Thiacalix[4]arene-based metal-organic framework/reduced graphene oxide composite for electrochemical detection of chlorogenic acid.

A novel metal-organic framework [CoLCl]·2DMF (Co-L) based on thiacalix[4]arene derivative was synthesized using the solvothermal method. Then Co-L was respectively mixed with reduced graphene oxide (RGO), multi-walled carbon nanotubes (MWCNT) and mesoporous carbon (MC) to prepare corresponding composite materials. PXRD, SEM and N adsorption-desorption illustrated that composite materials have been successfully prepared. After optimizing experimental conditions for detecting chlorogenic acid (CGA), the Co-L@RGO(1:1) composite material showed the optimal electrocatalytic activity for CGA, which may be because RGO possessed large specific surface area and hydroxyl and carboxyl groups that could form hydrogen-bonding with the oxide of CGA. Benefiting from the synergetic effect of Co-L and RGO, the glassy carbon electrode modified with Co-L@RGO(1:1) (Co-L@RGO(1:1)/GCE) exhibited a low limit of detection (LOD) of 7.24 nM for CGA within the concentration of 0.1-2 μM and 2-20 μM. Co-L@RGO(1:1)/GCE also showed excellent selectivity, stability, and reproducibility for the CGA detection. Co-L@RGO(1:1)/GCE could detect the CGA in honeysuckle with satisfactory results. This work provided a great example for the thiacalix[4]arene-based MOF in the application of electrochemical sensors.