Triboelectric charging involves frictional contact of two different materials, and their contact electrification usually relies on polarity difference in the triboelectric series. This limits the choices of materials for triboelectric contact pairs, hindering research and development of energy harvest devices utilizing triboelectric effect. A progressive approach to resolve this issue involves modification of chemical structures of materials for effectively engineering triboelectric properties of them. Here, we describe a facile method to change triboelectric property of a polymeric surface via atomic level chemical functionalizations using a series of halogens and amines, which allows a wide spectrum of triboelectric series over single material. Using this method, tunable triboelectric output power density is demonstrated in triboelectric generators. Furthermore, molecular scale calculation using density functional theory unveils that transferred electron through electrification is occupied at the PET group rather than the surface functional group. The work introduced here would open the ability to tune triboelectric property of materials by chemical modification of surface, and facilitate the development of energy harvesting devices and sensors exploiting triboelectric effect.

 http://pubs.acs.org/doi/abs/10.1021/acsnano.7b02156