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Electrocatalytic Reduction of Nitrate and Nitrite at CuRh Nanoparticles/C Composite Electrodes

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Abstract

Composites consisting of rhodium, copper, and copper-rhodium nanoparticles (2 nm in average diameter) dispersed in a high-surface area graphite powder (~ 10 wt.% of metal) have been synthesized by a wet chemical method. After characterization by ICP-OES and TEM, they have been tested for the electrochemical reduction of nitrates in alkaline media (10−1 mol L−1 KOH) using a cavity microelectrode. It is found that in the 0.02–0.5 V/RHE potential range, bimetallic composites exhibit a much higher electrocatalytic activity than single-metal composites. The peak current describes a volcano plot as a function of the composition, with a maximum for CuRh, which is 7.5 times higher than that obtained with pure rhodium (under identical metal wt.%). This synergistic effect can be rationalized directly from the electrochemical response of pure metals. It is then tentatively attributed to the fact that the first (rate determining) reduction step, corresponding to the formation of nitrites, takes place efficiently in copper-rich areas while the subsequent steps of nitrite reduction in ammonia (via hydroxylamine formation) occur in rhodium-rich areas. For the same mass of rhodium, the electrocatalytic conversion of nitrates to ammonia is 12 times more effective with CuRh than with pure rhodium. With the additional gain in active surface area due to the nanoparticle morphology compared to bulk or thin film forms, these results represent a step-forward in cost reduction of rhodium-based electrocatalysts for the conversion of nitrates to ammonia.

Composites of copper-rhodium nanoparticles in graphite powder were tested for the electrochemical reduction of nitrates in alkaline media. They exhibit a much higher electrocatalytic activity for the conversion of nitrates to ammonia than composites with pure rhodium nanoparticles, up to 12 times more at a composition close to CuRh.

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Acknowledgements

The authors acknowledge the support of the Centre National de la Recherche Scientifique and the University Paris-Est Créteil and thank Junxian Zhang for the ICP-OES analysis. P. Mirzaei acknowledges MBA Water Treatment Chemicals Co. for the financial support of his PhD.

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Author notes

  1. Peyman Mirzaei

    Present address: Université Paris Est, ICMPE (UMR 7182), CNRS, UPEC, F-94320, Thiais, France

Authors and Affiliations

  1. Université Paris Est, ICMPE (UMR 7182), CNRS, UPEC, F-94320, Thiais, France

    Stéphane Bastide, Julie Bourgon, Claudia Zlotea, Michel Laurent, Michel Latroche & Christine Cachet-Vivier

  2. MBA Water Treatment Chemicals Co., Ltd., No. 9 Tadayyon Alley, Shariati St., Tehran, Iran

    Peyman Mirzaei & Atieh Aghajani

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  1. Peyman Mirzaei
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Correspondence to Stéphane Bastide.

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Mirzaei, P., Bastide, S., Aghajani, A. et al. Electrocatalytic Reduction of Nitrate and Nitrite at CuRh Nanoparticles/C Composite Electrodes. Electrocatalysis 9, 343–351 (2018). https://doi.org/10.1007/s12678-017-0437-z

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