Cheng Xiaomin, Shui Xiaojuan, Yang Quan, Ma Huimin, Zhang Yuanyuan, Zeng Ting, Yang Juan, Wu Zhen, Zhang Xiuhua, Yang Nianjun
School of Chemistry and Environmental Engineering, School of Materials Science and Engineering, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan Institute of Technology, Wuhan, 430205, China.
School of Chemistry and Environmental Engineering, School of Materials Science and Engineering, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan Institute of Technology, Wuhan, 430205, China.
Anal Chim Acta. 2025 Jul 1;1357:344074. doi: 10.1016/j.aca.2025.344074. Epub 2025 Apr 14.
Hydroquinone (HQ) and catechol (CC), two important isomers with similar structures, are highly toxic, often coexisting, and impeding each other in the simultaneous detection. Electrochemical technique provides a promising alternative toward the quantification of HQ and CC, due to its inherent advantages in terms of highly sensitive reaction, ease of monitoring, low-cost, simplicity and quick response. Development of a sensing material with outstanding electrocatalytic capabilities and its utilization for the fabrication of an electrochemical sensor for highly selective monitoring of HQ and CC is of great significance.
In this study, a novel hierarchical nanostructure is fabricated where Co nanoparticles are anchored on N-doped carbon nanotube hollow sphere (Co/HNC) through the pyrolysis of ZIF-67@ZIF-8 hollow microsphere. On the Co/HNC modified electrode two well-defined and distinguishable peaks are displayed, resulting from electrochemical oxidation of both isomers. As an electrochemical sensor, the recorded peak current displays a linear relationship to the concentration of both HQ and CC from 0.1 to 100 μM under optimal conditions, coupled with their low detection limit of 23 nM and 37 nM, respectively. The probable application of this sensing platform was also checked for the detection of HQ and CC in real samples (e.g., lake water, tap water, detergents, ointment and orange juice), showing outstanding recovery rates. Moreover, simultaneous analysis of HQ and CC exhibited high reproducibility, selectivity and long-term stability.
As a highly efficient electrocatalyst, the unique hollow and porous microsphere structure of Co/HNC affords abundant active sites, short ion diffusion path, outstanding electronic conductivity and high electrocatalytic activity, thereby certifying excellent sensing capability for these two important isomers. This study thus efficiently explores the advances of metal/NC with hollow structure for the formation of selective dihydroxybenzene electrochemical sensors.
对苯二酚（HQ）和邻苯二酚（CC）是两种结构相似的重要异构体，毒性很强，经常共存，并且在同时检测时会相互干扰。电化学技术因其在高灵敏度反应、易于监测、低成本、简单和快速响应方面的固有优势，为HQ和CC的定量分析提供了一种有前景的替代方法。开发具有出色电催化能力的传感材料并将其用于制造用于高选择性监测HQ和CC的电化学传感器具有重要意义。
在本研究中，通过ZIF-67@ZIF-8中空微球的热解制备了一种新型的分级纳米结构，其中Co纳米颗粒锚定在N掺杂的碳纳米管空心球（Co/HNC）上。在Co/HNC修饰电极上显示出两个明确且可区分的峰，这是两种异构体的电化学氧化所致。作为电化学传感器，在最佳条件下，记录的峰电流与HQ和CC的浓度在0.1至100μM范围内呈线性关系，其检测限分别低至23 nM和37 nM。还检查了该传感平台在实际样品（例如湖水、自来水、洗涤剂、药膏和橙汁）中检测HQ和CC的可能应用，显示出出色的回收率。此外，HQ和CC的同时分析具有高重现性、选择性和长期稳定性。
作为一种高效的电催化剂，Co/HNC独特的中空和多孔微球结构提供了丰富的活性位点、短的离子扩散路径、出色的电子导电性和高电催化活性，从而证明了对这两种重要异构体具有出色的传感能力。因此，本研究有效地探索了具有中空结构的金属/氮碳材料在形成选择性二羟基苯电化学传感器方面的进展。
