Although triboelectrification is a well-known phenomenon, fundamental understanding of its principle on a material surface has not been studied systematically. Here, we demonstrated that the surface potential, especially the surface dipoles and surface electronic states, governed the triboelectrification by controlling the surface with various electron-donating and -withdrawing functional groups. The functional groups critically affected the surface dipoles and surface electronic states followed by controlling the amount of and even the polarity of triboelectric charges. As a result, only one monolayer with a thickness of less than 1 nm significantly changed the conventional triboelectric series. First-principles simulations confirmed the atomistic origins of triboelectric charges and helped elucidate the triboelectrification mechanism. The simulation also revealed for the first time where charges are retained after triboelectrification. This study provides new insights to understand triboelectrification.

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http://dx.doi.org/10.1021/acsami.6b02802DOI Listing

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