磁性硫化铜复合纳米材料的合成及其对水中汞离子的特异性吸附

doi:10.11944/j.issn.1000-0518.2020.11.200119

摘要/Abstract

摘要： 设计和合成吸附速率快、选择性好的吸附富集材料对Hg²⁺的高效吸附和精确检测具有重要意义。本文中,采用简单、经济的策略制备了磁性硫化铜复合纳米材料(Fe₃O₄@SiO₂@CuS),并且通过一系列吸附实验考察了核-壳结构的Fe₃O₄@SiO₂@CuS对水溶液中Hg²⁺的吸附性能。结果表明,Fe₃O₄@SiO₂@CuS显示出了快速的吸附富集速率和良好的吸附容量。同时,在多种金属离子共存的情况下,该材料表现出了优异的吸附选择性,Hg²⁺吸附率高达99.9%。由于该材料具备磁性,因此通过外加磁场即可实现吸附剂与水体简便快速的分离。以上结果表明,磁性金属硫化物纳米材料在吸附富集和检测领域具有良好的应用前景。

关键词: 磁性复合纳米材料, 硫化铜, 汞离子, 吸附, 富集

Abstract: Design and synthesis of adsorption/enrichment materials with rapid adsorption rate and good adsorption selectivity are significant for high-efficiency uptake and precise detection of Hg²⁺ ions. In this work, a magnetic CuS composite nanomaterial (Fe₃O₄@SiO₂@CuS) was successfully synthesized by a facile and economic strategy, and a series of adsorption experiments was carried out to investigate the adsorption performance of core-shell structured Fe₃O₄@SiO₂@CuS towards Hg²⁺ ions in aqueous solution. The results show that Fe₃O₄@SiO₂@CuS exhibits fast adsorption kinetics and excellent adsorption capacity. It also displays a superior selective capture of Hg²⁺ in the presence of other co-existing metal ions, and the removal efficiency of Hg²⁺ is as high as 99.9%. In addition, Fe₃O₄@SiO₂@CuS can be separated easily and fastly from samples under an external magnetic field, which is attributed to its magnetic property. These results demonstrate that magnetic metal sulfide composite nanomaterials have great application prospects in the areas of adsorption, enrichment and detection.

Key words: magnetic composite nanomaterials, CuS, mercury ion, adsorption, enrichment

中图分类号:

王秋实, 贺军辉. 磁性硫化铜复合纳米材料的合成及其对水中汞离子的特异性吸附[J]. 应用化学, 2020, 37(11): 1316-1323.

WANG Qiushi, HE Junhui. Synthesis of Magnetic CuS Composite Nanomaterial and Its Specific Adsorption of Hg(II) in Water[J]. Chinese Journal of Applied Chemistry, 2020, 37(11): 1316-1323.

