Dataset Information

Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid.

ABSTRACT: A series of mononuclear first-row transition metal pyrithione M(pyr) _n complexes (M = Ni(II), Mn(II), n = 2; M = Co(III), Fe(III), n = 3) have been prepared from the reaction of the corresponding metal salt with the sodium salt of pyrithione. Using cyclic voltammetry, the complexes have been shown to behave as proton reduction electrocatalysts albeit with varying efficiencies in the presence of acetic acid as the proton source in acetonitrile. The nickel complex displays the optimal overall catalytic performance with an overpotential of 0.44 V. An ECEC mechanism is suggested for the nickel-catalyzed system based on the experimental data and supported by density functional theory calculations.

SUBMITTER: Tang HM

PROVIDER: S-EPMC9948554 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid.

Tang Hui Min HM Fan Wai Yip WY

ACS omega 20230209 7

A series of mononuclear first-row transition metal pyrithione M(pyr) n complexes (M = Ni(II), Mn(II), n = 2; M = Co(III), Fe(III), n = 3) have been prepared from the reaction of the corresponding metal salt with the sodium salt of pyrithione. Using cyclic voltammetry, the complexes have been shown to behave as proton reduction electrocatalysts albeit with varying efficiencies in the presence of acetic acid as the proton source in acetonitrile. The nickel complex d ...[more]

PMID: 36844539

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Project description:Oxygen reduction reaction (ORR) remains a pivotal factor in assessing the overall efficiency of energy conversion and storage technologies. A promising family of ORR electrocatalysts is mixed transition-metal oxides (MTMOs), which have recently gained a growing research interest. In this study, we developed MTMOs with different compositions (designated as A x B3-x O4; A = Cu, B = Co or Mn) anchored on two different carbon supports (activated carbon Vulcan XC-72 (AC) and graphene (G)) for catalyzing ORR in neutral media. Four different MTMO electrocatalysts (i.e., MnO2-CuO/AC, CoO-CuO/AC, CoO-CuO/G, and MnO2-CuO/G) were synthesized by a simple and scalable co-precipitation method. We documented the morphology and electrocatalytic properties of MTMO electrocatalysts using transmission and scanning electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), energy dispersive X-ray (EDX), and electrochemical techniques. Generally, MTMOs exhibited remarkably high ORR electrocatalytic activity with MTMOs anchored on an activated carbon support outperforming their respective MTMOs anchored on a graphene support, highlighting the importance of the catalyst support in determining the overall ORR activity of electrocatalysts. MnO2-CuO/AC has the highest diffusion limiting current density (j) value of 4.2 mA cm-2 at -600 mV (vs. SHE), which is ∼1.1-1.7-fold higher than other tested electrocatalysts (i.e., 3.9, 3.5, and 2.7 mA cm-2 for CoO-CuO/AC, CoO-CuO/G, and MnO2-CuO/G, respectively), and slightly lower than Pt/C (5.1 mA cm-2) at the same potential value. Moreover, all electrocatalysts exhibited good linearity and parallelism of the Koutechy-Levich (K-L) plots, suggesting that ORR followed first-order reaction kinetics with the number of electrons involved being close to four. Benefiting from their remarkable ORR electrochemical activities and low cost, our results reveal that non-precious MTMOs are efficient enough to replace expensive Pt for broad applications in energy conversion and electrocatalysis in neutral media, such as microbial fuel cells.

Dataset Information

Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid.

Publications

Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid.

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