Postsynthetic-Modified PANI/MOF Composites with Tunable Thermoelectric and Photoelectric Properties

A 3D Co-based metal-organic framework (Co-MOF) with two kinds of large pores filled by free Co²⁺ ions and ligands was synthesized and characterized. To expand the MOF structure and conductivity, the free Co²⁺ ions and ligands were exchanged by conductive ionic liquid EtpyBr and photosensitive AgNO₃ through single crystal-to-single crystal transformation, which produced structure-changed 3D MOFs Co-MOF-Br and Co-Ag-MOF, which were characterized by single-crystal X-ray diffraction. Incorporating small quantities of doped polyaniline (PANI) with redox activity into the pores could further tune the stability and conductivity of the three MOFs. The PANI/MOFs all show outstanding electrical conductivity (≈10^-2  S cm^-1 ), and PANI/Co-MOF-Br has the largest p-type Seebeck coefficient of 66.6 μV K^-1 . PANI/Co-MOF-Br and PANI/Co-Ag-MOF have 4 and 15 times higher photocurrent density compared with PANI/Co-MOF, respectively. This work sheds light on the design of advanced electrically conductive 3D MOFs.