Regulating Work Function of [Ca24Al28O64]4+:4e- Electrides Via Changing Solvated Electron Characters

Since electrides behave as electron donors in catalytic reactions and device substrates due to the anionic electrons localized in periodic interstitial spaces, their work functions (Phi) could be used as key indicators in describing the high electron-donating power. Taking the [Ca24Al28O64](4+):4e(-) electride as an example, we here propose a new computational scheme of Phi and, further, characterize Phi of the bulk derivative structures of the electride for clarifying the relationship between structural characteristics and Phi. Results indicate that the external strain hardly affects Phi, but the interior heteroatom-doping and distortion bring about significant changes. All these unique variations of the bulk Phi are governed by the distribution and solvation character of anionic electrons in the cage conduction band states. The mechanism of regulating Phi revealed in this work may play a role in the rational design of electride-based catalysts and devices with a superior performance.

Automated summary

The study proposed a new computational scheme to describe the work function of electrides and investigated the relationship between structural characteristics and work function. The results show that external strain has little impact on the work function, but interior heteroatom doping and distortion can bring significant changes. These findings may contribute to the rational design of electride-based catalysts and devices.