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.

Construction of Highly Hierarchical Layered Structure Consisting of Titanate Nanosheets, Tungstate Nanosheets, Ru(bpy)32+, and Pt(terpy) for Vectorial Photoinduced Z-Scheme Electron Transfer.

To imitate the precisely ordered structure of the photoantennas and electron mediators in the natural photosynthesis system, we have constructed the Ru(bpy)32+-intercalated alternate-layered structure of titanate nanosheets and tungstate nanosheets via thiol-ene click reaction. Before nanosheet stacking, Pt(terpy) was immobilized at the edge of the titanate nanosheets. The visible-light-induced vectorial Z-scheme electron transfer reaction from the valence band of tungstate to the conduction band of titanate via the photoexcited Ru(bpy)32+ was demonstrated by the following two evidences: (1) From the results of the fluorescence decay of Ru(bpy)32+, the rate of the forward electron transfer from the photoexcited Ru(bpy)32+ to the conduction band of titanate was estimated as 1.16 × 108 s-1, which was 10 times faster than the backward electron transfer from the photoexcited Ru(bpy)3 to the conduction band of tungstate (1.02 × 107 s-1) due to a localization of Ru(bpy)32+ on the titanate nanosheets. (2) We observed the decrease of the electrons accumulated in the conduction band of the tungstate induced by photoexcitation of Ru(bpy)32+, demonstrating the forward electron transfer from the conduction band of tugnstate to the vacant highest occupied molecular orbital level of the photoexcitation Ru(bpy)32+. Finally, H2 gas was produced from the water dispersion of the alternate-layered structure under visible light irradiation, suggesting that the electrons getting to the conduction band of the titanate were transferred to the Pt(terpy) placed at the edge of the nanosheets, and reduced water to dihydrogen. Herein, n-octylamine species at the interlayer space played a role as hole scavenger; in other words, these molecules were oxidized by the hole in the conduction band of the tungstate nanosheets.

Hysteresis-free perovskite solar cells made of potassium-doped organometal halide perovskite.

Potassium-doped organometal halide perovskite solar cells (PSCs) of more than 20% power conversion efficiency (PCE) without I-V hysteresis were constructed. The crystal lattice of the organometal halide perovskite was expanded with increasing of the potassium ratio, where both absorption and photoluminescence spectra shifted to the longer wavelength, suggesting that the optical band gap decreased. In the case of the perovskite with the 5% K+, the conduction band minimum (CBM) became similar to the CBM level of the TiO2-Li. In this situation, the electron transfer barrier at the interface between TiO2-Li and the perovskite was minimised. In fact, the transient current rise at the maximum power voltages of PSCs with 5% K+ was faster than that without K+. It is concluded that stagnation-less carrier transportation could minimise the I-V hysteresis of PSCs.

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.

Microwave Effects on Co-Pi Cocatalysts Deposited on α-Fe2O3 for Application to Photocatalytic Oxygen Evolution.

We analyze the effects of microwave applied in the process of photoelectrochemical deposition of cobalt-based cocatalysts, Co-Pi, onto well-orientated flat α-Fe2O3 thin films, which were fabricated by pulsed laser deposition. As compared with conventional heating, microwave significantly affects the morphology, chemical composition, and photocatalytic activity of Co-Pi/α-Fe2O3 composite. A significant enhancement in photocurrent related to photocatalytic water oxidation is achieved by the Co-Pi catalyst prepared under microwave irradiation. This, along with its interfacial electron-transfer properties, is studied by means of electrochemical impedance spectroscopy.

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.

Rapid Synthesis of D-A'-π-A Dyes through a One-Pot Three-Component Suzuki-Miyaura Coupling and an Evaluation of their Photovoltaic Properties for Use in Dye-Sensitized Solar Cells.

Twenty-four D-A'-π-A dyes were rapidly synthesized through a one-pot three-component Suzuki-Miyaura coupling reaction, which was assisted by microwave irradiation. We measured the absorption spectra, electrochemical properties, and solar-cell performance of all the synthesized dyes. The D5 πA4 dye contained our originally designed rigid and nonplanar donor and exerted the highest efficiency at 5.4 %. The short-circuit current (Jsc ) was the most important parameter for the conversion efficiency (η) in the case of the organic D-A'-π-A dyes. Optimal ranges for the D-A'-π-A dyes were observed for high values of Jsc /λmax at λ=560-620 nm, an optical-absorption edge of λ=690-790 nm, and EHOMO and ELUMO values of <1.14 and -0.56 to -0.76 V, respectively.

Microwave-enhanced photocatalysis on CdS quantum dots--Evidence of acceleration of photoinduced electron transfer.

