The Preparation and Performance of SPE Packing of Bonded Ligand on the Surface of Nanometer Titanium Dioxide
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摘要: 有机配位体/无机纳米复合材料作为固相萃取填料用于重金属离子分离富集是当前分析化学研究的热点课题。本文将含有N、S配位原子的氨基硫脲通过缩合反应接枝于纳米二氧化钛表面，制备了一种新型纳米TiO2/TSC复合固相萃取填料。通过红外光谱、X射线衍射、X射线光电子能谱和扫描电镜表征，此填料与共混法制备的聚合物包覆纳米二氧化钛复合填料相比，二氧化钛粒子(尺寸200~300 nm)分布更均匀，结构更稳定。用该填料制备的固相萃取小柱静态吸附Sb3+、Cd2+和Ba2+在30℃时饱和吸附量分别为13.9 mg/g、12.9 mg/g和11.2 mg/g，在优化的实验条件下三种金属离子的吸附回收率分别达到97.94%、95.65%和94.04%，实验数据重现性高(RSD < 5.5%)，吸附性能优于聚苯乙烯-甲基丙烯醛-氨基硫脲包覆纳米二氧化钛和纳米二氧化钛两种填料。本填料结合ICP-MS测定水样中以上三种离子的检出限分别为0.061 μg/L、0.013 μg/L和0.075 μg/L。Abstract: At present, the solid phase extraction packing of organic ligand/nano inorganic composite material is used to separate and enrich metal ions, which has become a hot research topic in analytical chemistry. A novel nano-TiO2/TSC solid-phase extraction packing was prepared by grafting thiosemicarbazone containing N, S coordination atoms onto the surface of nano-TiO2 by condensation reaction and is described in this paper. The structures and the property of synthesized composite were characterized and analyzed by Infrared Spectroscopy, X-ray Diffraction Scanning, X-ray Photoelectron Spectroscopy, and Electron Microscopy. The composition and size distribution of the packing particle were more uniform (the particle size is 200-300 nm) and more stable than the solid phase extraction packing made by physical blending technology. The saturation adsorption capacities of Sb3+, Cd2+ and Ba2+ on the solid phase extraction column prepared by this method at 30℃ were 13.9 mg/g, 12.9 mg/g, and 11.2 mg/g, respectively. The recoveries of three metal ions were 97.94%, 95.65% and 94.04%, respectively under the optimal experimental conditions. The data has good reproducibility with RSD < 5.5%. Thus, the adsorption property of the new nanometer TiO2/TSC composite solid phase extraction packing is an improvement on the styrene-methyl acrolein-thiosemicarbazide coated nano-titanium dioxide packing and nano-titanium dioxide packing. The contents of Sb3+, Cd2+ and Ba2+ in water samples were determined by Inductively Coupled Plasma-Mass Spectrometry coupled with the TiO2/TSC composite solid phase extraction packing, which yields detection limits of 0.061 μg/L, 0.013 μg/L, and 0.075 μg/L for Sb3+, Cd2+ and Ba2+, respectively.
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Key words:
- nano-titanium dioxide /
- bond ligand /
- Solid Phase Extraction /
- adsorption property /
- heavy metals
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表 1 流速对金属离子回收率的影响
Table 1. The influence of velocity on recovery rate of metal ions
金属离子 不同流速下金属离子的回收率(%) 0.5 mL/min 1.0 mL/min 1.5 mL/min 2.0 mL/min Sb3+ 97.94 96.03 92.18 85.43 Cd2+ 95.65 94.44 90.57 86.74 Ba2+ 94.04 93.41 90.56 85.05 
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表 2 洗脱剂对金属离子洗脱率的影响
Table 2. The influence of the elution liquid on recovery rate of metal ions
洗脱剂 金属离子回收率(%) Sb3+ Cd2+ Ba2+ 10 mL 1 mol/L硝酸 88.45 89.92 90.94 10 mL 3 mol/L硝酸 92.46 91.54 93.26 10 mL 5 mol/L硝酸 95.03 96.05 96.72 10 mL 1 mol/L硝酸+0.25 mL三乙醇胺 91.78 92.65 92.82 10 mL 3 mol/L硝酸+0.25 mL三乙醇胺 94.43 96.91 96.09 10 mL 5 mol/L硝酸+0.25 mL三乙醇胺 98.43 98.28 99.07
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表 3 固相萃取填料的吸附性能对比
Table 3. A comparison of adsorption performance of the SPE packings
填料 回收率(%) RSD(%) Sb3+ Cd2+ Ba2+ Sb3+ Cd2+ Ba2+ 表面键合配位体二氧化钛 97.94 95.65 94.04 5.4 4.7 5.1 聚合物包覆纳米二氧化钛 96.87 94.23 93.67 10.2 11.6 9.9 纳米二氧化钛 88.33 85.26 86.84 11.5 9.3 8.8
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表 4 样品测定结果(n=6)及检出限(n=20)
Table 4. Analytical results (n=6) and detection limits (n=20) of the sample
样品 Sb3+测定值(μg/L) Cd2+测定值(μg/L) Ba2+测定值(μg/L) 江水 0.42 0.23 2.56 湖水 1.53 3.01 10.6 地下水 0.11 0.14 0.87 加标回收率(%) 97.6~106.0 98.8~103.0 99.2~101.0 检出限(μg/L) 0.061 0.013 0.075
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