Accelerating Sulfated Polysaccharides Extraction from Fast-Growing Ulva Green Seaweed by Frequency-Controlled Microwaves.

Ulva sp. is a type of green algae and is widely distributed in coastal areas around the world due to eutrophication. Effective utilization of Ulva sp. is expected for the establishment of carbon-neutral biochemical production. Microwave-assisted hydrothermal extraction is one of the most efficient ways of extracting highly functional polysaccharides called ulvan. Here, we demonstrate the importance of microwave frequency in enhancing ulvan extraction from Ulva meridionalis. We found that microwaves (2.45 GHz) selectively heat water solvent, while radio frequency (200 MHz) selectively heats ionic ulvan. Moreover, 2.45 GHz was more effective for extracting ulvan than 200 MHz. Then, we analyzed the conformational change in ulvan during microwave irradiation using in situ small-angle X-ray scattering. Microwaves initiated the loosening of ulvan bundles at temperatures lower than those of conventional heating. As a result, microwaves at 2.45 GHz selectively heat water and initiate ulvan structural change to enhance the extraction of ulvan from U. meridionalis.

Self-Sufficient Production of Lunar Regolith Gravels on the Moon by Ultrarapid Microwave Sintering.

A sintered lunar regolith is expected to be used to construct buildings, roads, and landing pads for spacecrafts on the Moon. Here, we demonstrate that focused microwave heating is effective for the rapid solidification of the lunar regolith simulant to obtain regolith gravel without any microwave susceptor. The conventional multimode microwave oven cannot heat lunar regolith simulants and requires microwave susceptors such as silicon carbide (SiC) and thermal insulators because of its low dielectric loss. We achieved rapid microwave heating of a lunar regolith simulant without using a susceptor or thermal insulator by forming an intense microwave electric field using a cavity resonator and a semiconductor microwave oscillator. Focused microwaves at 2.45 GHz produced the gravel-shaped and solidified lunar regolith at 300 °C lower temperature than a conventional electrical furnace, where more than 1050 °C temperature was required to sinter the lunar regolith simulant. In addition, we produced larger gravel of the lunar regolith simulant using 915 MHz. The intense electric field generated by the single-mode resonator promoted the solidification of the lunar regolith simulant without any additional substances. This process enables the local production of structured lunar regoliths on the Moon without the transport of any materials from the Earth.

Real-Time Facile Detection of the WO3 Catalyst Oxidation State under Microwaves Using a Resonance Frequency.

Microwaves (MWs) are often used to enhance various heterogeneous catalytic reactions. Here, we demonstrate real-time monitoring of a catalyst's oxidation state in a microwave catalytic reaction using a resonance frequency. The changes in the catalyst's oxidation state during the reaction induced changes in the resonance frequency in the cavity resonator. The resonance frequency was not affected by 2-propanol adsorption, while the frequency decreased with the reduction of WO3 → WO3-x. That is, the redox state of the WO3 catalyst could be detected using the resonance frequency. The oxidation state of the WO3 catalyst was then directly observed by the resonance frequency during the dehydration reaction of 2-propanol by microwaves as a model reaction. Resonance frequency monitoring revealed that the enhanced dehydration of 2-propanol by microwaves was attributable to the reduction of the WO3 catalyst. Moreover, the temporal changes in the oxidation state of the WO3 catalyst detected by the resonance frequency coincided with that observed by operando Raman spectroscopy. Therefore, real-time resonance frequency monitoring allowed facile detection of the bulk catalyst oxidation state under microwaves without using any spectroscopic apparatus.

Probing rapid carbon fixation in fast-growing seaweed Ulva meridionalis using stable isotope 13C-labelling.

