四硫代钼酸根/1-辛烷磺酸根/LEuH复合体发光性能及对Hg2+的识别

doi:10.7503/cjcu20180153

摘要/Abstract

摘要：

采用改进的均匀沉淀法合成了硝酸根插层的稀土铕层状氢氧化物(NO₃-LEuH), 通过离子交换法将阴离子型表面活性剂1-辛烷磺酸根(OS^-)及无机阴离子Mo$S_{4}^{2-}$共插层于LEuH的层间, 通过改变Mo$S_{4}^{2-}$和OS^-的投料比得到一系列发光强度不同的复合体(MoS₄)_xOS_1-_x-LEuH(x=0.02, 0.10, 0.20). 采用X射线粉末衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)和荧光分光光度计(PL)等研究了其结构及性质. 结果表明, Mo$S_{4}^{2-}$会明显削弱层板Eu³⁺的红光发射, 且在一定Mo$S_{4}^{2-}$/OS^-摩尔比范围内发光强度随Mo$S_{4}^{2-}$含量增加而降低. 选择Mo$S_{4}^{2-}$:OS^-摩尔比为0.02:0.98的复合体(MoS₄)_0.02OS_0.98-LEuH用于水体系重金属离子Hg²⁺, Cu²⁺, Ag⁺, Pb²⁺的荧光识别, 发现剥离态复合体对Hg²⁺具有选择性识别能力, 加入含Hg²⁺水溶液后发光有一定程度增强, 可用作off-on型荧光传感器件识别毒性Hg²⁺.

关键词: 1-辛烷磺酸根, 四硫代钼酸根, 层状稀土铕氢氧化物复合体, 荧光传感, Hg²⁺识别

Abstract:

NO₃-LEuH(LEuH=layered europium hydroxide) precursor was synthesized via a developed hydrothermal method, and co-intercalation of Mo$S_{4}^{2-}$ and OS^- into LEuH layers was achieved by an ion-exchange with N$O_{3}^{-}$, thus a series of composites of (MoS₄)_xOS_1-_x-LEuH(x=0.02, 0.10, and 0.20) with different molar ratios of Mo$S_{4}^{2-}$ to OS^- was obtained. The structure and property of(MoS₄)_xOS_1-_x-LEuH composites were investigated via powder X-ray diffraction(XRD) patterns, Fourier transformed infrared spectra(FTIR) and photoluminescence(PL) spectra. The delaminated (MoS₄)_xOS_1-_x-LEuH in formamide presented markedly quenched luminescence of layer Eu³⁺ ions at 614 nm, and higher Mo$S_{4}^{2-}$:OS^- molar ratios(from 0.02:0.98 to 0.20:0.80) resulted in weakened luminescence intensity. The fluorescence recognization ability towards heavy metal ions of Hg²⁺, Cu²⁺, Ag⁺ and Pb²⁺ of the delaminated (MoS₄)_0.02OS_0.98-LEuH composite was investigated. After addition of aqueous solutions of Hg²⁺(0.01—10 μmol/L), the (MoS₄)_0.02OS_0.98-LEuH exhibited enhanced luminescence of layer Eu³⁺.

Key words: 1-Octane sulfonate(OS^-), Mo$S_{4}^{2-}$, Layered europium hydroxide(LEuH) composite, Fluorescence chemosensor, Detection of Hg²⁺

中图分类号:

O614.3
O657

TrendMD:

李建, 谢林霞, 梁足培, 国荣, 刘晨昱, 马淑兰. 四硫代钼酸根/1-辛烷磺酸根/LEuH复合体发光性能及对Hg²⁺的识别. 高等学校化学学报, 2018, 39(10): 2154.

LI Jian,XIE Linxia,LIANG Zupei,GUO Rong,LIU Chenyu,MA Shulan. Luminescence Property and Detection Capability Towards Hg²⁺ of LEuH Composites with Mo $S 4 2 -$ and OS^- Anions^†. Chem. J. Chinese Universities, 2018, 39(10): 2154.

