Department of Chemistry, Northwestern University, Evanston, IL 60208.
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125.
Proc Natl Acad Sci U S A. 2019 Aug 13;116(33):16210-16215. doi: 10.1073/pnas.1906601116. Epub 2019 Jul 29.
Current approaches for electric power generation from nanoscale conducting or semiconducting layers in contact with moving aqueous droplets are promising as they show efficiencies of around 30%, yet even the most successful ones pose challenges regarding fabrication and scaling. Here, we report stable, all-inorganic single-element structures synthesized in a single step that generate electrical current when alternating salinity gradients flow along its surface in a liquid flow cell. Nanolayers of iron, vanadium, or nickel, 10 to 30 nm thin, produce open-circuit potentials of several tens of millivolt and current densities of several microA cm at aqueous flow velocities of just a few cm s The principle of operation is strongly sensitive to charge-carrier motion in the thermal oxide nanooverlayer that forms spontaneously in air and then self-terminates. Indeed, experiments suggest a role for intraoxide electron transfer for Fe, V, and Ni nanolayers, as their thermal oxides contain several metal-oxidation states, whereas controls using Al or Cr nanolayers, which self-terminate with oxides that are redox inactive under the experimental conditions, exhibit dramatically diminished performance. The nanolayers are shown to generate electrical current in various modes of application with moving liquids, including sliding liquid droplets, salinity gradients in a flowing liquid, and in the oscillatory motion of a liquid without a salinity gradient.
目前,在与移动水滴滴接触的纳米级导电或半导体层中发电的方法很有前途,因为它们的效率约为 30%,但即使是最成功的方法在制造和规模化方面也存在挑战。在这里,我们报告了在单个步骤中合成的稳定的全无机单元素结构,当在液体流动池中沿其表面流动的盐度梯度交替时,这些结构会产生电流。10 到 30nm 厚的铁、钒或镍纳米层在水的流速仅为几厘米每秒时会产生数十毫伏的开路电位和几微安厘米的电流密度。操作原理强烈依赖于在空气中自发形成然后自终止的热氧化纳米覆盖层中载流子的运动。事实上,实验表明,对于 Fe、V 和 Ni 纳米层,内氧化电子转移起着作用,因为它们的热氧化物包含几种金属氧化态,而使用 Al 或 Cr 纳米层作为对照,在实验条件下,它们的氧化物是氧化还原惰性的,表现出显著降低的性能。结果表明,纳米层在各种应用模式下,包括滑动液滴、流动液体中的盐度梯度以及没有盐度梯度的液体的振荡运动,都可以产生电流。