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

doi:10.1007/s40242-019-8392-z

高等学校化学研究 ›› 2019, Vol. 35 ›› Issue (3): 370-376.doi: 10.1007/s40242-019-8392-z

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

School of Chemistry, Dalian University of Technology, Dalian 116023, P. R. China

收稿日期:2018-12-17 修回日期:2019-01-20 出版日期:2019-06-01 发布日期:2019-03-27
通讯作者: WU Shuo E-mail:wushuo@dlut.edu.cn
基金资助:
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).

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

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).

摘要/Abstract

摘要： 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.

关键词: Photoelectrochemical probe, Ru(II) bipyridyl complex, Hg²⁺ detection, Nanocomposite

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

WU Shuo, YANG Xinlan, ZHAO Yanqiu. Ru(II) Bipyridyl Complex and TiO₂ Nanocomposite Based Biomolecule-free Photoelectrochemical Sensor for Highly Selective Determination of Ultra-trace Hg²⁺ in Aqueous Systems[J]. 高等学校化学研究, 2019, 35(3): 370-376.

参考文献 43

[1]	Pardo-Yissar V., Katz E., Wasserman J., Willner I., J. Am. Chem. Soc., 2003, 125, 622
[2]	Zhao W. W., Xu J. J., Chen H. Y., Chem. Soc. Rev., 2015, 44, 729
[3]	Li R. Y., Zhang Y., Tu W. W., Dai Z. H., ACS Appl. Mater. Interfaces, 2017, 9, 22289
[4]	Cao H. J., Liu S. S., Tu W. W., Bao J. C., Dai Z. H., Chem. Commun., 2014, 50, 13315
[5]	Fan G. C., Zhu H., Du D., Zhang J. R., Zhu J. J., Lin Y. H., Anal. Chem., 2016, 88, 3392
[6]	Li H. B., Li J., Xu Q., Hu X. Y., Anal. Chem., 2011, 83, 9681
[7]	Haddour N., Chauvin J., Gondran C., Cosnier S., J. Am. Chem. Soc., 2006, 128, 9693
[8]	Lin Y. X., Zhou Q., Lin Y. P., Lu M. H., Tang D. P., Anal. Chim. Acta, 2015, 887, 67
[9]	Zhang B., Tang D. P., Goryacheva I. Y., Niessner R., Knopp D., Chem. Eur. J., 2013, 19, 2496
[10]	Ma W. G., Wang L. N., Zhang N., Han D. X., Dong X. D., Niu L., Anal. Chem., 2015, 87, 4844
[11]	Li H.B., Li J., Zhu Y. Y., Xie W. Y., Shao R., Yao X. X., Gao A. Q., Yin Y. D., Anal. Chem., 2018, 90, 5496
[12]	Zhao W. W., Zhang L., Xu J. J., Chen H. Y., Chem. Commun., 2012, 48, 9456
[13]	Wu S., Song H. L., Song J., He C., Ni J., Zhao Y. Q., Wang X. Y., Anal. Chem., 2014, 86, 5922
[14]	Dong D., Zheng D., Wang F. Q., Yang X. Q., Wang N., Li Y. G., Guo L. H., Cheng J., Anal. Chem., 2004, 76, 499
[15]	Liang M. M., Liu S. L., Wei M. Y., Guo L. H., Anal. Chem., 2006, 78, 621
[16]	Wu Y. P., Zhang B. T., Guo L. H., Anal. Chem., 2013, 85, 6908
[17]	Wang D. M., Gai Q. Q., Huang R. F., Zheng X. W., Biosens. Bioelectron., 2017, 98, 134
[18]	Wang Q., Zakeeruddin S. M., Nazeeruddin M. K., Humphry-Baker R., Grätzel M., J. Am. Chem. Soc., 2006, 128, 4446