The high growth rate of Ulva seaweeds makes it a potential algal biomass resource. In particular, Ulva meridionalis grows up to fourfold a day. Here, we demonstrated strong carbon fixation by U. meridionalis using 13C stable isotope labelling and traced the 13C flux through sugar metabolites with isotope-ratio mass spectrometry (IR-MS), Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), 13C-nuclear magnetic resonance spectrometry (13C-NMR), and gas chromatography-mass spectrometry (GC-MS). U. meridionalis was first cultured in 13C-labelled enriched artificial seawater for 0-12 h, and the algae were collected every 4 h. U. meridionalis grew 1.8-fold (dry weight), and the 13C ratio reached 40% in 12 h, whereas 13C incorporation hardly occurred under darkness. At the beginning of the light period, 13C was incorporated into nucleic diphosphate (NDP) sugars in 4 h, and 13C labelled peaks were identified using FT-ICR-MS spectra. Using semiquantitative 13C-NMR measurements and GC-MS, 13C was detected in starch and matrix polysaccharides after the formation of NDP sugars. Moreover, the 14:10 light:dark regime resulted into 85% of 13C labelling was achieved after 72 h of cultivation. The rapid 13C uptake by U. meridionalis shows its strong carbon fixation capacity as a promising seaweed biomass feedstock.

Fourfold daily growth rate in multicellular marine alga Ulva meridionalis.

Microalgae with high growth rates have been considered as promising organisms to replace fossil resources with contemporary primary production as a renewable source. However, their microscopic size makes it hard to be harvested for industrial applications. In this regard, multicellular macroalgae are more suitable for harvesting. Here, we show that Ulva meridionalis has the highest growth rate ever reported for a multicellular autotrophic plant. Contrasted to the known bloom-forming species U. prolifera growing at an approximately two-fold growth rate per day in optimum conditions, U. meridionalis grows at a daily rate of over fourfold. The high growth ability of this multicellular alga would provide the most effective method for CO2 fixation and biomass production.

Microwave Irradiation Process for Al-Sc Alloy Production.

Scandium is being explored as an alloying element for aluminium alloys, which are gaining importance as high-performance lightweight structural alloys in the transportation industry. Sc-rich ScAlN thin films show strong piezoelectricity and can be fabricated on a hard substrate for use as wideband surface acoustic wave filters in next-generation wireless mobile communication systems. However, the use of ScAlN thin films in microelectromechanical system devices is limited by the high cost of metallic Sc, which is due to the difficulty in smelting of this material. Here, we propose a novel microwave irradiation process for producing Al-Sc alloys, with Mg ions as a reducing agent. Although scandium oxide is thermodynamically stable, intermetallic Al3Sc is obtained in high yield (69.8%) via a low-temperature (660 °C) reduction reaction under microwave irradiation. Optical spectroscopy results and thermodynamic considerations suggest a non-thermal equilibrium reaction with the univalent magnesium ions excited by microwave irradiation.

Probing the temperature of supported platinum nanoparticles under microwave irradiation by in situ and operando XAFS.

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.

Kinetic analysis of microwave-enhanced cellulose dissolution in ionic solvents.

Cellulose dissolution in mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate with dimethylsulfoxide, [C2C1Im][OAc] + DMSO, have been kinetically compared using conventional heating and microwave heating in a single-mode cavity with a semiconductor generator. Microwaves led to enhancements in the dissolution rate between 21 and 57% under different conditions of temperature and concentration of ionic liquid. Rate enhancement by microwaves prominently occurred at temperatures above 60 °C. Based on an Arrhenius plot and wide-band dielectric measurements we advance the hypothesis that the faster dissolution is caused by ionic motion induced by microwaves in the timescale of formation and breaking of hydrogen bonds between cellulose chains and acetate anions.

Fractionation of plant-cuticle-based bio-oils by microwave-assisted methanolysis combined with hydrothermal pretreatment and enzymatic hydrolysis.

Microwave-assisted methanolysis was performed to fractionate a mixture of fatty acid methyl-esters from the cuticles of various wild plants and agricultural wastes. A combination of hydrothermal pretreatment and enzymatic hydrolysis effectively removed hemicellulose and cellulose to afford plant cuticles concentrated in residual materials. The subsequent methanolysis treatment afforded bio-oil from plant cuticles in ∼10% yield with a maximum higher heating value (HHV) of 32 MJ kg-1 from bagasse. The proposed cascading treatments allow the total use of herbaceous soft biomass by utilizing hemicellulose and cellulose fractions as well as plant cuticles to produce bio-oils with high HHVs.

Remote Control of Electron Transfer Reaction by Microwave Irradiation: Kinetic Demonstration of Reduction of Bipyridine Derivatives on Surface of Nickel Particle.

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 Δ G 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.

Enhancement of Fixed-bed Flow Reactions under Microwave Irradiation by Local Heating at the Vicinal Contact Points of Catalyst Particles.