参考文献

[1] Hadavifar M,Bahramifar N,Younesi H,et al. Adsorption of Mercury Ions from Synthetic and Real Wastewater Aqueous Solution by Functionalized Multi-Walled Carbon Nanotube with both Amino and Thiolated Groups[J]. Chem Eng J,2014,237:217-228.
[2] Jeong H Y,Klaue B,Blum J D,et al. Sorption of Mercuric Ion by Synthetic Nanocrystalline Mackinawite (FeS)[J]. Environ Sci Technol,2007,41(22):7699-7705.
[3] Peng C,He M,Chen B,et al. Magnetic Sulfur-Doped Porous Carbon for Preconcentration of Trace Mercury in Environmental Water Prior to ICP-MS Detection[J]. Analyst,2017,142(23):4570-4579.
[4] Klímová K,Pumera M,Luxa J,et al. Graphene Oxide Sorption Capacity Towards Elements over the Whole Periodic Table:A Comparative Study[J]. J Phys Chem C,2016,120(42):24203-24212.
[5] Ma L,Islam S M,Xiao C,et al. Rapid Simultaneous Removal of Toxic Anions [HSeO₃]^-, [SeO₃]^2-, and [SeO₄]^2-, and Metals Hg²⁺, Cu²⁺, and Cd²⁺ by MoS^2-₄ Intercalated Layered Double Hydroxide[J]. J Am Chem Soc,2017,139(36):12745-12757.
[6] Halder S,Mondal J,Ortega-Castro J,et al. A Ni-Based MOF for Selective Detection and Removal of Hg²⁺ in Aqueous Medium:A Facile Strategy[J]. Dalton Trans,2017,46(6):1943-1950.
[7] Huang L,He M,Chen B,et al. Facile Fabrication of N-Doped Magnetic Porous Carbon for Highly Efficient Mercury Removal[J]. ACS Sustainable Chem Eng,2018,6(8):10191-10199.
[8] Li J,Liu Y,Ai Y,et al. Combined Experimental and Theoretical Investigation on Selective Removal of Mercury Ions by Metal Organic Frameworks Modified with Thiol Groups[J]. Chem Eng J,2018,354:790-801.
[9] Zhang L,Wang J,Du T,et al. NH₂-MIL-53(Al) Metal-Organic Framework as the Smart Platform for Simultaneous High-Performance Detection and Removal of Hg²⁺[J]. Inorg Chem,2019,58(19):12573-12581.
[10] Yap P L,Kabiri S,Tran D N H,et al. Multifunctional Binding Chemistry on Modified Graphene Composite for Selective and Highly Efficient Adsorption of Mercury[J]. ACS Appl Mater Interfaces,2019,11(6):6350-6362.
[11] Bandaru N M,Reta N,Dalal H,et al. Enhanced Adsorption of Mercury Ions on Thiol Derivatized Single Wall Carbon Nanotubes[J]. J Hazard Mater,2013,261:534-541.
[12] Ram B,Chauhan G S. New Spherical Nanocellulose and Thiol-Based Adsorbent for Rapid and Selective Removal of Mercuric Ions[J]. Chem Eng J,2018,331:587-596.
[13] Ke F,Qiu L G,Yuan Y P,et al. Thiol-Functionalization of Metal-Organic Framework by a Facile Coordination-Based Postsynthetic Strategy and Enhanced Removal of Hg²⁺ from Water[J]. J Hazard Mater,2011,196:36-43.
[14] Ai K,Ruan C,Shen M,et al. MoS₂ Nanosheets with Widened Interlayer Spacing for High-Efficiency Removal of Mercury in Aquatic Systems[J]. Adv Funct Mater,2016,26(30):5542-5549.
[15] Jia F,Wang Q,Wu J,et al. Two-Dimensional Molybdenum Disulfide as a Superb Adsorbent for Removing Hg²⁺ from Water[J]. ACS Sustainable Chem Eng,2017,5(8):7410-7419.
[16] Song Y,Lu M,Huang B,et al. Decoration of Defective MoS₂ Nanosheets with Fe₃O₄ Nanoparticles as Superior Magnetic Adsorbent for Highly Selective and Efficient Mercury Ions (Hg²⁺) Removal[J]. J Alloys Compd,2018,737:113-121.
[17] Hu M,Tian H,He J. Unprecedented Selectivity and Rapid Uptake of CuS Nanostructures toward Hg(II) Ions[J]. ACS Appl Mater Interfaces,2019,11(21):19200-19206.
[18] Zhu M,Zhang W,Li Y,et al. Multishell Structured Magnetic Nanocomposites Carrying a Copolymer of Pyrrole-Thiophene for Highly Selective Au(III) Recovery[J]. J Mater Chem A,2016,4(48):19060-19069.
[19] Stöber W,Fink A,Bohn E. Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range[J]. J Colloid Interface Sci,1968,26(1):62-69.
[20] ZHANG Xinyu,SUN Xiaomin,YUAN Guofu,et al. Primary Analysis of Water pH and Salinity Monitoring Data on Chinese Ecosystem Research Network(CERN)[J]. Adv Earth Sci,2009,24(9):1042-1050(in Chinese).
张心昱,孙晓敏,袁国富,等. 中国生态系统研究网络水体pH和矿化度监测数据初步分析[J]. 地球科学进展,2009,24(9):1042-1050.
[21] Powell K J,Brown P L,Byrne R H,et al. Chemical Speciation of Environmentally Significant Heavy Metals with Inorganic Ligands.Part 1:The Hg²⁺-Cl^-, OH^-, CO^2-₃, SO^2-₄, and PO^3-₄ Aqueous Systems (IUPAC Technical Report)[J]. Pure Appl Chem,2005,77(4):739-800.
[22] Dubale A A,Tamirat A G,Chen H M,et al. Highly Stable CuS and CuS-Pt Catalyzed Cu₂O/CuO Heterostructure as Efficient Photocathode for Hydrogen Evolution Reaction[J]. J Mater Chem A,2015,4(6):2205-2216.
[23] Leloup J,Ruaudelteixier A,Barraud A,et al. XPS Study of Copper Sulfides Inserted into a Langmuir-Blodgett Matrix[J]. Appl Surf Sci,1993,68(2):231-242.
[24] Pearson R G. Hard and Soft Acids and Bases[J]. J Am Chem Soc,1963,85(22):3533-3539.
[25] Behra P,Bonnissel-Gissinger P,Alnot M,et al. XPS and XAS Study of the Sorption of Hg(II) onto Pyrite[J]. Langmuir,2001,30(1):269-272.
[26] Tang J,Ni S,Chen Q,et al. CuS@Cu Freestanding Electrode via Electrochemical Corrosion for High Performance Li-Ion Batteries[J]. Mater Lett,2017,201:13-17.