Molecular Biophysics and Integrated Bioimaging Division and §Molecular Foundry Division, Lawrence Berkeley National Laboratory, University of California , Berkeley, California 94720, United States.
ACS Nano. 2018 Jan 23;12(1):533-541. doi: 10.1021/acsnano.7b07125. Epub 2018 Jan 9.
Macroscale arrays of cobalt oxide-silica core-shell nanotubes with high aspect ratio and ultrathin walls of less than 20 nm have been fabricated. The silica shells feature embedded oligo-para(phenylenevinylene) molecules for charge transport across the insulating silica layer, which is tightly controlled by their electronic properties. The assembly is based on the use of a sacrificial Si nanorod array template combined with atomic layer deposition, covalent anchoring of organic wire molecules, and dry cryo-etching. High-resolution TEM imaging of samples prepared by microtome affords structural details of single core-shell nanotubes. The integrity of silica-embedded organic wire molecules exposed to atomic layer deposition, thermal treatment, and harsh etching procedures is demonstrated by grazing angle ATR FT-IR, FT-Raman, and XPS spectroscopy. The inorganic oxide-based core-shell nanotubes with ultrathin gas-impermeable, proton-conducting silica shells functionalized by molecular wires enable complete nanoscale photosynthetic units for CO reduction by HO under membrane separation. Arrays of massive numbers of such core-shell nanotube units afford a design that extends the separation of the incompatible HO oxidation and CO reduction catalysis environments across the continuum of length scales from nanometers to centimeters.
已经制备出具有高纵横比和小于 20nm 的超薄壁的钴氧化物-二氧化硅核壳纳米管的宏观阵列。二氧化硅壳层具有嵌入式低聚对（苯乙炔）分子，用于在绝缘二氧化硅层中传输电荷，这可以通过其电子特性来严格控制。该组装基于使用牺牲 Si 纳米棒阵列模板结合原子层沉积、有机线分子的共价锚定以及干冷冻蚀刻来实现。通过微切片制备的样品的高分辨率 TEM 成像提供了单个核壳纳米管的结构细节。通过掠角 ATR FT-IR、FT-Raman 和 XPS 光谱证明了暴露于原子层沉积、热处理和苛刻蚀刻程序的嵌入二氧化硅的有机线分子的完整性。具有超薄、气体不可渗透、质子导电的二氧化硅壳层的基于无机氧化物的核壳纳米管通过分子线官能化，使完整的纳米级光合作用单元能够在膜分离下通过 HO 还原 CO。这种核壳纳米管单元的大量阵列提供了一种设计，可以将不相容的 HO 氧化和 CO 还原催化环境的分离扩展到从纳米到厘米的连续长度尺度。
