Atomically dispersed Pt-N<sub>4</sub> sites as efficient and selective electrocatalysts for the chlorine evolution reaction.

Lim, Taejung; Jung, Gwan Yeong; Kim, Jae Hyung; Park, Sung O; Park, Jaehyun; Kim, Yong-Tae; Kang, Seok Ju; Jeong, Hu Young et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Chlorine evolution reaction (CER) is a critical anode reaction in chlor-alkali electrolysis. Although precious metal-based mixed metal oxides (MMOs) have been widely used as CER catalysts, they suffer from the concomitant generation of oxygen during the CER. Herein, we demonstrate that atomically dispersed Pt-N<sub>4</sub> sites doped on a carbon nanotube (Pt<sub>1</sub>/CNT) can catalyse the CER with excellent activity and selectivity. The Pt<sub>1</sub>/CNT catalyst shows superior CER activity to a Pt nanoparticle-based catalyst and a commercial Ru/Ir-based MMO catalyst. Notably, Pt<sub>1</sub>/CNT exhibits near 100% CER selectivity even in acidic media, with low Cl<sup>-</sup> concentrations (0.1 M), as well as in neutral media, whereas the MMO catalyst shows substantially lower CER selectivity. In situ electrochemical X-ray absorption spectroscopy reveals the direct adsorption of Cl<sup>-</sup> on Pt-N<sub>4</sub> sites during the CER. Density functional theory calculations suggest the PtN<sub>4</sub>C<sub>12</sub> site as the most plausible active site structure for the CER.