Department of NanoEngineering, University of California, San Diego , La Jolla, California 92093, United States.
ACS Nano. 2018 Jan 23;12(1):432-440. doi: 10.1021/acsnano.7b06667. Epub 2018 Jan 11.
A variety of nanoporous transition metals, Fe, Co, Au, Cu, and others, have been readily formed by a scalable, room-temperature synthesis process. Metal halide compounds are reacted with organolithium reductants in a nonpolar solvent to form metal/lithium halide nanocomposites. The lithium halide is then dissolved out of the nanocomposite with a common organic solvent, leaving behind a continuous, three-dimensional network of metal filaments that form a nanoporous structure. This approach is applicable to both noble metals (Cu, Au, Ag) and less-noble transition metals (Co, Fe, Ni). The microstructures of these nanoporous transition metals are tunable, as controlling the formation of the metal structure in the nanocomposite dictates the final metal structure. Microscopy studies and nitrogen adsorption analysis show these materials form pores ranging from 2 to 50 nm with specific surface areas from 1.0 m/g to 160 m/g. Our analysis also shows that pore size, pore volume, and filament size of the nanoporous metal networks depend on the mobility of target metal and the amount of lithium halide produced by the conversion reaction. Further, it has been demonstrated that hybrid nanoporous structures of two or more metals could be synthesized by performing the same process on mixtures of precursor compounds. Metals (e.g., Co and Cu) have been found to stabilize each other in nanoporous forms, resulting in smaller pore sizes and higher surface areas than each element in their pure forms. This scalable and versatile synthesis pathway greatly expands our access to additional compositions and microstructures of nanoporous metals.
各种纳米多孔过渡金属,如 Fe、Co、Au、Cu 等,已经通过一种可扩展的、室温合成工艺很容易地形成。将卤化金属化合物与有机锂还原剂在非极性溶剂中反应,形成金属/卤化锂纳米复合材料。然后,用常见的有机溶剂将卤化锂从纳米复合材料中溶解出来,留下一个连续的、三维的金属丝网络,形成纳米多孔结构。这种方法适用于贵金属(Cu、Au、Ag)和较不活泼的过渡金属(Co、Fe、Ni)。这些纳米多孔过渡金属的微观结构是可调的,因为控制纳米复合材料中金属结构的形成决定了最终的金属结构。显微镜研究和氮气吸附分析表明,这些材料形成的孔从 2nm 到 50nm 不等,比表面积从 1.0m/g 到 160m/g 不等。我们的分析还表明,纳米多孔金属网络的孔径、孔体积和丝径取决于目标金属的迁移率以及转化反应产生的卤化锂的量。此外,通过对前体化合物混合物进行相同的处理,已经证明可以合成两种或更多种金属的混合纳米多孔结构。在纳米多孔形式下,金属(如 Co 和 Cu)被发现可以相互稳定,导致孔径更小,比表面积更高,比其纯形式的每个元素都要高。这种可扩展的多功能合成途径极大地扩展了我们对纳米多孔金属的更多组成和微观结构的访问。