Kishimoto Fuminao, Matsuhisa Masayuki, Kawamura Shinichiro, Fujii Satoshi, Tsubaki Shuntaro, Maitani Masato M, Suzuki Eiichi, Wada Yuji
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology. E4-3, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
Research Fellow of Japan Society for the Promotion of Science, Kojimachi Business Center Building, 5-3-1 Kojimachi, Chiyoda-ku, Tokyo 102-0083, Japan.
Sci Rep. 2016 Oct 14;6:35554. doi: 10.1038/srep35554.
Various microwave effects on chemical reactions have been observed, reported and compared to those carried out under conventional heating. These effects are classified into thermal effects, which arise from the temperature rise caused by microwaves, and non-thermal effects, which are attributed to interactions between substances and the oscillating electromagnetic fields of microwaves. However, there have been no direct or intrinsic demonstrations of the non-thermal effects based on physical insights. Here we demonstrate the microwave enhancement of oxidation current of water to generate dioxygen with using an α-FeO electrode induced by pulsed microwave irradiation under constantly applied potential. The rectangular waves of current density under pulsed microwave irradiation were observed, in other words the oxidation current of water was increased instantaneously at the moment of the introduction of microwaves, and stayed stably at the plateau under continuous microwave irradiation. The microwave enhancement was observed only for the α-FeO electrode with the specific surface electronic structure evaluated by electrochemical impedance spectroscopy. This discovery provides a firm evidence of the microwave special non-thermal effect on the electron transfer reactions caused by interaction of oscillating microwaves and irradiated samples.
人们已经观察、报道了微波对化学反应的各种影响,并将其与传统加热条件下的反应进行了比较。这些影响可分为热效应和非热效应,热效应源于微波引起的温度升高,而非热效应则归因于物质与微波振荡电磁场之间的相互作用。然而,尚未基于物理见解对非热效应进行直接或本质的论证。在此,我们展示了在恒定外加电势下,利用脉冲微波辐照诱导的α-FeO电极,微波增强水的氧化电流以生成氧气的过程。观察到了脉冲微波辐照下电流密度的矩形波,也就是说,在引入微波的瞬间,水的氧化电流瞬间增加,并在连续微波辐照下稳定地保持在平台期。仅在通过电化学阻抗谱评估具有特定表面电子结构的α-FeO电极上观察到了微波增强效应。这一发现为振荡微波与被辐照样品相互作用引起的微波对电子转移反应产生特殊非热效应提供了确凿证据。