Abstract
Designing highly conducting metal–organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation. Herein, a strategic design in which a metal–sulfur plane is integrated within a MOF to achieve high electrical conductivity, is successfully demonstrated. The MOF {[Cu2(6-Hmna)(6-mn)]·NH4}n (1, 6-Hmna = 6-mercaptonicotinic acid, 6-mn = 6-mercaptonicotinate), consisting of a two dimensional (–Cu–S–)n plane, is synthesized from the reaction of Cu(NO3)2, and 6,6′-dithiodinicotinic acid via the in situ cleavage of an S–S bond under hydrothermal conditions. A single crystal of the MOF is found to have a low activation energy (6 meV), small bandgap (1.34 eV) and a highest electrical conductivity (10.96 S cm−1) among MOFs for single crystal measurements. This approach provides an ideal roadmap for producing highly conductive MOFs with great potential for applications in batteries, thermoelectric, supercapacitors and related areas.
Highlights
Designing highly conducting metal–organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation
We report on the preparation of single crystals of a Cu-based MOF with a copper–sulfur plane that shows a high electrical conductivity (10.96 S cm−1) measured on a single crystal
An FTIR spectrum of 1 showed a peak at 1697 cm−1 which corresponds to the C=O stretching of an uncoordinated carboxylic group, three peaks at 1585, 1435, and 1312 cm−1 corresponding to aromatic C=C stretching, and an additional peak at 525 cm−1, corresponding to Cu–S bending (Supplementary Fig. 3)
Summary
Designing highly conducting metal–organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation. We report on the preparation of single crystals of a Cu-based MOF with a copper–sulfur plane that shows a high electrical conductivity (10.96 S cm−1) measured on a single crystal. The contacts for the electrical measurements were fabricated using a focused ion beam (FIB) method (Supplementary Fig. 12).
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