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配位工程化的钌-氧化铌纳米反应器与组氨酸功能化的石墨烯量子点集成用于新鲜果汁中抗坏血酸的超灵敏和选择性电化学检测。

Coordination-engineered Ru-NbO nanoreactor integrated with histidine-functionalized graphene quantum dot for ultrasensitive and selective electrochemical detection of ascorbic acid in fresh juices.

作者信息

Ye Wang, Xiaoshan Li, Ruiyi Li, Zaijun Li

机构信息

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, School of Life Science and Health Engineering, Jiangnan University, Wuxi, 214122, China.

出版信息

Mikrochim Acta. 2025 Jul 11;192(8):495. doi: 10.1007/s00604-025-07353-0.

Abstract

A coordination-driven synthetic approach is proposed to engineer Ru-NbO-HGQD nanoreactor through synergistic assembly of histidine-functionalized graphene quantum dot (HGQD). The approach involves sequential coordination of niobium oxalate and ruthenium chloride with HGQD, forming water-soluble Ru/Nb-HGQD precursor, followed by two-stage controlled thermal annealing in N to yield Ru-NbO-HGQD. The resulting Ru-NbO-HGQD offers a quasi-spherical morphology (46.5 ± 1.4 nm) featuring Ru-embedded interconnected nanochannels, abundant low-valent Nb species, and graphene-modified interfaces. This unique architecture facilitates enhanced electron/ion transport kinetics, exposes catalytically active sites, and amplifies interfacial interactions with polar electrolyte. The incorporation of NbO elevates the electrochemically active surface area by 1.55-fold, resulting in more than 2.24-fold enhancement in catalytic activity over Ru-HGQD. The ascorbic acid sensor with Ru-NbO-HGQD demonstrates a broad linear range (0-600 μM) at 0.056 V, an ultralow detection limit (1.2 × 10 M, S/N = 3), and exceptional selectivity against interferents. Long-term stability and reproducibility further validate its reliability for ascorbic acid quantification in fresh juice. This work also establishes a paradigm for designing high-performance oxide-supported metal nanomaterials in sensing, catalysis, and energy storage and conversion.

摘要

提出了一种配位驱动的合成方法,通过组氨酸功能化石墨烯量子点(HGQD)的协同组装来构建Ru-NbO-HGQD纳米反应器。该方法包括草酸铌和氯化钌与HGQD的顺序配位,形成水溶性Ru/Nb-HGQD前驱体,然后在氮气中进行两阶段控制热退火以生成Ru-NbO-HGQD。所得的Ru-NbO-HGQD呈现准球形形态(46.5±1.4纳米),具有嵌入Ru的相互连接的纳米通道、丰富的低价铌物种和石墨烯修饰的界面。这种独特的结构促进了电子/离子传输动力学的增强,暴露了催化活性位点,并放大了与极性电解质的界面相互作用。NbO的掺入使电化学活性表面积提高了1.55倍,催化活性比Ru-HGQD提高了2.24倍以上。具有Ru-NbO-HGQD的抗坏血酸传感器在0.056 V时显示出宽线性范围(0-600μM)、超低检测限(1.2×10 M,S/N = 3)以及对干扰物的优异选择性。长期稳定性和重现性进一步验证了其在鲜榨果汁中抗坏血酸定量分析的可靠性。这项工作还为在传感、催化以及能量存储与转换领域设计高性能氧化物负载金属纳米材料建立了范例。

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