RuCu Cage/Alloy Nanoparticles with Controllable Electroactivity for Specific Electroanalysis Applications

Electrochemical nanotags with controllable and multiresponse electroactivity have a great capacity for overcoming the drawbacks of limited target monitoring and inaccurate detection results for electrochemical sensors. In this contribution, double electro-oxidative Ru and Cu metals were integrated into RuCu nanostructures for the generation of dual electro-oxidative signals. A facial approach was proposed for the controllable fabrication of RuCu cage nanoparticles (NPs) and RuCu alloy NPs by simply adjusting the pH value of the reaction system. RuCu cage NPs and RuCu alloy NPs demonstrated inherent different electro-oxidative responses owing to the remarkable distinction of structures with different metal valences. RuCu cage NPs showed a single electro-oxidization peak at 0.84 V, assigned to the exposure of more Ru⁰ electroactive sites on the hollow cage structures. RuCu alloy NPs illustrated dual electro-oxidization peak at 0.84 and -0.16 V, attributing to the presence of Ru⁰ and Cu⁺ electroactive sites on the alloy structures, respectively. RuCu cage NPs and RuCu alloy NPs served as specific electroactive tags, achieving the selective monitoring of Na₂S and ratiometric electrochemical detection of xanthine in monosodium glutamate, respectively. The limits of detection were as low as 27 pM for Na₂S and 70 nM for xanthine. The rational design of multimetal nanostructures holds enormous potential for the generation of multiresponse electroactivity with the impetus for exploring the capacity of specific electrochemical sensing.