聚苯乙烯/银纳米粒子复合微球的合成及催化性能

doi:10.7503/cjcu20170159

摘要/Abstract

摘要：

首先通过乳液聚合和浓硫酸酸化制备表面富含磺酸根的磺化聚苯乙烯(PS)微球(直径532 nm), 再用其静电吸附[Ag(NH₃)₂]⁺离子, 最后采用聚乙烯吡咯烷酮还原表面吸附的[Ag(NH₃)₂]⁺ 离子, 得到了负载银纳米粒子的PS/Ag NPs复合微球. 采用扫描电子显微镜、透射电子显微镜、紫外-可见光谱、红外光谱和X射线衍射表征了PS/Ag NPs复合微球, 并考察了其对甲基蓝(MB)的催化性能. 结果表明, Ag纳米粒子高度分散在磺化PS微球表面; 该PS/Ag NPs复合微球对催化转化MB有较高的催化活性, 并可多次重复利用. 本研究在催化降解有机污染物方面有一定的实用价值.

关键词: 聚苯乙烯微球, 银纳米粒子, 催化, 甲基蓝, 有机污染物

Abstract:

This study reports the preparation of polystyrene/Ag nanoparticles(PS/Ag NPs) composite spheres and their catalytic application toward MB conversion. The composite spheres were prepared by synthesis of PS speres, their sulfonation, and finally reduction of [Ag(NH₃)₂]⁺ ions absorbed on sulfonated PS spheres using polyvinyl pyrrolidone. The resultant PS/Ag NPs composite spheres were characterized using scanning electron miscroscopy, transmission electron microscopy, UV-Vis spectroscopy, Infrared spectroscopy and X-ray diffraction spectroscopy, and their catalytic properties were examined. These results show that small Ag NPs with diameter of about 9—18 nm were well dispersed on the PS spheres and the PS/Ag NPs composite exhibits excellent catalytic activity towards MB conversion without obvious deteriorating after five cycles of running. This study, thus, may have impact on the degradation of organic contaminants in water.

Key words: Polystyrene sphere, Ag nanoparticles, Catalysis, Methyl blue, Organic contaminant

中图分类号:

O643

TrendMD:

申晓华, 胡家文. 聚苯乙烯/银纳米粒子复合微球的合成及催化性能. 高等学校化学学报, 2017, 38(11): 2015.

SHEN Xiaohua, HU Jiawen. Synthesis of Polystyrene/silver Nanoparticels Composite Spheres and Their Catalytical Application^†. Chem. J. Chinese Universities, 2017, 38(11): 2015.

图/表 11

Fig.1 SEM images of PS spheres(A) and sulfonated PS spheres(B)

Fig.2 FTIR spectra for PS spheres(A) and sulfonated PS spheres(B)

Fig.3 SEM images of the PS/Ag NPs composite spheres prepared from 0.29 mol/L(A), 0.58 mol/L(B), 0.87 mol/L(C) and 1.16 mol/L(D) [Ag(NH3)2]+ solutions

Fig.4 TEM images(A—D) for the PS/Ag NPs composite spheres prepared from 0.29 mol/L(A, A'), 0.58 mol/L(B, B'), 0.87 mol/L(C, C') and 1.16 mol/L(D, D') [Ag(NH3)2]+ solutions and corresponding size distributions(A'—D') of Ag NPs on the PS spheres

Fig.5 XRD patterns(A) for PS spheres(a), PS/Ag NPs composite spheres(b) and standard pattern for Ag(c) and UV-Vis spectra(B) of PS/Ag NPs composite crospheres prepared from 0.29 mol/L(a), 0.58 mol/L(b), 0.87 mol/L(c) and 1.16 mol/L(d) [Ag(NH3)2]+ solutions

Fig.6 Schematic showing the reduction mechanism of MB on the PS/Ag NPs composite spheres(A) and time-dependent UV-Vis spectra for MB solution(0.04 mmol/L) without catalyst(B) and in the presence of sulfonated PS spheres(C) and pure Ag NPs(D)

Fig.7 Time-dependent UV-Vis spectra for MB solution(0.04 mmol/L) in the presence of PS/Ag NPs composite spheres prepared from 0.29(A), 0.58(B), 0.87(C) and 1.16 mol/L(D) [Ag(NH3)2]+ solutions

Fig.8 Conversion efficiency of MB solution with different initial concentration in the presence of PS/Ag NPs composite(1.1 mg, prepared from 1.16 mol/L [Ag(NH3)2]+ solution)

Fig.9 Natural logarithm of the absorbance ratio(A/A0) at λmax vs. the reduction time extracted from the time-dependent UV-Vis spectra

Table 1 Comparison of normalized kinetic constant of different catalysts used for the conversion of MB

Material	Temperature/℃	Ag NPs diameter/nm	k/(s^-1·mg^-1)	Ref.
Poly(S-co-HEA)/Ag NPs	r. t.	23.0	6.60×10^-4	[25]
Fe₃O₄@polydopamine-Ag microspheres	25	25.0	1.43×10^-3	[24]
Ag NPs on Fe₃O₄@C nanocomposites	25	10.0	5.67×10^-4	[26]
LCPS/Ag NPs	25	40.0	1.62×10^-3	[27]
P(St-NaSS)/Ag NPs	25	19.2	2.60×10^-3	[28]
PS/Ag NPs composite spheres	25	18.5	2.42×10^-3	This work

Fig.10 Covertic degradation kinetics for MB solution in five cycles with the presence of PS/Ag NPs composite spheres(prepared from 1.16 mol/L [Ag(NH3)2]+ solution)(A) and absorbance intensity variation for each cycle(B)

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