In-situ precipitation zero-valent Co on Co2VO4 to activate oxygen vacancies and enhance bimetallic ions redox for efficient detection toward Hg(II)

Zhi-Wei Gao; Hao Li; Pei-Hua Li; Yong-Yu Li; Jia-Qing Quan; Na Ma; Shi-Hua Chen; Xing-Jiu Huang; Zong-Yin Song; Meng Yang

doi:10.1016/j.aca.2024.342612

In-situ precipitation zero-valent Co on Co₂VO₄ to activate oxygen vacancies and enhance bimetallic ions redox for efficient detection toward Hg(II)

Anal Chim Acta. 2024 Jun 1:1306:342612. doi: 10.1016/j.aca.2024.342612. Epub 2024 Apr 16.

Authors

Zhi-Wei Gao¹, Hao Li², Pei-Hua Li³, Yong-Yu Li³, Jia-Qing Quan⁴, Na Ma⁵, Shi-Hua Chen⁶, Xing-Jiu Huang⁷, Zong-Yin Song⁸, Meng Yang⁹

Affiliations

¹ Institute of Environment, Hefei Comprehensive National Science Center, Hefei, 230088, 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; Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China; State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, 200050, China.
² 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; Wan Jiang New Industry Technology Development Center, Tongling, 244000, China.
³ 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.
⁴ Wan Jiang New Industry Technology Development Center, Tongling, 244000, China.
⁵ Institute of Environment, Hefei Comprehensive National Science Center, Hefei, 230088, China.
⁶ 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; State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, 200050, China. Electronic address: chenshh@issp.ac.cn.
⁷ Institute of Environment, Hefei Comprehensive National Science Center, Hefei, 230088, 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; Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China. Electronic address: xingjiuhuang@iim.ac.cn.
⁸ 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. Electronic address: zysong@issp.ac.cn.
⁹ Institute of Environment, Hefei Comprehensive National Science Center, Hefei, 230088, 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; Wan Jiang New Industry Technology Development Center, Tongling, 244000, China. Electronic address: myang@iim.ac.cn.

PMID: 38692793
DOI: 10.1016/j.aca.2024.342612

Abstract

Despite the widespread utilization of variable valence metals in electrochemistry, it is still a formidable challenge to enhance the valence conversion efficiency to achieve excellent catalytic activity without introducing heterophase elements. Herein, the in-situ precipitation of Co particles on Co₂VO₄ not only enhanced the concentration of oxygen vacancies (Ov) but also generated a greater number of low-valence metals, thereby enabling efficient reduction towards Hg(II). The electroanalysis results demonstrate that the sensitivity of Co/Co₂VO₄ towards Hg(II) was measured at an impressive value of 1987.74 μA μM^-1 cm^-2, significantly surpassing previously reported results. Further research reveals that Ov acted as the main adsorption site to capture Hg(II). The redox reactions of Co²⁺/Co³⁺ and V^3+/V⁴⁺ played a synergistic role in the reduction of Hg(II), accompanied by the continuous supply of electrons from zero-valent Co to expedite the valence cycle. The Co/Co₂VO₄/GCE presented remarkable selectivity towards Hg(II), with excellent stability, reproducibility, and anti-interference capability. The electrode also exhibited minimal sensitivity fluctuations towards Hg(II) in real water samples, underscoring its practicality for environmental applications. This study elucidates the mechanism underlying the surface redox reaction of metal oxides facilitated by zero-valent metals, providing us with new strategies for further design of efficient and practical sensors.

Keywords: Bimetallic ions cycle; Hg(II); Oxygen vacancy; Sensitivity and selectivity; Zero-valent co.