Graphitic carbon nitride nanosheet supported silica nanochannel film for enhanced electrochemiluminescence sensing of 2,4,6-trichlorophenol and prochloraz

Abstract

The development of simple, rapid, and sensitive methods for detecting pesticide in environmental and food samples holds significant importance. Electrochemiluminescence (ECL) sensing platforms with high resistance to interference and contamination, and reduced consumption of ECL emitters, are highly desirable for such applications. In this work, we present an ECL sensing platform based on a graphitic carbon nitride nanosheets (CNNS) supported vertically ordered mesoporous silica film (VMSF) modified glassy carbon electrode (GCE) for the highly sensitive detection of the environmental pollutant 2,4,6-trichlorophenol (TCP) and the broad-spectrum insecticide prochloraz. Two-dimensional (2D) CNNS were synthesized by exfoliating bulk graphitic carbon nitride (g-C₃N₄) using concentrated sulfuric acid, serving as a novel conductive and adhesive layer for the growth of a stable VMSF on GCE via an electrochemical assistance self-assembly (EASA) method to prepare VMSF/CNNS/GCE. The electrostatic enrichment capability of VMSF nanochannels for the positively charged ECL emitter tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) realized stable and significantly enhanced ECL signals at a low concentration of Ru(bpy)₃²⁺ (10 μM). Based on the quenching effect of TCP on the ECL signal of Ru(bpy)₃²⁺, highly sensitive ECL detection of TCP was achieved by the VMSF/CNNS/GCE with a linear range from 10 nM to 0.7 mM and a low detection limit (DL) of 2.2 nM. As the metabolic end product of prochloraz is TCP, indirect ECL detection of prochloraz was also accomplished by measuring the produced TCP. Combined with anti-fouling and anti-interference abilities, as well as signal amplification of VMSF, the developed VMSF/CNNS/GCE sensor enabled the sensitive ECL detection of TCP in pond water and prochloraz in orange peel extract.