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Peer-reviewedCC BY-NC 4.0Chemsuschem

Tuning the Selectivity of Glycerol Electrooxidation via Catalyst Composition and Operating Conditions

  • Martí Molera1,2
  • Viktoria Golovanova3
  • F. Pelayo García de Arquer3
  • Angel Cuesta4,5
  • Teresa Andreu1
5 affiliations
  1. 1Sustainable Electrochemical Processes (SEP), Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Facultat de Química Universitat de Barcelona (UB) Barcelona Spain
  2. 2Departament d’Enginyeria Electrònica i Biomèdica, Facultat de Física Universitat de Barcelona (UB) Barcelona Spain
  3. 3Institut de Ciències Fotòniques (ICFO), Barcelona Institute of Science and Technology Castelldefels Spain
  4. 4Advanced Centre for Energy and Sustainability (ACES) School of Natural and Computing Sciences University of Aberdeen Aberdeen UK
  5. 5Instituto de Química Física Blas Cabrera Madrid Spain
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Abstract

The electrooxidation of glycerol presents a promising route for upgrading a biodiesel byproduct into high‐value chemicals while lowering the energy cost of electrochemical hydrogen production, but its mechanistic understanding remains incomplete. This work investigates the influence of temperature and catalyst composition on glycerol electrooxidation using three distinct electrocatalysts: first‐row transition‐metal NiCo oxide, noble metal AuIn alloy, and hybrid PdNi alloy. Electrochemical, in situ UV–vis reflectance and in situ Raman measurements reveal catalyst‐specific oxidation mechanisms: an oxyhydroxide‐mediated path for NiCo, an adsorbed hydroxide‐mediated path for AuIn which suffers from inhibition, and a dual mechanism for PdNi. Oxyhydroxide mechanisms favor formic acid, whereas adsorbed hydroxide pathways selectively promote C3 products such as glyceric acid and dihydroxyacetone. Flow cell electrolysis across a range of temperatures and flow rates relevant to industrial application shows that elevated temperature enhances reaction rates and mitigates catalyst inhibition, a relevant effect for the hybrid catalyst. These findings provide key mechanistic insights and practical guidelines for optimizing continuous‐flow glycerol electrooxidation systems.

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Cite

BibTeXRIS
BibTeX
@article{molera2026tuning,
  title = {{Tuning the Selectivity of Glycerol Electrooxidation via Catalyst Composition and Operating Conditions}},
  author = {Martí Molera and Viktoria Golovanova and F. Pelayo García de Arquer and Angel Cuesta and Teresa Andreu},
  journal = {Chemsuschem},
  year = {2026},
  month = oct,
  doi = {10.1002/cssc.71189},
  url = {https://doi.org/10.1002/cssc.71189},
  note = {CC BY-NC 4.0},
}
RIS
TY  - JOUR
TI  - Tuning the Selectivity of Glycerol Electrooxidation via Catalyst Composition and Operating Conditions
AU  - Martí Molera
AU  - Viktoria Golovanova
AU  - F. Pelayo García de Arquer
AU  - Angel Cuesta
AU  - Teresa Andreu
PY  - 2026
DA  - 2026/10/27
JO  - Chemsuschem
DO  - 10.1002/cssc.71189
UR  - https://doi.org/10.1002/cssc.71189
AB  - The electrooxidation of glycerol presents a promising route for upgrading a biodiesel byproduct into high‐value chemicals while lowering the energy cost of electrochemical hydrogen production, but its mechanistic understanding remains incomplete. This work investigates the influence of temperature and catalyst composition on glycerol electrooxidation using three distinct electrocatalysts: first‐row transition‐metal NiCo oxide, noble metal AuIn alloy, and hybrid PdNi alloy. Electrochemical, in situ UV–vis reflectance and in situ Raman measurements reveal catalyst‐specific oxidation mechanisms: an oxyhydroxide‐mediated path for NiCo, an adsorbed hydroxide‐mediated path for AuIn which suffers from inhibition, and a dual mechanism for PdNi. Oxyhydroxide mechanisms favor formic acid, whereas adsorbed hydroxide pathways selectively promote C3 products such as glyceric acid and dihydroxyacetone. Flow cell electrolysis across a range of temperatures and flow rates relevant to industrial application shows that elevated temperature enhances reaction rates and mitigates catalyst inhibition, a relevant effect for the hybrid catalyst. These findings provide key mechanistic insights and practical guidelines for optimizing continuous‐flow glycerol electrooxidation systems.
SN  - 1864-5631
SN  - 1864-564X
ER  -