Chemical Research in Chinese Universities ›› 2019, Vol. 35 ›› Issue (3): 370-376.doi: 10.1007/s40242-019-8392-z

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Ru(II) Bipyridyl Complex and TiO2 Nanocomposite Based Biomolecule-free Photoelectrochemical Sensor for Highly Selective Determination of Ultra-trace Hg2+ in Aqueous Systems

WU Shuo, YANG Xinlan, ZHAO Yanqiu   

  1. School of Chemistry, Dalian University of Technology, Dalian 116023, P. R. China
  • Received:2018-12-17 Revised:2019-01-20 Online:2019-06-01 Published:2019-03-27
  • Contact: WU Shuo E-mail:wushuo@dlut.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21675018), the Foundamental Research Funds for the Central Universities of China(No.DUT18LK37) and the Foundation of the State Key Laboratory of Analytical Chemistry for Life Science, China(No.SKLACLS1705).

Abstract: A biomolecule-free photoelectrochemical(PEC) probe(denoted as Ru-1) was designed, synthesized and coupled with TiO2 nanoparticles(NPs) for the highly sensitive and selective PEC detection of Hg2+, a model analyte with hypertoxicity to both human health and ecosystem. The probe Ru-1 was designed with Ru(Ⅱ) bipyridyl complex as the chromophore, thiocyanate ligand as the recognition unit, and carboxylate group as the linkage site to connect Ru-1 to TiO2 nanoparticles. Under irradiation, Ru-1 shows strong affinity to TiO2 and good photophysical properties of strong visible light absorption, slow electron-hole(e-h+) recombination, and fast photoelectron injection to TiO2 nanoparticles via the π-bridge of 4-(2,2'-bipyridin)-4-yl-thiophene moiety. However, the specific coordination of Hg2+ with Ru-1 via the thiol moiety in the thiocyanate enlarges the band gap of the complex and reduces the photocurrent significantly. The synergistic interaction between TiO2 nanoparticles and the Ru-1 complex led to a selective PEC sensing strategy for Hg2+ detection. Detectable linear ranges from 10-12 g/mL to 10-7 g/mL and from 10-7 g/mL to 10-3 g/mL were obtained without the interference from possibly co-existed metal ions. The good analytical performances indicate the chemical probe based biomolecule-free PEC platform may offer a new route for the detection of biologically and environmentally important small molecules.

Key words: Photoelectrochemical probe, Ru(II) bipyridyl complex, Hg2+ detection, Nanocomposite