Inverse kinetic isotope effect of ammonia decomposition over Ru/CeO2 using deuterated ammonia.

This study investigated the ammonia decomposition mechanism over Ru/CeO2. Isotopic tests using ND3 revealed that the rate-determining step involves adsorbed nitrogen atoms on Ru. Moreover, an inverse kinetic isotope effect where ND3 decomposition was faster than NH3 was clearly observed. The origin of the inverse effect was explained by the lower D coverage on the catalyst surface compared to H coverage for mitigating the inhibition of ND3 activation.

Electron Storage in Monolayer Tungstate Nanosheets Produced via a Scalable Exfoliation Method.

Inorganic nanosheet materials with atomic thinness have been widely studied as (photo)catalytic materials due to their unique electronic states and surface structures. One scalable and reproducible method of producing monolayer nanosheets is a top-down approach based on the exfoliation of layered parent compounds using an alkylammonium solution as a surfactant. However, H2W2O7 layered tungstates dissolve in basic aqueous solutions, making them unsuitable for the exfoliation process. This work proposes a scalable method to obtain monolayer WO3 nanosheets with a very high external field responsiveness. This work shows that H2W2O7 topochemically swells in a concentrated octylamine (C8N17NH2) aqueous solution with a concentration above the solubility of octylamine in water. Water was added for exfoliation of the liquid crystalline phase into isolated W2O72- nanosheets with octylammonium (C8N17NH3+) protection. Crystalline WO3 nanosheets on the n-Si substrate obtained with calcination exhibited electron richness in the conduction band due to static electron transfer at the interface.

Drastic Photoemission Color Alternation from a Single Molecule as a Starting Material Introduced in Acid-Treated Zeolites: From Pure Blue to White.

Since high-purity blue- and white-light emitters are an indispensable group of materials for the creation of next-generation optical devices, a number of light-emitting materials have been developed from both inorganic and organic synthetic chemistry. However, these synthetic chemical methods are far from the perspective of green chemistry due to the multistep synthetic process and the use of toxic reagents and elements. Herein, we demonstrate that the introduction of simple unsubstituted anthracenes into zeolite-like pores can create a wide variety of luminescent materials, from ultrapure blue luminescent materials (emission peak at 465 nm with a full width of half-maximum of 8.57 nm) to efficient white luminescent materials [CIE coordination at (0.31, 0.33) with a quantum efficiency of 11.0% under 350 nm excitation light]. The method for rational design of the luminescent materials consists of the following two key strategies: one is molecular orbital confinement of the anthracene molecules in the zeolite nanocavity for regulating the molecular coordination associated with photoexcitation and emission and the other is the interaction of unsubstituted anthracenes with extra-framework aluminum species to stabilize the 2-dehydride anthracene cation in the zeolite cavity.

Direct microwave energy input on a single cation for outstanding selective catalysis.

Microwave (MW)-driven catalytic systems are attracting attention not only as an aggressive electrification strategy of the chemical industry but also as creating a unique catalytic reaction field that conventional equilibrium heating cannot achieve. This study unlocked direct and selective heating of single alkali metal cations in the pores of aluminosilicate zeolites under MW. Selectively heated Cs+ cations in FAU zeolite exhibited selective CH4 combustion performance, that is, COx generation at the heated Cs+ cations selectively occurred while side reactions in the low-temperature gas phase were suppressed. The Cs-O pair distribution function revealed by synchrotron-based in situ x-ray total scattering gave us direct evidence of peculiar displacement induced by MW, which was consistent with the results of molecular dynamics simulation mimicking MW heating. The concept of selective monoatomic heating by MW is expected to open a next stage in "microwave catalysis" science by providing physicochemical insights into "microwave effects."

Photocatalytic formation of a gas permeable layer selectively deposited on supported metal nanoparticles for sintering-resistant thermal catalysis.

