物理化学学报 >> 2026, Vol. 42 >> Issue (1): 100144.doi: 10.1016/j.actphy.2025.100144

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共价键调控电荷转移以实现自供能电化学传感平台对重金属离子的灵敏分析

陈芸1,3,4, 邓代洁2, 徐丽2, 朱兴旺1,*(), 李赫楠2,*(), 孙成明1,3,4   

  1. 1 扬州大学智慧农业研究院, 农学院, 环境科学与工程学院, 机械工程学院, 江苏 扬州 225009
    2 江苏大学化学化工学院, 能源研究院, 江苏 镇江 212013
    3 江苏省作物遗传生理国家重点实验室培育点, 扬州大学, 江苏 扬州 225009
    4 江苏省粮食作物现代产业技术协同创新中心, 扬州大学, 江苏 扬州 225009
  • 收稿日期:2025-04-29 修回日期:2025-06-22 录用日期:2025-07-31 发布日期:2025-11-01
  • 通讯作者: Email: zxw@yzu.edu.cn (朱兴旺)Email: lhn@ujs.edu.cn (李赫楠)

Covalent bond modulation of charge transfer for sensitive heavy metal ion analysis in a self-powered electrochemical sensing platform

Yun Chen1,3,4, Daijie Deng2, Li Xu2, Xingwang Zhu1,*(), Henan Li2,*(), Chengming Sun1,3,4   

  1. 1 Research Institute of Smart Agriculture, Agricultural College, College of Environmental Science and Engineering, College of Mechanical Engineering, Yangzhou University, Yangzhou 225009, Jiangsu Province, China
    2 School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China
    3 Cultivation and Construction Site of National Key Laboratory for Crop Genetics and Physiology in Jiangsu Province, Yangzhou University, Yangzhou 225009, Jiangsu Province, China
    4 Jiangsu Co-Innovation Center for Modern Production Technology of Grain Crops, Yangzhou University, Yangzhou 225009, Jiangsu Province, China
  • Received:2025-04-29 Revised:2025-06-22 Accepted:2025-07-31 Published:2025-11-01
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摘要：

光催化燃料电池光阳极活性材料的合理设计对开发高灵敏自供能电化学传感器至关重要。实现光阳极中电荷定向迁移和缩短传输路径是提升光催化燃料电池析氧反应性能的挑战。本文设计了一种具有N–W–O共价键的钨原子分散富碳石墨相氮化碳(W-CN-C)光阳极，用于构建对重金属铜离子检测的自供能光催化燃料电池传感器。通过自组装、剥离和热诱导相结合制备W-CN-C。N–W–O共价键作为界面电荷传输通道，促进电荷载流子分离与迁移。形成的富碳结构增加碳含量，进而增强W-CN-C的π-电子离域，从而显著拓宽太阳光响应范围。原子分散的钨提供活性位点，增强W-CN-C光阳极与电解质界面间的析氧反应动力学。这些协同效应显著提高可见光吸收能力和电荷分离与转移效率，增强W-CN-C光阳极的光电转换效率，表现出优异的析氧反应性能。基于Pt@C电催化剂阴极优异的氧还原反应性能，所构建的光催化燃料电池平台展现出增强的开路电位。在W-CN-C光阳极表面锚定对铜离子特异性识别的探针，构建了自供能光催化燃料电池传感平台，用于检测铜离子。铜离子与探针形成的复合物阻碍W-CN-C光阳极的电子传输，改变光催化燃料电池的输出检测信号。所构筑的传感器表现出跨越五个数量级的宽检测范围(2.0 × 10−2–9.2 × 102 nmol L−1)、低检测限(7.0 pmol L−1)、对常见干扰物的高选择性，以及对水生环境中重金属铜离子检测的可行性。此外，以万用表作为信号输出装置，传感平台实现对铜离子的自供能和便携式检测，检测范围为0.25–1.3 × 102 nmol L−1，检测限为84 pmol L−1。这项工作利用原子分散级金属引入的共价键作为电荷转移通道设计高性能光阳极，为构筑对环境检测的高灵敏自供能电化学传感器提供了思路。

关键词: 光催化燃料电池, 自供能电化学传感器, 析氧反应, 氮化碳, 电荷传输通道

Abstract:

Rational design of photoelectric active materials for photoanodes in photocatalytic fuel cells is crucial for developing highly sensitive self-powered electrochemical sensors. Achieving directional migration and shortening transmission pathways of charge in photoanodes remains a fundamental challenge for enhancing the oxygen evolution reaction performance of photocatalytic fuel cells. Herein, tungsten species atomically dispersed on carbon-rich graphitic carbon nitride (W-CN-C) with the N–W–O covalent bond was designed as the photoanode for constructing a self-powered photocatalytic fuel cell sensing of heavy metal copper ions. W-CN-C was synthesized by self-assembly, exfoliation, and thermal-induced treatment process. The N–W–O covalent bonds by anchoring tungsten atoms on carbon-rich carbon nitride served as an interfacial charge transport channel, facilitating the separation and migration of charge carriers. The carbon content increase by forming a carbon-rich structure can enhance π-electron delocalization in the W-CN-C, significantly broadening sunlight utilization range. The dispersed tungsten atoms provide effectively active sites, promoting the kinetics of the oxygen evolution reaction between the W-CN-C photoanode and electrolyte interface. The synergistic effects significantly enhance the visible light absorption ability and charge separation and transfer efficiency, improving the photoelectric conversion efficiency of W-CN-C photoanode, exhibiting superior oxygen evolution reaction performance, leading to the amplified open circuit potential in the photocatalytic fuel cell system based on excellent oxygen reduction reaction performance of the Pt@C electrocatalyst cathode. The specific identification probe for copper ions was effectively anchored on the W-CN-C photoanode to construct a self-powered photocatalytic fuel cell sensing platform for copper ions detection. The complex formed by copper ions and the probe hindered electron transport at the W-CN-C photoanode, altering the output detection signal of the photocatalytic fuel cell, thus demonstrating a broad detection range spanning five orders of magnitude (2.0 × 10−2–9.2 × 102 nmol L−1), a low limit of detection (7.0 pmol L−1), high selectivity against common interferents, and applicability for detecting heavy metal copper ions in the aquatic environment. Furthermore, the platform allowed for self-powered and portable determination of copper ions using a multimeter as a signal output device, achieving a detection range of 0.25–1.3 × 102 nmol L−1 and a limit of 84 pmol L−1. This work proposes an approach for developing a high-performance photoanode utilizing atomically dispersed metals to introduce covalent bonds as charge transfer channels, paving the way for highly sensitive self-powered electrochemical sensors for environmental monitoring.

Key words: Photocatalytic fuel cell, Self-powered electrochemical sensor, Oxygen evolution reaction, Carbon nitride, Charge transfer channel