负载金纳米粒子的聚苯乙烯/聚丙烯酸微球的合成及pH响应性能

doi:10.7503/cjcu20160084

摘要/Abstract

摘要：

以两步聚合法合成的聚苯乙烯(PS)/聚丙烯酸(PAA)核-壳结构复合微凝胶为载体, 硼氢化钠为还原剂, 柠檬酸钠为稳定剂, 通过原位控制性还原获得pH敏感性微凝胶负载纳米金粒子的PS/PAA-Au复合材料. 研究发现, 不同酸碱条件时, 复合微凝胶壳层高分子链的溶胀/收缩变化, 不仅可以调节纳米金粒子的表面等离子吸收, 还可以调节反应底物的扩散传质, 即借助载体微环境的变化来调控纳米金光学性能和催化性能, 从而实现复合纳米金材料的pH调控性.

关键词: 高分子微凝胶, pH敏感性, 纳米金, 表面等离子共振, 载体催化剂

Abstract:

The core-shell polystyrene(PS)/poly(acrylic acid)(PAA) composite microgels with pH sensitivity were synthesized via two-step polymerization method. Au nanoparticles were supported onto pH sensitivity composite microgels via in situ reduction of chloroauric acid(HAuCl₄) using NaBH₄ as reduction agent and sodium citrate as stabilizer. The results demonstrated that the plasmonic coupling of gold nanoparticles could be regulated, and the diffusion of reactive substrates availably controlled, due to the shrinkage and swelling performance of the shell chains under the different acid and alkali conditions. The optical property and catalytic activity of Au NPs could be regulated by changing the micro-environment of composite microgels. Therefore, the performance of composite materials could be realized the pH-controllable.

Key words: Polymer microgel, pH sensitivity, Au nanoparticle, Localized surface plasmon resonance(LSPR), Supported catalyst

中图分类号:

O648

TrendMD:

滕小波, 张春霞, 张颖. 负载金纳米粒子的聚苯乙烯/聚丙烯酸微球的合成及pH响应性能. 高等学校化学学报, 2016, 37(8): 1509.

TENG Xiaobo,ZHANG Chunxia,ZHANG Ying. Synthesis of the Supported Au Polystyrene/poly(acrylic acid) Composite Microspheres and Their pH Regulated Performance^†. Chem. J. Chinese Universities, 2016, 37(8): 1509.

图/表 12

Fig.1 Schematic diagram for the synthesis of PS/PAA-Au composite materials

Fig.2 TEM images of PS microspheres(A) and PS/PAA core-shell composite materials(B)

Fig.3 HRTEM images of PS/PAA-Au composite materials

Fig.4 Dark field scanning STEM image(A) and Au elemental mapping image(B) of PS/PAA-Au composite materials

Fig.5 XPS spectra(A) and Au4f XPS fitting curve(B) of the composite materials (A) a. PS/PAA; b. PS/PAA-Au.

Fig.6 XRD patterns(A), UV-Vis spectra(B) and TGA curves(C) of PS/PAA(a) and PS/PAA-Au(b)

Fig.7 UV-Vis spectra(A) and digital photos of suspension solution of PS/PAA-Au composite materials with different pH values(B1—B3) pH: (B1) 3.5; (B2) 5.5; (B3) 10.

Fig.8 Dispersity of PS/PAA-Au composite materials in water/chloroform with different pH values pH: (A) 3.5; (B) 5.5; (C) 10.

Fig.9 UV-Vis absorption spectra during the catalytic reduction of 4-NP with different pH values in the presence of PS/PAA-Au pH: (A) 3.08; (B) 3.92; (C) 5.16; (D) 6.48; (E) 8.05; (F) 9.0.

Fig.10 Plots of ln(At/A0) vs. time for the reduction of 4-NP with different pH values before(A) and after(B) deleting the introduction period and plots of the kapp as a function of pH(C)

Fig.11 Possible catalytic mechanism of the supported catalyst in the catalytic reduction of 4-NP

Fig.12 Conversion of 4-NP in five successive cycles with PS/PAA-Au composite materials

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