▎ 摘　　要

Modulating the conductivity of microporous metal-organic frameworks (MOFs) through formulation of composites with graphene (G), as the conductive element, is demonstrated, without being limited to a particular MOF composition or topology. The synthesis allows for varying G content within the composite systematically, resulting in highly electrically conductive composites beyond 30 wt% G. The charge percolation model can effectively be utilized to describe the macroscopic electrical conductivity of the synthesized composites. Starting from a non-conductive MOF (HKUST-1, sigma = 2*10(-8) S m(-1)), enhanced conductivity can be accessed through increasing the G wt%, reaching more than nine orders of magnitude increase in conductivity up to 23.3 S m(-1) for the composite containing 59.4 wt% G. A charge percolation threshold of 30 wt% G was observed, where sufficient G-G contacts were established within the composite. The ab initio DFT calculations on Cu-paddlewheel@G model indicated several non-covalent interactions, including OH center dot center dot center dot pi and pi-pi interactions, governing the deposition of the MOF on top of G (range of-101.3 kJ/mol to-113.8 kJ/mol). This approach is potentially transferable to the vast majority of MOFs, as surface functionalization of the conductive filler is not a prerequisite for the attainment of bottom-up assembly of the MOF@G. (C) 2020 Elsevier Ltd. All rights reserved.