Owing to their great significance for energy storage and sensing applications, multi-layer papers consisting of graphene oxide-carbon nanotube (GO-CNT) hybrid sheets were prepared by in situ exfoliation of graphite oxide in the presence of oxidized CNTs (oCNTs). For the first time we elucidate the influence of oCNTs on chemisorbed water (CW), i.e. the water molecules inherently bound to the oxygen functional groups (OFGs) of graphene oxide (GO) and responsible for irreversible structural damage upon thermal reduction processes. We show that oCNTs self-assemble onto GO sheets during the liquid phase processing steps by forming cooperatively strengthened OH···O[double bond, length as m-dash]C hydrogen bonds between the carboxylic groups of the oCNTs and OFGs of GO. At oCNT amounts of about 10 to 15 wt% this leads to the displacement of considerable amounts of CW without altering the original chemical composition of GO. The thermally reduced GO-CNT (rGO-CNT) papers reveal improved sp2 character and an enhancement of the specific capacitance by 75% with respect to thermally reduced GO (rGO), largely due to the effective removal of CW by oxidized CNTs. These findings disclose the relevance of the cooperative hydrogen bonding phenomena in graphene oxide paper/film electrodes for the development of improved electrochemical energy storage and sensing devices.
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