The formation of local high temperature regions, or so-called "hot spots", in heterogeneous reaction systems has been suggested as a critical factor in the enhancement of chemical reactions using microwave heating. In this paper, we report the generation of local high temperature regions between catalyst particles under microwave heating. First, we demonstrated that reaction rate of the dehydrogenation of 2-propanol over a magnetite catalyst was enhanced 17- (250 °C) to 38- (200 °C) fold when heated with microwave irradiation rather than an electrical furnace. Subsequently, the existence of microwave-generated specific local heating was demonstrated using a coupled simulation of the electromagnetic fields and heat transfer as well as in situ emission spectroscopy. Specific high-temperature regions were generated at the vicinal contact points of the catalyst particles due to the concentrated microwave electric field. We also directly observed local high temperature regions at the contact points of the particles during microwave heating of a model silicon carbide spherical material using in situ emission spectroscopy. We conclude that the generation of local heating at the contact points between the catalyst particles is a key factor for enhancing fixed-bed flow reactions under microwave irradiation.

Radio frequency alternating electromagnetic field enhanced tetraruthenium polyoxometalate electrocatalytic water oxidation.

Application of radio frequency (RF) electromagnetic waves enhances the electrocatalytic water oxidation by protonated tetraruthenium polyoxometalate ([Ru4(µ-O)4(µ-OH)2(H2O)4(γ-SiW10O36)2]10-). In particular, an enhancement factor of 3.6 is achieved when the level of proton substitution of protonated tetraruthenium polyoxometalate is changed from zero to 9 under application of RF at 200 MHz.

Proton-Enhanced Dielectric Properties of Polyoxometalates in Water under Radio-Frequency Electromagnetic Waves.

Electromagnetic waves, such as microwaves, have been used to enhance various chemical reactions over polyoxometalates. The dielectric properties of catalysts are among the relevant parameters facilitating catalytic reactions under electromagnetic radiation. This study describes the dielectric properties of polyoxometalate catalysts in aqueous and organic solutions to understand the mechanism of interactions between polyoxometalates and electromagnetic waves. Specific loss factors of polyoxometalates were observed at lower frequencies (<1 GHz) by the ionic conduction of the polyoxometalate solution. The evolution of ionic conduction depended strongly on cations rather than anions. Proton-type polyoxometalates exhibited significantly higher loss factors than other cations did. The activation energy for ionic conduction in protonated silicotungstic acid (H4SiW12O40) was significantly low in water (7.6⁻14.1 kJ/mol); therefore, the high loss factor of protonated polyoxometalates in water was attributed to the proton relay mechanism (i.e., Grotthuss mechanism). The results suggested that the proton relay mechanism at the radio-frequency band is critical for generating selective interactions of polyoxometalates with applied electromagnetic fields.

Effect of Aspect Ratio on the Permittivity of Graphite Fiber in Microwave Heating.

Microwave (MW) heating has received attention as a new heating source for various industrial processes. Some materials are expected to be a more effective absorber of MW, and graphite is observed as a possible candidate for high-temperature application. We investigated the dependence of the aspect ratio of graphite fibers on both their heating behavior and permittivity under a 2.45 GHz MW electric field. In these experiments, both loss tangent and MW heating behavior indicated that the MW absorption of conductive fibers increases with their aspect ratio. The MW absorption was found to be well accounted for by the application of a spheroidal model for a single fiber. The absorption of graphite fibers decreases with increasing aspect ratio when the long axis of the ellipsoid is perpendicular to the electric field, whereas it increases with the aspect ratio when the long axis is parallel to the electric field. The analytical model indicated that MW heating of the conductive fibers is expected to depend on both the shape and arrangement of the fibers in the electric field.

Smelting of Scandium by Microwave Irradiation.

Scandium is being explored as an alloying element for aluminum alloys, which are gaining importance as high-performance lightweight structural alloys in the transportation industry. A few years ago, Sc was also found to be suitable for use in electrical devices. High-Sc-content ScAlN thin films have attracted significant attention because of their strong piezoelectricity. The piezoelectric response of ScAlN suggests that ScAlN thin films formed on a hard substrate would be suitable surface acoustic wave wideband filters for next-generation wireless communication systems. However, it is often difficult to use ScAlN thin films in MEMS devices-including acoustic ones-because of the extremely high price of metallic Sc, given the difficulty associated with smelting it. Here, we propose a novel process for smelting Sc metal by microwave irradiation. Sc metal was able to be obtained successfully from ScF3 through a microwave-irradiation-based carbon reduction reaction. The reaction temperature for this reduction process was approximately 880°C, which is half of that for the conventional smelting process involving reduction with Ca. Thus, the proposed microwave irradiation process has significant potential for use in the smelting of Sc metal.

