Li Lei, Niu Rui, Zhang Ying
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an 710062 P. R. China
RSC Adv. 2018 Apr 3;8(22):12428-12438. doi: 10.1039/c8ra01343h. eCollection 2018 Mar 26.
Herein, we present the synthesis of Ag-Au bimetallic nanocomposites stabilized with organic-inorganic hybrid microgels. The aim is to get both the surface plasmon resonance (SPR) and catalytic performance of the composite material can be changed in response to external stimuli. Ag@poly(-isopropylacrylamide--3-methacryloxypro-pyltrimethoxysilane) (Ag@P(NIPAM--MAPTMS)) hybrid microgels were synthesized by seed-emulsion polymerization using Ag nanoparticles (NPs) as the core and NIPAM/MAPTMS as monomers. Ag-Au@P(NIPAM--MAPTMS) bimetallic hybrid microgels were prepared by a galvanic replacement (GR) reaction between Ag NPs and HAuCl, with the composition and structure of these bimetallic nanocomposites being determined by the amount of added HAuCl. The highly porous organic-inorganic microgel layer provided confined space for the GR reaction, effectively preventing the aggregation of Ag-Au NPs. The shell layer of P(NIPAM--MAPTMS) three-dimensional network chains not only enhanced nanocomposite dispersity and stability, but also provided highly porous gel microdomains that could increase the diffusion of the substrate and hence enhanced catalytic activity. Additionally, the SPR and catalytic properties of Ag-Au@P(NIPAM--MAPTMS) are reversibly sensitive to external temperature. With increase of temperature, the maximum absorption peak of bimetallic nanocomposites shifted to longer wavelengths, and the catalytic activity of these composites for the reduction of 4-nitrophenol by NaBH remarkably increased. The features above mentioned are related to presence of the thermosensitive PNIPAM chains and the highly porous structure constructed by rigid MAPTMS segments intersected between NIPAM chains.
在此,我们展示了用有机-无机杂化微凝胶稳定的Ag-Au双金属纳米复合材料的合成。目的是使复合材料的表面等离子体共振(SPR)和催化性能都能响应外部刺激而改变。以Ag纳米颗粒(NPs)为核,NIPAM/MAPTMS为单体,通过种子乳液聚合合成了Ag@聚(N-异丙基丙烯酰胺-3-甲基丙烯酰氧基丙基三甲氧基硅烷)(Ag@P(NIPAM-MAPTMS))杂化微凝胶。通过Ag NPs与HAuCl之间的电化学生成(GR)反应制备了Ag-Au@P(NIPAM-MAPTMS)双金属杂化微凝胶,这些双金属纳米复合材料的组成和结构由添加的HAuCl的量决定。高度多孔的有机-无机微凝胶层为GR反应提供了受限空间,有效防止了Ag-Au NPs的聚集。P(NIPAM-MAPTMS)三维网络链的壳层不仅增强了纳米复合材料的分散性和稳定性,还提供了高度多孔的凝胶微区,可增加底物的扩散,从而增强催化活性。此外,Ag-Au@P(NIPAM-MAPTMS)的SPR和催化性能对外部温度具有可逆敏感性。随着温度升高,双金属纳米复合材料的最大吸收峰向更长波长移动,并且这些复合材料对NaBH还原4-硝基苯酚的催化活性显著增加。上述特征与热敏性PNIPAM链的存在以及由NIPAM链之间相交的刚性MAPTMS链段构建的高度多孔结构有关。