Enhancement of electrocatalytic oxygen evolution by chiral molecular functionalization of hybrid 2D electrodes

• Published in: Nature communications 2022-06, Vol.13 (1), p.3356-3356, Article 3356
• Main Authors: Liang, Yunchang, Banjac, Karla, Martin, Kévin, Zigon, Nicolas, Lee, Seunghwa, Vanthuyne, Nicolas, Garcés-Pineda, Felipe Andrés, Galán-Mascarós, José R., Hu, Xile, Avarvari, Narcis, Lingenfelder, Magalí
• Format: Article
• Language: English
• Subjects: 147/138; 147/3; 639/301/357/551; 639/638/161/886; 639/638/542/970; 639/925/357/341; Adsorption; Binding energy; Catalysis; Catalysts; Catalytic activity; Chemical Sciences; Electrocatalysts; Electrode polarization; Electrodes; Electron spin; Energy conversion; Energy storage; Evolution; Humanities and Social Sciences; Intermediates; Iron compounds; Laboratories; multidisciplinary; Nickel compounds; Oxygen; Oxygen evolution reactions; Polarization; Polarization (spin alignment); Science; Science (multidisciplinary); Thermodynamics; Thiadiazoles
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-31096-8

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes such as thiadiazole-[7]helicene and bis(thiadiazole)-[8]helicene, to boost the oxygen evolution reaction (OER) by up to ca. 130 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D Ni- and NiFe-based catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given. While solar-to-fuel catalysis requires the careful transfer of electrons, there are still challenges understanding how electron spin contributes to reactivity. Here, authors employ chiral fused thiadiazole-helicenes to control spin polarization in oxygen evolution electrocatalysts.