Smelting Magnesium Metal using a Microwave Pidgeon Method.

Magnesium (Mg) is a lightweight metal with applications in transportation and sustainable battery technologies, but its current production through ore reduction using the conventional Pidgeon process emits large amounts of CO2 and particulate matter (PM2.5). In this work, a novel Pidgeon process driven by microwaves has been developed to produce Mg metal with less energy consumption and no direct CO2 emission. An antenna structure consisting of dolomite as the Mg source and a ferrosilicon antenna as the reducing material was used to confine microwave energy emitted from a magnetron installed in a microwave oven to produce a practical amount of pure Mg metal. This microwave Pidgeon process with an antenna configuration made it possible to produce Mg with an energy consumption of 58.6 GJ/t, corresponding to a 68.6% reduction when compared to the conventional method.

Enhancement of anodic current attributed to oxygen evolution on α-Fe2O3 electrode by microwave oscillating 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.

In situ temperature measurements of reaction spaces under microwave irradiation using photoluminescent probes.

We demonstrate two novel methods for the measurement of the temperatures of reaction spaces locally heated by microwaves, which have been applied here to two example systems, i.e., BaTiO3 particles covered with a SiO2 shell (BaTiO3-SiO2) and layered tungstate particles. Photoluminescent (PL) probes showing the temperature-sensitivity in their PL lifetimes are located in the nanospaces of the above systems. In the case of BaTiO3-SiO2 core-shell particles, rhodamine B is loaded into the mesopores of the SiO2 shell covering the BaTiO3 core, which generates the heat through the dielectric loss of microwaves. The inner nanospace temperature of the SiO2 shell is determined to be 28 °C higher than the bulk temperature under microwave irradiation at 24 W. On the other hand, Eu(3+) is immobilized in the interlayer space of layered tungstate as the PL probe, showing that the nanospace temperature of the interlayer is only 4 °C higher than the bulk temperature. This method for temperature-measurement is powerful for controlling microwave heating and elucidates the ambiguous mechanisms of microwave special effects often observed in chemical reactions, contributing greatly to the practical application of microwaves in chemistry and materials sciences.

Microwave-assisted hydrothermal extraction of sulfated polysaccharides from Ulva spp. and Monostroma latissimum.

Microwave-assisted hydrothermal extraction was applied for production of sulfated polysaccharides from Ulva spp. and Monostroma latissimum. The maximum ulvan yields attained 40.4±3.2% (Ulva meridionalis) and 36.5±3.1% (Ulva ohnoi) within 4min of come-up time and 10min of extraction time at 160°C, respectively. The rhamnan sulfate yield from M. latissimum further attained 53.1±7.2% at 140°C. The sulfated polysaccharides were easily recovered from the extract by simple ethanol precipitation. In addition, molecular weights and viscosity of the extracted polysaccharides could be controlled by varying the extraction temperature. Dielectric measurement revealed that ionic conduction was the important parameter that affect the microwave susceptibility of algae-water mixture. The sulfated polysaccharides extracts are expected as potential feedstock for medical and food applications.

Effects of ionic conduction on hydrothermal hydrolysis of corn starch and crystalline cellulose induced by microwave irradiation.

This study investigated the effects of ionic conduction of electrolytes under microwave field to facilitate hydrothermal hydrolysis of corn starch and crystalline cellulose (Avicel), typical model biomass substrates. Addition of 0.1M NaCl was effective to improve reducing sugar yield by 1.61-fold at unit energy (kJ) level. Although Avicel cellulose was highly recalcitrant to hydrothermal hydrolysis, addition of 0.1M MgCl2 improved reducing sugar yield by 6.94-fold at unit energy (kJ). Dielectric measurement of the mixture of corn starch/water/electrolyte revealed that ionic conduction of electrolytes were strongly involved in facilitating hydrothermal hydrolysis of polysaccharides.