图/表 11

Fig.1 XRD patterns of NO3-LEuH(a), OS-LEuH(b, b’), (MoS4)0.02OS0.98-LEuH(c, c’), (MoS4)0.10OS0.90-LEuH(d, d’) and (MoS4)0.20OS0.80-LEuH(e, e’)The d-values are given in nm. a—e. Wide angle XRD; b’—e’. Small angle XRD.

Fig.2 FTIR spectra of NO3-LEuH(a), OS-LEuH(b), (MoS4)0.02OS0.98-LEuH(c),(MoS4)0.10OS0.90-LEuH(d) and (MoS4)0.20OS0.80-LEuH(e)

Table 1 Chemical composition of NO3-LEuH and OS-LEuH and (MoS4)0.02OS0.98-LEuH

Sample	Chemical formula	Found(calcd.)(%)
Sample	Chemical formula	Eu	Mo	C	H	N
NO₃-LEuH	Eu(OH)_2.41(NO₃)_0.49(CO₃)_0.05·0.8H₂O	62.10 (62.50)	—	0.28 (0.25)	1.61 (1.73)	2.71 (2.83)
OS-LEuH	Eu(OH)_2.41(C₈H₁₇O₃S)_0.64(NO₃)_0.01·0.8H₂O	44.72 (45.88)	—	18.05 (18.52)	4.13 (4.49)	0.04 (0.04)
(MoS₄)_0.02OS_0.98-LEuH	Eu(OH)_2.41(OS)_0.51(MoS₄)_0.03(NO₃)_0.02·1.6H₂O	46.11 (46.31)	0.82 (0.88)	14.74 (14.92)	4.01 (4.35)	0.09 (0.09)

Fig.3 Photoluminescence emission spectra of solid samples(A) and colloidal suspensions(B) of OS-LEuH(a), (MoS4)0.02·OS0.98-LEuH(b), (MoS4)0.10OS0.90-LEuH(c) and (MoS4)0.20OS0.80-LEuH(d)(λex=395 nm)

Fig.4 UV-Vis adsorption spectra of MoS42- in FM solution(a) and excitation spectra of OS-LEuH colloidal suspension in FM(b)(λem=614 nm)a. 5 mg (NH4)2MoS4 was dissolved in 100 mL FM.

Fig.5 Photoluminescence emission spectra of (MoS4)0.02OS0.98-LEuH colloidal suspension in FM(a)[0.02 g(MoS4)0.02OS0.98-LEuH dispersed in 10 mL FM], 1 mL colloidal suspension+3 mL FM(b) and 1 mL colloidal suspension+3 mL H2O(c)(λex=395 nm)

Fig.6 Photoluminescence emission spectra of 1 mL(MoS4)0.02OS0.98-LEuH colloidal suspension+3 mL H2O(a) and aqueous solutions of Hg2+ with concetrations of 0.050 μmol/L(b), 0.50 μmol/L(c), 5.0 μmol/L(d) and 50 μmol/L(e), respectively(λex=395 nm)

Fig.7 Photoluminescence emission spectra of 1 mL (MoS4)0.02OS0.98-LEuH colloid+3 mL H2O or aqueous solutions of Cu2+ with concetrations of 0.16, 1.6, 16 and 160 μmol/L, respectively(λex=395 nm)

Fig.8 Photoluminescence emission spectra of 1 mL(MoS4)0.02OS0.98-LEuH colloid+3 mL H2O or aqueous solutions of Ag+ with concetrations of 0.092, 0.92, 9.2 and 92 μmol/L, respectively(λex=395 nm)

Fig.9 Photoluminescence emission spectra of 1 mL(MoS4)0.02OS0.98-LEuH colloidal suspension+3 mL H2O or aqueous solutions of Pb2+ with concetrations of 0.048, 0.48, 4.8 and 48 μmol/L, respectively(λex=395 nm)

Fig.10 Intercalation and ion-exchange of MoS42- with NO3-LEuH and the formed (MoS4)0.02OS0.98-LEuH composite showing photoluminescence quenching in FM and enhanced emission in Hg2+/H2O case

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四硫代钼酸根/1-辛烷磺酸根/LEuH复合体发光性能及对Hg²⁺的识别

Luminescence Property and Detection Capability Towards Hg²⁺ of LEuH Composites with Mo $S 4 2 -$ and OS^- Anions^†

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