[19]	Coronado E., Galán-Mascarós J. R., Martí-Gastaldo C., Palomares E., Durrant J. R., Vilar R., Gratzel M., Nazeeruddin M. K., J. Am. Chem. Soc., 2005, 127, 12351
[20]	Nazeeruddin M. K., Censo D. D., Humphry-Baker R., Grätzel M., Adv. Funct. Mater., 2006, 16, 189
[21]	Jiang X., Karlsson K. M., Gabrielsson E., Johansson E. M. J., Quintana M., Karlsson M., Sun L. C., Boschloo G., Hagfeldt A., Adv. Funct. Mater., 2011, 21, 2944
[22]	Oregan B., Gratzel M., Nature, 1991, 353, 737
[23]	Brown D. G., Schauer P. A., Borau-Garcia J., Fancy B. R., Berlinguette C. P., J. Am. Chem. Soc., 2013, 135, 1692
[24]	Galliano S., Bella F., Gerbaldi C., Falco M., Viscardi G., Grätzel M., Barolo C., Energy Technol., 2017, 5, 300
[25]	Park H., Bae E., Lee J. J., Park J., Choi W., J. Phys. Chem. B, 2006, 110, 8740
[26]	Kilså K., Mayo E. I., Brunschwig B. S., Gray H. B., Lewis N. S., Winkler J. R., J. Phys. Chem. B, 2004, 108, 15640
[27]	Palaniappan V., Sathaiah S., Bist H. D., Agarwala U. M., J. Am. Chem. Soc., 1988, 110, 6403
[28]	Hao Y. Q., Cui Y. L., Qu P., Sun W. Z., Liu S. P., Zhang Y. T., Li D. L., Zhang F. Q., Xu M. T., Electrochim. Acta, 2018, 259, 179
[29]	Li J., Lu L. P., Kang T. F., Cheng S. Y., Biosens. Bioelectron., 2016, 77, 740
[30]	Suherman A. L., Ngamchuea K., Tanner Ed. E. L., Sokolov S. V., Holter J., Young N. P., Compton R. G., Anal. Chem., 2017, 89, 7166
[31]	Hong M. Q., Wang M. Y., Wang J., Xu X. Q., Lin Z. Y., Biosens. Bioelectron., 2017, 94, 19
[32]	Ru J. X., Tang X. L., Ju Z. H., Zhang G. L., Dou W., Mi X. G., Wang C. M., Liu W. S., ACS Appl. Mater. Interfaces, 2015, 7, 4247
[33]	Tang W. X., Wang Z. Z., Yu J., Zhang F., He P. G., Anal. Chem., 2018, 90, 8337
[34]	Gumpu M. B., Veerapandian M., Krishnand U. M., Rayappan J. B. B., Talanta, 2017, 162, 574
[35]	Zhang Y., Shoaib A., Li J. J., Ji M. W., Liu J. J., Xu M., Tong B., Zhang J. T., Wei Q., Biosens. Bioelectron., 2016, 79, 866
[36]	Wu S., Tu W. J., Zhao Y. Q., Wang X. Y., Song J., Yang X. L., Anal. Chem., 2018, 90(24), 14423
[37]	Zhang B., Meng H. Y., Wang X., Li J., Chang H. H., Wei W. L., Sens. Actuators B:Chem., 2018, 255, 2531
[38]	Li S., Zhang F. H., Chen L. S., Zhang H., Li H. X., Sens. Actuators B:Chem., 2018, 257, 9
[39]	Wang D. M., Gai Q. Q., Huang R. F., Zheng X. W., Biosens. Bioelectron., 2017, 98, 134
[40]	Roy S., Prasad A., Tevatia R., Saraf F. R., Electrochem. Commun., 2018, 86, 94
[41]	Hao Y. Q., Cui Y. L., Qu P., Sun W. Z., Liu S. P., Zhang Y. T., Li D. L., Zhang F. Q., Xu M. T., Electrochim. Acta, 2018, 259, 179
[42]	Zhang L., Cole M. J., ACS Appl. Mater. Interfaces, 2015, 7, 3427
[43]	Fournier M., Hoogeveen A. D., Bonke A. S., Spiccia L., Simonov N. A., Sustan. Eng. Fuels, 2018, 2, 1707

