Uemura Takashi, Ohba Masaaki, Kitagawa Susumu
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Inorg Chem. 2004 Nov 15;43(23):7339-45. doi: 10.1021/ic0488435.
Prussian blue (PB) nanoparticles protected by organic polymers such as poly(vinylpyrrolidone) (PVP) and poly(diallyldimethylammonium chloride) (PDDA) were prepared. Different experimental conditions (concentrations of Fe ions and feed ratios of Fe to the polymers) have been investigated to control the size of the PB nanoparticles. For example, the averaged dimensions of the PB nanoparticles were tuned from 12 to 27 nm by use of PVP in the different conditions. Addition of PDDA produced the PB nanoparticles with very small dimensions (5-8 nm) by an effective electrostatic interaction. We found that the surface environments of the PB nanoparticles affect the inherent properties of PB. The shifts of charge transfer (CT) absorptions from Fe(2+) to Fe(3+) in the PB nanoparticles resulted from the surface-protecting polymers. Especially, the PB nanoparticles with the PVP protection show high solubility in a variety of organic solvents and a solvent-dependent CT absorption. Measurement of the magnetic properties of the PB nanoparticles showed unprecedented size-dependency, surface effect, and superparamagnetic properties.
制备了由诸如聚乙烯吡咯烷酮(PVP)和聚二烯丙基二甲基氯化铵(PDDA)等有机聚合物保护的普鲁士蓝(PB)纳米颗粒。研究了不同的实验条件(铁离子浓度以及铁与聚合物的进料比)以控制PB纳米颗粒的尺寸。例如,在不同条件下使用PVP将PB纳米颗粒的平均尺寸从12纳米调整到27纳米。通过有效的静电相互作用,添加PDDA产生了尺寸非常小(5 - 8纳米)的PB纳米颗粒。我们发现PB纳米颗粒的表面环境会影响PB的固有性质。PB纳米颗粒中从Fe(2+)到Fe(3+)的电荷转移(CT)吸收峰的位移是由表面保护聚合物引起的。特别是,具有PVP保护的PB纳米颗粒在多种有机溶剂中表现出高溶解性以及溶剂依赖性的CT吸收。对PB纳米颗粒磁性的测量显示出前所未有的尺寸依赖性、表面效应和超顺磁性。