Xu Wenjuan, Zhao Yujie, Wang Huarui, Wang Hongfei, Pan Fangfang, Xu Ruixue, Hou Hongwei
The College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
The College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, 471022, China.
Chemistry. 2021 Mar 12;27(15):5011-5018. doi: 10.1002/chem.202005474. Epub 2021 Feb 19.
A 3D Co-based metal-organic framework (Co-MOF) with two kinds of large pores filled by free Co ions and ligands was synthesized and characterized. To expand the MOF structure and conductivity, the free Co ions and ligands were exchanged by conductive ionic liquid EtpyBr and photosensitive AgNO 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 S cm ), and PANI/Co-MOF-Br has the largest p-type Seebeck coefficient of 66.6 μV K . 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.
合成并表征了一种具有两种由游离钴离子和配体填充的大孔的三维钴基金属有机框架（Co-MOF）。为了扩展MOF结构和导电性，通过单晶到单晶转变，用导电离子液体EtpyBr和光敏AgNO3交换游离的钴离子和配体，从而产生结构改变的三维MOF Co-MOF-Br和Co-Ag-MOF，通过单晶X射线衍射对其进行了表征。在孔中掺入少量具有氧化还原活性的掺杂聚苯胺（PANI）可以进一步调节三种MOF的稳定性和导电性。PANI/MOFs均表现出出色的电导率（≈10 S cm），并且PANI/Co-MOF-Br具有最大的p型塞贝克系数66.6 μV K。与PANI/Co-MOF相比，PANI/Co-MOF-Br和PANI/Co-Ag-MOF的光电流密度分别高出4倍和15倍。这项工作为先进的导电三维MOF的设计提供了思路。
