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Trifunctional Catalysts for Overall Water Splitting and Oxygen Reduction Reaction Derived from Co,Ni MOFs

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Abstract

In order to obtain platinum-group-metal-free catalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in alkaline electrolyzers, nitrogen-doped mesoporous carbons were prepared from pyrolysis of two cobalt metal organic frameworks (MOFs), one linear coordination polymer and one complex. The catalyst derived from cobalt 2,3-pyrazinedicarboxylate polymer (700 °C) had a Tafel slope of 90 mV dec−1 and 130 mV dec−1 for the HER and OER respectively, a current density of 10 mA cm−2 was reached at − 0.23 V and 1.56 V vs RHE for the HER and OER respectively. In order to prove the bifunctional catalytic activity towards the overall water splitting, a two electrode electrolyzer was constructed depositing the catalyst on carbon paper. H2 and O2 evolved volumes followed the Faraday law, showing efficiency very close to 100%. The same materials also showed catalytic activity towards the oxygen reduction reaction (ORR), reaching an electron transfer number close to 4 and low H2O2 yields. The acid leached catalyst derived from Cobalt 2,3-pyrazinedicarboxylate polymer (700 °C) reached a ∆E = Ej = 10(OER) −E½(ORR) = 0.80 V, making it an useful oxygen catalyst for metal-air batteries.

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reproduced with permission from ref [31]. Copyright 2017 Elsevier. b Linear sweep voltammograms on the Co(CO2)2Pz 700 °C (not acid leached) derived catalysts at different rotation speeds (ω). c Koutecky-Levich plot showing the linear relation between j−1 and ω−1/2 for the ORR on the different studied catalysts at 0.6 V vs RHE. Electron transfer numbers are shown on the plot. d Percentage of H2O2 produced as function of the disk potential at 100 rpm disk rotation rate for the ORR on the studied catalysts

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Acknowledgements

This work was supported by the Agencia Nacional de Promoción Científica y Tecnológica (Project PICT-2016-3017), the Commission for Atomic Energy of Argentina (CNEA), and the Research Council of Argentina (CONICET). FR is a researcher of CONICET and A.K.D.D. held a doctoral fellowship of this institution. The authors acknowledge Daniel R. Vega for obtaining the XRD patterns, and Silvia A. Dominguez, for the SEM images.

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Authors and Affiliations

  1. Departamento de Física de la Materia Condensada, Gerencia de Investigación y Aplicaciones, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica (CNEA), Avenida General Paz 1499, 1650, San Martín, Buenos Aires, Argentina

    Ana Katherine Díaz-Duran, Emilia B. Halac & Federico Roncaroli

  2. Instituto de Nanociencia y Nanotecnología (CNEA-CONICET), Centro Atómico Constituyentes, Avenida General Paz 1499, 1650, San Martín, Buenos Aires, Argentina

    Ana Katherine Díaz-Duran & Federico Roncaroli

  3. Departamento de Química Inorgánica Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428, Ciudad de Buenos Aires, Argentina

    Ana Katherine Díaz-Duran, Guido Iadarola-Pérez & Federico Roncaroli

  4. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Godoy Cruz 2290, 1425, Ciudad de Buenos Aires, Argentina

    Ana Katherine Díaz-Duran & Federico Roncaroli

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  1. Ana Katherine Díaz-Duran
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Díaz-Duran, A.K., Iadarola-Pérez, G., Halac, E.B. et al. Trifunctional Catalysts for Overall Water Splitting and Oxygen Reduction Reaction Derived from Co,Ni MOFs. Top Catal 65, 887–901 (2022). https://doi.org/10.1007/s11244-022-01611-8

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