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

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

可视化

摘要/Abstract

引用本文

使用本文

参考文献 43

相关文章 15

编辑推荐

Metrics

本文评价

[1]	GAO Huimin, SHI Rui, ZHU Youliang, QIAN Hujun and LU Zhongyuan. Coarse-grained Dynamics Simulation in Polymer Systems: from Structures to Material Properties[J]. 高等学校化学研究, 2022, 38(3): 653-670.
[2]	Hakan, AHAL, Gülben TORĞUT, Erdal CANPOLAT. Optimization of Electrical Conductivity of SA-graphene Nanocomposites Using Response Surface Methodology[J]. 高等学校化学研究, 2022, 38(2): 596-602.
[3]	LAN Weifei, HU Ruifeng, HUANG Danrong, DONG Xu, SHEN Gangyi, CHANG Shan, DAI Dongsheng. Palladium Nanoparticles/Graphdiyne Oxide Nanocomposite with Excellent Peroxidase-like Activity and Its Application for Glutathione Detection[J]. 高等学校化学研究, 2022, 38(2): 529-534.
[4]	CHAI Jingshan, LI Qiushi, ZHAO Yu, LIU Yang. Nanocomposites Facilitate the Removal of Aβ Fibrils for Neuroprotection[J]. 高等学校化学研究, 2022, 38(2): 522-528.
[5]	PAN Chuanqi, LIU Xiaoxuan, ZHANG Xiang, MAO Feihong, XU Peiyan, ZHU Yuhua, DENG Hongtao, LUO Zhu, SUN Hongwei, ZHANG Lizhi, GUO Yanbing. Fabrication and Excellent Antibacterial Activity of Well-defined CuO/Graphdiyne Nanostructure[J]. 高等学校化学研究, 2021, 37(6): 1341-1347.
[6]	XIANG Siyuan, MENG Qingnan, ZHANG Kai, GU Yue, LIU Wendong, YANG Bai. Facile Synthesis of ZnO-Au Nanopetals and Their Application for Biomolecule Determinations[J]. 高等学校化学研究, 2019, 35(5): 924-928.
[7]	GUAN Renquan, ZHAI Hongju, SUN Dewu, ZHANG Junkai, WANG Yan, LI Jiaxin. Effects of Ag Doping Content and Dispersion on the Photocatalytic and Antibacterial Properties in ZnO Nanoparticles[J]. 高等学校化学研究, 2019, 35(2): 271-276.
[8]	HAN Donglai, LI Boxun, XING Guoliang, ZHANG Yuanyuan, CHEN Yue, SUN Yantao, ZHANG Yongjun, LIU Yang, YANG Jinghai. Facile Synthesis of Fe₃Pt-Ag Nanocomposites for Catalytic Reduction of Methyl Orange[J]. 高等学校化学研究, 2018, 34(6): 871-876.
[9]	ZHANG Jindi, WANG Jun, ZHAO Lina, YANG Wenlong, BI Meng, WANG Yuchang, NIU Hongyan, LI Yuxin, WANG Binsong, GAO Yachen, LI Chensha, HUANG Xuezhen. Photo Responsive Silver Nanoparticles Incorporated Liquid Crystalline Elastomer Nanocomposites Based on Surface Plasmon Resonance[J]. 高等学校化学研究, 2017, 33(5): 839-846.
[10]	FENG Huiyun, GAO Lei, YE Xinhui, WANG Lei, XUE Zechun, KONG Jinming, LI Lianzhi. Synthesis of a Heptapeptide and Its Application in the Detection of Mercury(II) Ion[J]. 高等学校化学研究, 2017, 33(2): 155-159.
[11]	LI Xiaoshuang, LIU Yuan, GUO Chaofeng, LIU Haiyang, WANG Gang, CAI Qiang, YAO Youwei. Influence of Layered Aluminoborophosphate on Flame Retardance, Crystallization Behaviors and Mechanical Properties of Polyamide 66 Systems[J]. 高等学校化学研究, 2016, 32(1): 127-133.
[12]	CAO Wei, MA Yiran, ZHOU Wei, GUO Lin. One-pot Hydrothermal Synthesis of rGO-Fe₃O₄ Hybrid Nanocomposite for Removal of Pb(II) via Magnetic Separation[J]. 高等学校化学研究, 2015, 31(4): 508-513.
[13]	WEI Junchao, GUO-WANG Peiyao, CUI Liguo, ZHANG Haobin, DAI Yanfeng, LIU Tianxi. Novel Method to Graft Chitosan on the Surface of Hydroxyapatite Nanoparticles via “Click” Reaction[J]. 高等学校化学研究, 2014, 30(6): 1063-1065.
[14]	LÜ Leilei, CHEN Zhimin, XU Guiheng, ZHANG Jianan, XU Qun. Pine Needle-like Nanocomposite：Supercritical CO₂ Assisted Polythiophene Synthesis on Carbon Nanotubes[J]. 高等学校化学研究, 2014, 30(3): 521-526.
[15]	ZHANG Yinan, JIANG Dong, HE Zhi, YU Yunwu, ZHANG Haibo, JIANG Zhenhua. Hydrothermal Synthesis of PEG-capped ZnS：Mn²⁺ Quantum Dots Nanocomposites[J]. 高等学校化学研究, 2014, 30(1): 176-180.