Layman Brady R, Dick Jeffrey E
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
Elmore Family School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907, United States.
J Am Chem Soc. 2024 Jan 10;146(1):707-713. doi: 10.1021/jacs.3c10505. Epub 2023 Dec 29.
Several groups have reported on the curious chemistry and reaction acceleration in confined volumes. These complex multiphase systems most closely resemble natural processes, and new measurement tools are necessary to probe chemistry in such environments. Generally, electrochemiluminescence (ECL) reports on processes immediately near (within a few micrometers) the electrode surface. Here, we introduce through-space ECL, reporting on dynamics of processes far away (100s of μm) from the electrode surface. We achieved this by collecting reflected ECL light. During the heterogeneous oxidation of CO in an aqueous phase adjacent to a 1,2-dichlorethane droplet, CO accumulates in the 1,2-dichloroethane droplet. Upon buildup, we demonstrate that a CO bubble forms in the nonaqueous phase and is surprisingly trapped at the water|1,2-dichloroethane interface and continues to grow. The co-oxidation of tris(bipyridine)ruthenium(II) in the aqueous phase lights up the electrode surface and reflects off the edges of the bubble, revealing the bubble growth over time even when the bubble is fractions of a millimeter from the surface. We extend our results to quantifying bubble forces at the water-oil interface at remote distances from the electrode surface.
多个研究小组报道了受限空间内奇特的化学现象和反应加速情况。这些复杂的多相系统与自然过程最为相似,因此需要新的测量工具来探测此类环境中的化学过程。一般来说,电化学发光(ECL)反映的是电极表面附近(几微米范围内)的过程。在此,我们引入了通过空间的ECL,它反映的是距离电极表面较远(数百微米)处的过程动态。我们通过收集反射的ECL光实现了这一点。在与1,2 - 二氯乙烷液滴相邻的水相中CO的非均相氧化过程中,CO在1,2 - 二氯乙烷液滴中积累。积累之后,我们证明在非水相中形成了一个CO气泡,并且令人惊讶的是,该气泡被困在了水|1,2 - 二氯乙烷界面处并持续生长。水相中三(联吡啶)钌(II)的共氧化使电极表面发光,并从气泡边缘反射,即使气泡距离表面只有几分之一毫米,也能揭示其随时间的生长情况。我们将结果扩展到了量化距电极表面较远的油水界面处的气泡力。