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.
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Youli Yu
Yifeng Wang
Hanzhi Ye
Journal of the American Chemical Society
Imperial College London
Tohoku University
Diamond Light Source
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Yu et al. (Tue,) studied this question.
www.synapsesocial.com/papers/69d895046c1944d70ce060b1 — DOI: https://doi.org/10.1021/jacs.6c00726
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