Local Mo⁶⁺ Coordination and Textural Accessibility, Rather than Bulk Phase, Correlate with the Peroxidase-Mimetic Reactivity of CoMoO₄ Nanopowders.
4 affiliations
- 1"Vinča" Institute of Nuclear Sciences, National Institute of the Republic of Serbia, University of Belgrade, Mike Petrovića Alasa 12-14, 11351 Belgrade, Serbia.
- 2Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, 11000 Belgrade, Serbia.
- 3Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade, Serbia.
- 4Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade, Serbia.
Abstract
Whether the bulk crystallographic phase determines the H₂O₂ reactivity of oxide nanopowders has direct implications for catalyst design. Three glycine-nitrate-derived CoMoO₄ nanopowders-as-synthesized, calcined at 450 °C (both β-CoMoO₄ by XRD), and calcined at 1000 °C (α-CoMoO₄)-were studied by ATR-FTIR spectroscopy, the Briggs-Rauscher (BR) oscillatory reaction, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. Deconvolution of the Mo-O stretching region with a uniform Voigt line shape resolves octahedral (α-type) and tetrahedral (β-type) Mo⁶⁺ components in both β-classified powders, indicating short-range coordination heterogeneity not detected by XRD. In the BR reaction (n = 3), the 450 °C powder suppresses oscillations at ≤0.002 g, whereas the as-synthesized powder still oscillates at 0.040 g (slope of the τosc decrease is 5172 ± 406 s g⁻¹), and the bulk-α 1000 °C powder is about four times less active per gram than the as-synthesized powder. CV supports the highest activity of the 450 °C powder. A semi-quantitative descriptor, Φ = ρα × SBET, combining the FTIR α-type band-area fraction with the BET surface area, identifies the most active powder but does not discriminate between the two less active ones. Within this series, bulk phase identity alone does not predict peroxidase-mimetic activity.
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BibTeX
@article{rosic2026local,
title = {{Local Mo⁶⁺ Coordination and Textural Accessibility, Rather than Bulk Phase, Correlate with the Peroxidase-Mimetic Reactivity of CoMoO₄ Nanopowders.}},
author = {Milena Rosić and Zorica Mojović and Maja C Pagnacco and Jelena V Senćanski and Jelena P Maksimović and Dragana Jordanov and Maria Čebela},
journal = {Materials (Basel, Switzerland)},
year = {2026},
month = oct,
doi = {10.3390/ma19204318},
url = {https://europepmc.org/article/MED/42941058},
note = {CC BY},
}
RIS
TY - JOUR
TI - Local Mo⁶⁺ Coordination and Textural Accessibility, Rather than Bulk Phase, Correlate with the Peroxidase-Mimetic Reactivity of CoMoO₄ Nanopowders.
AU - Milena Rosić
AU - Zorica Mojović
AU - Maja C Pagnacco
AU - Jelena V Senćanski
AU - Jelena P Maksimović
AU - Dragana Jordanov
AU - Maria Čebela
PY - 2026
DA - 2026/10/14
JO - Materials (Basel, Switzerland)
DO - 10.3390/ma19204318
UR - https://europepmc.org/article/MED/42941058
AB - Whether the bulk crystallographic phase determines the H₂O₂ reactivity of oxide nanopowders has direct implications for catalyst design. Three glycine-nitrate-derived CoMoO₄ nanopowders-as-synthesized, calcined at 450 °C (both β-CoMoO₄ by XRD), and calcined at 1000 °C (α-CoMoO₄)-were studied by ATR-FTIR spectroscopy, the Briggs-Rauscher (BR) oscillatory reaction, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. Deconvolution of the Mo-O stretching region with a uniform Voigt line shape resolves octahedral (α-type) and tetrahedral (β-type) Mo⁶⁺ components in both β-classified powders, indicating short-range coordination heterogeneity not detected by XRD. In the BR reaction (n = 3), the 450 °C powder suppresses oscillations at ≤0.002 g, whereas the as-synthesized powder still oscillates at 0.040 g (slope of the τosc decrease is 5172 ± 406 s g⁻¹), and the bulk-α 1000 °C powder is about four times less active per gram than the as-synthesized powder. CV supports the highest activity of the 450 °C powder. A semi-quantitative descriptor, Φ = ρα × SBET, combining the FTIR α-type band-area fraction with the BET surface area, identifies the most active powder but does not discriminate between the two less active ones. Within this series, bulk phase identity alone does not predict peroxidase-mimetic activity.
SN - 1996-1944
ER -