The rate of electron transfer is critical in determining the efficiency of photoenergy conversion systems and is controlled by changing the relative energy gap of components, their geometries, or surroundings. However, the rate of electron transfer has not been controlled by the remote input of an external field without changing the geometries or materials of the systems. We demonstrate here that an applied microwave field can enhance the photocatalytic reduction of bipyridinium ion using CdS quantum dots (QDs) by accelerating electron transfer. Analysis of the time-resolved emission decay profiles of CdS quantum dots immersed in aqueous solutions of bipyridinium exhibited the shortening of their emission lifetimes, because of the accelerated electron transfer from QDs to bipyridinium under microwave irradiation. This discovery leads us to a new methodology using microwaves as an external field to enhance photocatalytic reactions.

Rapid Synthesis of Thiophene-Based, Organic Dyes for Dye-Sensitized Solar Cells (DSSCs) by a One-Pot, Four-Component Coupling Approach.

This one-pot, four-component coupling approach (Suzuki-Miyaura coupling/C-H direct arylation/Knoevenagel condensation) was developed for the rapid synthesis of thiophene-based organic dyes for dye-sensitized solar cells (DSSCs). Seven thiophene-based, organic dyes of various donor structures with/without the use of a 3,4-ethylenedioxythiophene (EDOT) moiety were successfully synthesized in good yields based on a readily available thiophene boronic acid pinacol ester scaffold (one-pot, 3-step, 35-61%). Evaluation of the photovoltaic properties of the solar cells that were prepared using the synthesized dyes revealed that the introduction of an EDOT structure beside a cyanoacrylic acid moiety improved the short-circuit current (Jsc) while decreasing the fill factor (FF). The donor structure significantly influenced the open-circuit voltage (Voc), the FF, and the power conversion efficiency (PCE). The use of a n-hexyloxyphenyl amine donor, and our originally developed, rigid, and nonplanar donor, both promoted good cell performance (η=5.2-5.6%).

Elucidating the structure-property relationships of donor-π-acceptor dyes for dye-sensitized solar cells (DSSCs) through rapid library synthesis by a one-pot procedure.

The creation of organic dyes with excellent high power conversion efficiency (PCE) is important for the further improvement of dye-sensitized solar cells. We wish to describe the rapid synthesis of a 112-membered donor-π-acceptor dye library by a one-pot procedure, evaluation of PCEs, and elucidation of structure-property relationships. No obvious correlations between ε, and the η were observed, whereas the HOMO and LUMO levels of the dyes were critical for η. The dyes with a more positive E(HOMO), and with an E(LUMO)<-0.80 V, exerted higher PCEs. The proper driving forces were crucial for a high J(sc), and it was the most important parameter for a high η. The above criteria of E(HOMO) and E(LUMO) should be useful for creating high PCE dyes; nevertheless, that was not sufficient for identifying the best combination of donor, π, and acceptor blocks. Combinatorial synthesis and evaluation was important for identifying the best dye.

Visible-light-induced electron transfer between alternating stacked layers of tungstate and titanate mediated by excitation of intercalated dye molecules.

Visible-light-induced electron transfer from a tungstate to a titanate layer was demonstrated to be mediated by excited rhodamine B (RhB) intercalated by ion exchange between the two layers. The distance of only 1 nm between the layers provides a large contact area that enables the efficient mediation of electron transfer by RhB.

Collaborational effect of heterolytic layered configuration for enhancement of microwave heating.

Microwave irradiation efficiently heats up the microwave-inert materials in the range of applied frequencies when two microwave-inert materials are brought into contact in the layered configuration. This heating is applied for annealing TiO2 nanoporous films for dye-sensitized solar cells achieving a one order of magnitude more rapid annealing process for comparable performances.

Facile synthesis of bimetallic Cu-Ag nanoparticles under microwave irradiation and their oxidation resistance.

Air-stable bimetallic Cu-Ag nanoparticles in the range of 12-30 nm have been synthesized at gram scale by a facile alcohol reduction in the absence of surfactants with the assistance of microwave irradiation. The synthesized nanoparticles were analyzed by x-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning TEM, ultraviolet-visible spectroscopy, x-ray photoelectron spectroscopy and thermogravimetry (TG). The stability of the bimetallic nanoparticles against oxidation was examined by TG and in situ temperature-programmed XRD analyses in the atmosphere. No oxidation of copper was confirmed by XRD after storing for longer than 6 months in the atmosphere at room temperature. No oxidation took place below 118 ° C and the Cu(200) diffraction peak decreased by only 7% after heating at 100 ° C for 30 min. The oxidation resistance has been ascribed to a Cu core-Ag shell structure, probably owing to the suppressive effect of Ag on the surface through the electronic interaction with Cu and a physical barrier of oxygen.

Sequential coupling approach to the synthesis of nickel(II) complexes with N-aryl-2-amino phenolates.

