Gao Zhi-Wei, Li Yong-Yu, Li Pei-Hua, Yang Yuan-Fan, Zhao Yong-Huan, Yang Meng, Chen Shi-Hua, Song Zong-Yin, Huang Xing-Jiu
Key Laboratory of Environmental Optics and Technology, And Environmental Materials and Pollution Control Laboratory, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, China; Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China.
Key Laboratory of Environmental Optics and Technology, And Environmental Materials and Pollution Control Laboratory, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, China.
J Hazard Mater. 2024 Feb 5;463:132842. doi: 10.1016/j.jhazmat.2023.132842. Epub 2023 Oct 26.
Despite significant advancements in the detection of cadmium (Cd(II)) based on nanomaterial adsorbability, limited research has been conducted on ultra-sensitive and selective detection mechanisms, resulting in a lack of guidance for designing efficient interface materials to detect Cd(II). Herein, reductive Fe doping on CoP facilitates an efficient Fe-Co-P electron transfer path, which renders P the electron-rich site and subsequently splits a new orbital peak that matches with that of Cd(II) for excellent electrochemical performance. The sensitivity of Cd(II) was remarkably up to 109.75 μA μM on the Fe-CoP modified electrode with excellent stability and repeatability, surpassing previously reported findings. Meanwhile, the electrode exhibits exceptional selectivity towards Cd(II) ions compared to some bivalent heavy metal ions (HMIs). Moreover, X-ray absorption fine structure (XAFS) analysis reveals the interaction between P and Cd(II), which is further verified via density functional theory (DFT) calculation with the new hybrid peaks resulting from the splitting peak of P atoms coupled with the orbital energy level of Cd(II). Generally, doping engineering for specific active sites and regulation of orbital electrons not only provides valuable insights for the subsequent regulation of electronic configuration but also lays the foundation for customizing highly sensitive and selectivity sensors.
尽管基于纳米材料吸附性在镉（Cd(II)）检测方面取得了显著进展，但对超灵敏和选择性检测机制的研究有限，导致在设计用于检测Cd(II)的高效界面材料时缺乏指导。在此，在CoP上进行还原铁掺杂促进了高效的Fe-Co-P电子转移路径，使P成为富电子位点，随后分裂出一个与Cd(II)相匹配的新轨道峰，从而具有优异的电化学性能。在Fe-Co-P修饰电极上，Cd(II)的灵敏度显著高达109.75 μA μM，具有出色的稳定性和重复性，超过了先前报道的结果。同时，与一些二价重金属离子（HMI）相比，该电极对Cd(II)离子表现出优异的选择性。此外，X射线吸收精细结构（XAFS）分析揭示了P与Cd(II)之间的相互作用，通过密度泛函理论（DFT）计算进一步验证，P原子的分裂峰与Cd(II)的轨道能级产生了新的混合峰。一般来说，针对特定活性位点的掺杂工程和轨道电子的调控不仅为后续电子构型的调控提供了有价值的见解，也为定制高灵敏度和选择性传感器奠定了基础。
