Department of Chemistry and Life Science, United States Military Academy, West Point, NY 10996, USA.
Department of Mathematical Sciences, United States Military Academy, West Point, NY 10996, USA.
Molecules. 2018 Jun 9;23(6):1405. doi: 10.3390/molecules23061405.
Noble metal aerogels offer a wide range of catalytic applications due to their high surface area and tunable porosity. Control over monolith shape, pore size, and nanofiber diameter is desired in order to optimize electronic conductivity and mechanical integrity for device applications. However, common aerogel synthesis techniques such as solvent mediated aggregation, linker molecules, sol⁻gel, hydrothermal, and carbothermal reduction are limited when using noble metal salts. Here, we present the synthesis of palladium aerogels using carboxymethyl cellulose nanofiber (CNF) biotemplates that provide control over aerogel shape, pore size, and conductivity. Biotemplate hydrogels were formed via covalent cross linking using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) with a diamine linker between carboxymethylated cellulose nanofibers. Biotemplate CNF hydrogels were equilibrated in precursor palladium salt solutions, reduced with sodium borohydride, and rinsed with water followed by ethanol dehydration, and supercritical drying to produce freestanding aerogels. Scanning electron microscopy indicated three-dimensional nanowire structures, and X-ray diffractometry confirmed palladium and palladium hydride phases. Gas adsorption, impedance spectroscopy, and cyclic voltammetry were correlated to determine aerogel surface area. These self-supporting CNF-palladium aerogels demonstrate a simple synthesis scheme to control porosity, electrical conductivity, and mechanical robustness for catalytic, sensing, and energy applications.
贵金属气凝胶由于其高比表面积和可调孔隙率,提供了广泛的催化应用。为了优化电子电导率和机械完整性,以满足器件应用的要求,需要对整体形状、孔径和纳米纤维直径进行控制。然而,在使用贵金属盐时,溶剂介导聚集、连接分子、溶胶-凝胶、水热和碳热还原等常见的气凝胶合成技术受到限制。在这里,我们提出了使用羧甲基纤维素纳米纤维(CNF)生物模板合成钯气凝胶的方法,该方法可以控制气凝胶的形状、孔径和电导率。生物模板水凝胶通过使用 1-乙基-3-(3-二甲基氨基丙基)碳化二亚胺盐酸盐(EDC)与羧甲基化纤维素纳米纤维之间的二胺连接子进行共价交联形成。生物模板 CNF 水凝胶在钯盐前体溶液中平衡,用硼氢化钠还原,然后用水和乙醇进行冲洗,进行超临界干燥以产生独立支撑的气凝胶。扫描电子显微镜表明存在三维纳米线结构,X 射线衍射证实了钯和钯氢化物相。气体吸附、阻抗谱和循环伏安法被关联起来以确定气凝胶的比表面积。这些自支撑的 CNF-钯气凝胶展示了一种简单的合成方案,可以控制催化、传感和能源应用的多孔性、导电性和机械鲁棒性。