In this section
@article{Yu:2026:10.1021/jacs.6c00726,
author = {Yu, Y and Wang, Y and Ye, H and Halder, S and Yang, G and Ye, B and Kumar, S and Held, G and Durrant, JR and Titirici, M-M and Rao, RR},
doi = {10.1021/jacs.6c00726},
journal = {J Am Chem Soc},
title = {Mechanistic Study of Glycerol Electro-Oxidation on Ni(OH)2/NiOOH Electrodes.},
url = {http://dx.doi.org/10.1021/jacs.6c00726},
year = {2026}
}
TY - JOUR
AB - Glycerol oxidation reaction (GOR) is a promising valorization route to upgrade the biodiesel by-product while coproducing green hydrogen at the cathode in electrolyzers. However, the working mechanism of transition-metal-based catalysts such as Ni(OH)2 remains poorly understood. Here, we employed a multioperando spectroelectrochemical approach combining UV-vis optical spectroscopy, X-ray absorption spectroscopy, and time-resolved stepped-potential spectroscopy to investigate the active oxidizing species and charge-transfer dynamics under OER and GOR conditions. We identified NiOOH (Ni3+) as the active species for GOR, whereas the formation of higher-valent NiOO (Ni4+) species is completely suppressed in the presence of glycerol. The accumulation of surface-adsorbed glycerol molecules is the rate-determining step (τ ∼ 27.9 s at 1.47 VRHE), occurring slower than the intrinsic catalytic step of glycerol reaction (τ ∼ 3.2 s at 1.47 VRHE), which involves oxidation and bond cleavage. In contrast, the kinetics of the OER are significantly slower (τ ∼ 167 s at 1.47 VRHE), resulting in the dominance of GOR and suppression of oxygen evolution in the presence of glycerol. The potential-independent production of formic acid during GOR follows an apparent first-order dependence on NiOOH concentration, suggesting continuous C-C bond cleavage activated by reactive O species. These findings link oxidizing species with charge-transfer dynamics, providing insight for the rational design of Ni-based catalysts for glycerol and other biomass-derived molecule oxidations.
AU - Yu,Y
AU - Wang,Y
AU - Ye,H
AU - Halder,S
AU - Yang,G
AU - Ye,B
AU - Kumar,S
AU - Held,G
AU - Durrant,JR
AU - Titirici,M-M
AU - Rao,RR
DO - 10.1021/jacs.6c00726
PY - 2026///
TI - Mechanistic Study of Glycerol Electro-Oxidation on Ni(OH)2/NiOOH Electrodes.
T2 - J Am Chem Soc
UR - http://dx.doi.org/10.1021/jacs.6c00726
UR - https://www.ncbi.nlm.nih.gov/pubmed/41945599
ER -
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