A sequential multicomponent coupling approach is a powerful method for the construction of combinatorial libraries because structurally complex and diverse molecules can be synthesized from simple materials in short steps. In this paper, an efficient synthesis of nickel(II) complexes with N-aryl-2-amino phenols via a sequential three-step coupling approach is described, for potential use in nonlinear optical materials, bioinspired catalytic systems, and near-infrared absorbing filters. Seventeen N-aryl-2-amino phenolates were successfully synthesized in high yields based on the coupling of 3,5-di-tert-butylbenzene-1,2-diol with a pivotal aromatic scaffold, 4-bromo-2-iodo-aniline, followed by sequential Suzuki-Miyaura coupling with aryl boronates. A total of 16 analytically pure nickel(II) complexes with N-aryl-2-amino phenolates were obtained from 17 complexation trials. The procedure allowed us to assemble 4 components in high yields without protection, deprotection, oxidation or reduction steps. Various building blocks that included electron-donating, electron-withdrawing, and basic were used, and readily available, nontoxic and environmentally benign substrates and reagents were employed with no generation of toxic compounds. No strict anhydrous or degassed conditions were required. Absorption spectroscopic measurement of the synthesized nickel(II) complexes revealed that the ortho-substituent Ar(1) exerted more influence on the absorption wavelength of the complexes than the para-substituent Ar(2). On the other hand, both substituents Ar(1) and Ar(2) influenced the molar absorptivity values. These observations should be useful for the design of new and useful nickel(II) complexes as near-infrared chromophores.

Issues and challenges in vapor-deposited top metal contacts for molecule-based electronic devices.

Metal vapor deposition to form ohmic contacts is commonly used in the fabrication of organic electronic devices because of significant manufacturability advantages. In the case of single molecular layer devices, however, the extremely small thickness, typically ~1-2nm, presents serious challenges in achieving good contacts and device integrity. This review focuses on recent scientific aspects of metal vapor deposition on monolayer thickness molecular films, particularly self-assembled monolayers, ranging across mechanisms of metal nucleation, metal-molecular group interactions and chemical reactions, diffusion of metal atoms within and through organic films, and the correlations of these and other factors with device function. Results for both non-reactive and reactive metal deposition are reviewed. Finally, novel strategies are considered which show promise for providing highly reliable and durable metal/organic top contacts for use in metal-molecule-metal junctions for device applications.

Crossed-nanowire molecular junctions: a new multispectroscopy platform for conduction--structure correlations.

We report a crossed-nanowire molecular junction array platform that enables direct measurement of current-voltage-temperature characteristics simultaneously with inelastic electron tunneling and Raman vibrational spectra on the same junction. Measurements on dithiol-terminated oligo(phenylene-ethynylene) junctions show both spectroscopies interrogate the gap-confined molecules to reveal distinct molecular features. This versatile platform allows investigation of advanced phenomena such as molecular switching and cooperative effects with the flexible ability to scale both the junction geometries and array sizes.

Moth olfactory trichoid sensilla exhibit nanoscale-level heterogeneity in surface lipid properties.

Chemical force microscopy (CFM) based on tapping mode Atomic force microscopy (AFM) utilized with topographic and phase-shift analyses was used to investigate the topography and surface chemical properties, respectively, of the long trichoid sensilla on the antennae of male Helicoverpa zea. AFM topographic imaging revealed regular series of step-ridges along nearly the entire length of each sensillum, except for the basal ca. 1/3 portions, which were devoid of such ridges. Inter-ridge regions were flat, with regularly spaced pores, ca. 30 nm in diameter populating these planar areas. Many pores exhibited a raised dome that often nearly completely spanned the depression, with only the edges of the depressed portion of the pore still visible. Some pores were observed also along the bases of the ridges. CFM probing of the surface for chemical interactions with the SiO(2) hydrophilic tip revealed consistently diminished hydrogen bonding of the ridge edge areas with the tip than along the flat planar inter-ridge regions. Surfaces of domes over the pores also tended to have less hydrogen bonding with the tip than the planar surfaces. Functionalizing the CFM tip by bonding octadecyl-hydrocarbon to it eliminated these surface chemical-CFM tip interactions and no differences in tip interaction with the sensillar surfaces were observed. Trichoid sensilla from the male antennae of a second species, Utethesia ornatrix, did not exhibit similar heterogeneity between ridge edges versus planar areas with regard to hydrogen bonding with the SiO(2) hydrophilic tip. Pores on U. ornatrix sensilla occurred only along the bases of ridges on their trichoid sensilla. We suggest that the surface lipids of the H. zea sensilla are distributed in a chemically heterogeneous fashion to aid adsorption and transport of aldehyde pheromone component molecules through the pores into the sensillum lumen, possibly through solubilization in an epicuticular lipid layer. The trichoid sensilla of U. ornatrix do not exhibit such surface chemical heterogeneity, and this species-difference may be due to the usage by U. ornatrix of hydrocarbon molecules rather than aldehydes for their sex pheromone components.