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Engineering Cu–N active sites in diaminonaphthalene–copper nanocomposites for efficient nitrate electroreduction and ultrasensitive sensing
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DOI：10.1007/s10853-026-13531-z.png)
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Abstract
En 中文
Nitrate contamination is a major environmental concern that threatens both water quality and human health, creating an urgent need for sensitive, reliable, and cost-effective analytical platforms. Herein, we report a nanostructured electrochemical sensor based on electrodeposited copper nanoparticles combined with electropolymerized poly(1,5-diaminonaphthalene) (poly(1,5-DAN)) for efficient nitrate detection. The influence of the electropolymerization mode and applied potential on the electrochemical performance was systematically investigated and directly correlated with the copper nucleation mechanism. Chronoamperometric analysis revealed that electropolymerization at 0.8 V versus Ag/AgCl follows a diffusion-controlled instantaneous nucleation mechanism, leading to the formation of a thin polymer film that promotes the uniform deposition of copper nanoparticles with high density of electrocatalytic active sites. Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) confirmed the coexistence of Cu(I)/Cu(II) species and strong Cu–N coordination. The resulting architecture facilitated rapid interfacial electron transfer, enhanced nitrate adsorption, and accelerated the multistep electroreduction of nitrate to ammonia. Under the optimized square-wave voltammetry conditions, the sensor exhibited a linear response over the 1–100 μM concentration range with a low detection limit of 0.26 μM, excellent selectivity, reproducibility, and operational stability. The practical applicability of the developed sensor was successfully demonstrated through the determination of nitrate in real water samples, highlighting the potential of these nanocomposites a robust, low-cost, and high-performance platform for environmental nitrate monitoring.
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