Design, Reactivity, and Active Site of Atomically Dispersed Pt Catalysts for Electrochemical Chlorine Evolution Reaction

The electrochemical chlorine evolution reaction (CER) is a key anodic reaction in the chlor−alkali process for Cl 2 production, on-site generation of ClO – , and Cl 2 -mediated electrosynthesis. 1−3 For more than a half-century precious metal-based mixed metal oxides (MMOs) have been mainstays as CER catalysts, however, they intrinsically suffer from the selectivity problem arising from a parasitic oxygen evolution reaction (OER). We have recently developed a new CER catalyst based on atomically dispersed Pt sites on a carbon nanotube (Pt 1 /CNT), which catalyzes the CER with excellent activity and selectivity. 4 The Pt 1 /CNT catalyst shows superior CER activity to a commercial Ru/Ir-based MMO and a Pt nanoparticle-based catalyst. Importantly, Pt 1 /CNT exhibits very high CER selectivity near 100% even in low Cl − concentrations (0.1 M) and neutral media, under which the OER is favored over the CER. In situ X-ray absorption spectroscopy and density functional theory calculations reveal that the CER over Pt 1 /CNT augments with the direct adsorption of Cl − ion on Pt, which can break the scaling relationship between CER and OER. The Pt 1 /CNT catalyst also shows unusual potential-dependent switching behavior of CER kinetics and rate-determining step. 5 Pt 1 /CNT shows a reaction order of ~1.8 in the low overpotential regime, where the Volmer step is the rate-determining step (RDS). Interestingly, in the high overpotential region, the CER over Pt 1 /CNT proceeds with a lower reaction order and the RDS switches to the Heyrovský step. We also show that the Pt 1 /CNT catalyst is comprised of multiple Pt sites with different coordination environments and identify a genuine active site in Pt 1 /CNT catalysts for the CER. 6 K. B. Karlsson and A. Cornell, Selectivity between Oxygen and Chlorine Evolution in the Chlor-Alkali and Chlorate Processes. Chem. Rev. 116 , 2982–3028 (2016). S. Exner, T. Lim, and S. H. Joo, Circumventing the OCl vs. OOH Scaling Relation in the Chlorine Evolution Reaction: Beyond Dimensionally Stable Anodes. Curr. Opin. Electrochem. 34 , 100979 (2022). Trasatti, Electrocatalysis: Understanding the Success of DSA. Electrochim. Acta 45 , 2377–2385 (2000). Lim, G. Y. Jung, J. H. Kim, S. O. Park, J. Park, Y.-T. Kim, S. J. Kang, H. Y. Jeong, S. K. Kwak, and S. H. Joo, Atomically Dispersed Pt−N 4 Sites as Efficient and Selective Electrocatalysts for the Chlorine Evolution Reaction, Nat. Commun. 11 , 412 (2020). Lim, J. H. Kim, J. Kim, D. S. Baek, T. J. Shin, H. Y. Jeong, K.-S. Lee, K. S. Exner, and S. H. Joo, General Efficacy of Atomically Dispersed Pt Catalysts for the Chlorine Evolution Reaction: Potential-Dependent Switching of the Kinetics and Mechanism, ACS Catal. 11 , 12232−12246 (2021). Cho, T. Lim, H. Kim, L. Meng, J. Kim, J. H. Lee, G. Y. Jung, F. Viñes, F. Illas, K. S. Exner, S. H. Joo, and C. H. Choi, Importance of Broken Geometric Symmetry of Single-Atom Pt Sites for Efficient Electrocatalysis, Nat. Commun. 14 , 3233 (2023).