U.S. Army Research Laboratory, Macromolecular Science & Technology Branch, Aberdeen Proving Ground, MD 21005, United States.
Carbohydr Polym. 2013 Jun 20;95(2):760-7. doi: 10.1016/j.carbpol.2013.03.041. Epub 2013 Mar 21.
In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images.
在这项工作中,我们描述了纳米原纤纤维素(NFC)水凝胶、气凝胶和薄膜的功能化,使用银作为例子。用于生产 NFC 的 TEMPO 工艺会产生带负电荷的表面羧酸基团,使其对过渡金属物种(如 Ag(+))具有高结合能力。首次揭示了过渡单价金属离子引发的 NFC 凝胶化。这种相互作用用于将 Ag(+)结合在 NFC 表面,并同时诱导 NFC-Ag(+)水凝胶的形成,其中 Ag(+)在没有额外还原剂的情况下被 NFC 上的羟基缓慢还原为 Ag 纳米颗粒。NFC-Ag(+)水凝胶的形成是由 NFC 上的羧酸基团与 Ag(+)的强烈结合以及足够的 NFC 表面电荷减少引发的。这种刚性水凝胶的储能模量在 ~6800Pa 的平台值处达到稳定。通过冷冻干燥或低浓度 Ag(+)的 NFC-Ag(+)分散体的溶液浇铸,分别制备了具有 Ag 纳米颗粒装饰的多孔气凝胶和平坦的 NFC 薄膜,然后进行 UV 还原。从 AFM 相图可以看出,NFC 上 Ag 物种的存在减少了薄膜形成过程中纳米原纤的聚集。