Microwave irradiation can cause high local temperatures at supported metal nanoparticles, which can enhance reaction rates. Here we discuss the temperature of platinum nanoparticles on γ-Al2O3 and SiO2 supports under microwave irradiation using the Debye–Waller factor obtained from in situ extended X-ray absorption fine structure (EXAFS) measurements. Microwave irradiation exhibits considerably smaller Deby–Waller factors than conventional heating, indicating the high local temperature at the nanoparticles. The difference in the average temperatures between the platinum nanoparticles and the bulk under microwaves reaches 26 K and 132 K for Pt/Al2O3 and Pt/SiO2, respectively. As a result, Pt/SiO2 exhibits considerably more reaction acceleration for the catalytic dehydrogenation of 2-propanol under microwave irradiation than Pt/Al2O3. We also find microwaves enhance the reduction of PtOx nanoparticles by using operando X-ray absorption near edge structure (XANES) spectroscopy. The present results indicate that significant local heating of platinum nanoparticles by microwaves is effective for the acceleration of catalytic reactions.

We studied the effects of surface morphology and carrier distribution of α-Fe2O3 electrodes on the enhancement of water electrolysis under microwave (MW) irradiation. We deposited α-Fe2O3 electrodes with various morphologies on Nb-doped rutile TiO2 (100) substrates. α-Fe2O3 films with rough and flat surfaces were deposited using electrodeposition (ED) and pulsed laser deposition (PLD), respectively. The ED α-Fe2O3 film showed a larger response to the MW electric field applied to the electrodes than did the PLD film. In addition, the response was linearly correlated with the MW electric field intensity. Using scanning MW microscopy, we found that the local MW susceptibility of the α-Fe2O3 electrode was enhanced at the grain boundary of the ED α-Fe2O3 film. Analysis of the surface band structure of both ED and PLD α-Fe2O3 films using electrochemical impedance spectroscopy showed that the ED α-Fe2O3 film had a wider depleted layer, indicating increased accumulation of holes on the surface of the electrode to enhance water oxidation. We concluded that the accumulation of holes at the grain boundary of the ED α-Fe2O3 film determines the enhancement of water oxidation under an MW electric field.

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-Fe2O3 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-Fe2O3 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.

Materials that are thermodynamically stable at ultrahigh pressures (>10 GPa) often exhibit unique physical properties. However, few studies have addressed the fabrication of epitaxial thin films of ultrahigh-pressure phases. Herein, we combine epitaxial thin film growth techniques with ultrahigh-pressure synthetic methods. We demonstrate the synthesis of single-phase epitaxial thin films of an ultrahigh-pressure polymorph of TiO2, α-PbO2-type TiO2. A rutile TiO2(100) epitaxial thin film is used as a precursor, and a structural phase transition is induced at 8 GPa and 800–1000 °C. This study demonstrates a new synthetic route to obtain ultrahigh-pressure-phase materials. The fabrication of epitaxial thin film ultrahigh-pressure phases paves the way for investigating the physical properties that arise at surfaces and interfaces of materials.

Microwave irradiation has great potential to control chemical reactions remotely, particularly reactions that involve electron transfer. In this study, we found that the reduction reaction of bipyridine derivatives on metal nickel particles was accelerated or decelerated by 2.45 GHz microwaves without an alteration of the reaction temperature. The order of the extent of the microwave acceleration of the electron transfer reaction coincided with the negativity of the redox potential of the bipyridine derivatives, i.e., the electron transfer with smaller ΔG was significantly enhanced by microwave irradiation. By applying Marcus’ electron transfer theory, we propose two mechanisms of the microwave effect on electron transfer reactions, i.e., vibration of the electrons in Ni particles to make the electron transfer easier and rotation of the water molecules to prevent the reorganization of the hydrated systems after the electron transfer reaction.