Anomalous interfacial electron transfer kinetics in twisted trilayer graphene caused by layer-specific localization

Abstract

Interfacial electron-transfer (ET) reactions underpin the interconversion of electrical and chemical energy. Pioneering experiments showed that the ET rate depends on the Fermi Dirac distribution of the electronic density of states (DOS) of the electrode, formalized in the Marcus Hush Chidsey (MHC) model. Here, by controlling interlayer twists in well-defined trilayergraphene moires, we show that ET rates are strikingly dependent on electronic localization in each atomic layer, and not the overall DOS. The large degree of tunability inherent to moire electrodes leads to local ET kinetics that range over three orders of magnitude across different constructions of only three atomic layers, even exceeding rates at bulk metals. Our results demonstrate that beyond the ensemble DOS, electronic localization is critical in facilitating interfacial ET, with implications for understanding the origin of high interfacial reactivity typically exhibited by defects at electrode electrolyte interfaces.