi electrocatalyst show that incorporating crude glycerol oxidation into integrated electrochemical systems can simultaneously simplify their design and significantly improve solar-to-hydrogen rates.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Arkansas, Fayetteville, AR (United States); University of Arkansas, Fayetteville, AR (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020301

OSTI ID:: 2951724

Alternate ID(s):: OSTI ID: 1860612

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 3 Vol. 5; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

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