Effects of Surface Functional Groups on Electron Transfer at Liquid–Solid Interfacial Contact Electrification

Contact electrification (CE) at interfaces is sensitive to the functional groups on the solid surface, but its mechanism is poorly understood, especially for the liquid-solid cases. A core controversy is the identity of the charge carriers (electrons or/and ions) in the CE between liquids and solids. Here, the CE between SiO₂ surfaces with different functional groups and different liquids, including DI water and organic solutions, is systematically studied, and the contribution of electron transfer is distinguished from that of ion transfer according to the charge decay behavior at surfaces at specific temperature, because electron release follows the thermionic emission theory. It is revealed that electron transfer plays an important role in the CE between liquids and functional group modified SiO₂. Moreover, the electron transfer between the DI water and the SiO₂ is found highly related to the electron affinity of the functional groups on the SiO₂ surfaces, while the electron transfer between organic solutions and the SiO₂ is independent of the functional groups, due to the limited ability of organic solutions to donate or gain electrons. An energy band model for the electron transfer between liquids and solids is further proposed, in which the effects of functional groups are considered. The discoveries in this work support the "two-step" model about the formation of an electric double-layer (Wang model), in which the electron transfer occurs first when the liquids contact the solids for the very first time.