Zhao Tong, Niu Xia, Pei Wen-Yuan, Ma Jian-Fang
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Anal Chim Acta. 2023 Oct 2;1276:341653. doi: 10.1016/j.aca.2023.341653. Epub 2023 Jul 24.
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.
采用溶剂热法合成了一种基于硫杂杯[4]芳烃衍生物的新型金属有机框架[CoLCl]·2DMF（Co-L）。然后将Co-L分别与还原氧化石墨烯（RGO）、多壁碳纳米管（MWCNT）和介孔碳（MC）混合，制备相应的复合材料。粉末X射线衍射（PXRD）、扫描电子显微镜（SEM）和N吸附-脱附表明已成功制备出复合材料。在优化检测绿原酸（CGA）的实验条件后，Co-L@RGO(1:1)复合材料对CGA表现出最佳的电催化活性，这可能是因为RGO具有大的比表面积以及能与CGA氧化物形成氢键的羟基和羧基。受益于Co-L和RGO的协同效应，用Co-L@RGO(1:1)修饰的玻碳电极（Co-L@RGO(1:1)/GCE）在0.1 - 2 μM和2 - 20 μM浓度范围内对CGA的检测限低至7.24 nM。Co-L@RGO(1:1)/GCE对CGA检测还表现出优异的选择性、稳定性和重现性。Co-L@RGO(1:1)/GCE能够检测金银花中的CGA，结果令人满意。这项工作为基于硫杂杯[4]芳烃的金属有机框架在电化学传感器中的应用提供了一个很好的范例。