Nanoparticle aggregation of supported metal catalysts at high temperatures is a serious problem that causes a drop in catalytic performance. This study investigates the protection of metal nanoparticles from sintering by selectively forming nanoscale SiO2 shells on Pd supported on TiO2 by ultraviolet (UV) light irradiation. The proton-coupled reduction reaction increases the local pH around Pd nanoparticles, resulting in hydrolysis of tetraethoxyorthosilicate (TEOS) in only the vicinity of the metal. An apparent quantum efficiency of only 0.6% is obtained for the Pd/TiO2 catalyst in H2 evolution from ethanol-containing water under 370 nm excitation light. Therefore, the pH of raw slurry solution should be precisely controlled to that slightly below the threshold value for the TEOS hydrolysis reaction before the photodeposition. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) clearly show that the particle size of the Pd nanoparticles (∼40 nm) with the SiO2 shell (∼20 nm) was almost unchanged by the high-temperature treatment at 900 °C in air, suggesting that the SiO2 shell prevented thermal aggregation of Pd nanoparticles. The Pd/TiO2 without SiO2 shell decoration exhibited a drop in the number of active sites, which was likely due to aggregation of the Pd catalysts. However, the number of active sites on the Pd@SiO2/TiO2 catalyst was maintained even after the catalyst was calcined at 900 °C. Consequently, the Pd@SiO2/TiO2 catalyst maintained its catalytic performance for simulated exhaust gas purification even after treatment at 900 °C. This study presents a methodology to produce sintering-tolerant supported metal nanoparticles using the photocatalytic gas permeable layer fabrication method.

A hygroscopic nano-membrane coating achieves efficient vapor-fed photocatalytic water splitting.

Efficient water vapor splitting opens a new strategy to develop scalable and corrosion-free solar-energy-harvesting systems. This study demonstrates highly efficient overall water splitting under vapor feeding using Al-doped SrTiO3 (SrTiO3:Al)-based photocatalyst decorated homogeneously with nano-membrane TiOx or TaOx thin layers (<3 nm). Here, we show the hygroscopic nature of the metal (hydr)oxide layer provides liquid water reaction environment under vapor, thus achieving an AQY of 54 ± 4%, which is comparable to a liquid reaction. TiOx coated, CoOOH/Rh loaded SrTiO3:Al photocatalyst works for over 100 h, under high pressure (0.3 MPa), and with no problems using simulated seawater as the water vapor supply source. This vapor feeding concept is innovative as a high-pressure-tolerant photoreactor and may have value for large-scale applications. It allows uniform distribution of the water reactant into the reactor system without the potential risk of removing photocatalyst powders and eluting some dissolved ions from the reactor.

Photocatalytic oxygen evolution triggered by photon upconverted emission based on triplet-triplet annihilation.

A visible light responsive photocatalyst, Mo-doped BiVO4 (Mo:BVO), was shown to promote oxygen evolution from water in response to photon upconverted emission based on triplet-triplet annihilation (TTA) in the same aqueous dispersion. Composites comprising a triplet sensitizer (Pt(ii) octaethylporphyrin; PtOEP) and a singlet emitter (9,10-diphenylanthracene; DPA) intercalated in a layered clay compound (montmorillonite or saponite) were prepared using a facile but versatile solvothermal method. These composites were capable of converting green incident light (λ = 535 nm) to blue light (λ = 430 nm) even in air. The host layered clay as well as the co-intercalated surfactant evidently functioned as barriers against water and oxygen to prevent the quenching of the active compounds. The TTA upconversion driven photocatalytic oxygen evolution using the aqueous mixture of the dyes-clay composite and particulate photocatalysts can be a potential approach to eliminate the undesired optical losses and thus be a breakthrough for future industrial and large-scale installation in an inexpensive manner.

Aryl radical initiators accumulated within layered silicates realize polystyrene with directly and regioselectively bonded aryl-terminal groups.

The arbitrary design of a terminal group of polymers exploits the still-veiled functions of polymers with potential for application in fields such as drug delivery systems, photonics, and energy conversions. Here we demonstrate for the first time that polystyrenes with directly and regioselectively bonded aryl-terminal groups can be obtained via styrene radical polymerization initialized by arbitrary aryl radicals accumulated within the interlayer space of smectite clay minerals, which can be prepared by our developed 'Clay Catalysed ab intra Deamination (CCD)' method.

Water-Dispersible Triplet-Triplet Annihilation Photon Upconversion Particle: Molecules Integrated in Hydrophobized Two-Dimensional Interlayer Space of Montmorillonite and Their Application for Photocatalysis in the Aqueous Phase.

Green incident light (λ = ∼500 nm) is converted to blue light (λ = 400-450 nm) in air using bulky alkylammonium (DMDOA+), 9,10-diphenylanthracene (DPA), and Ru(dmb)32+ (dmb = 4,4'-dimethyl-2,2'-bipyridine) intercalated in a layered clay compound called "montmorillonite" [MMT-DMDOA+-DPA-Ru(dmb)32+]. The two-dimensional interstitial space has an interlayer spacing of a few nanometers. Emitter DPA is present in this interlayer spacing, having an intermolecular distance of approximately 3.0 nm at a high concentration. Sensitizer Ru(dmb)32+ is relatively dilute, having an intermolecular distance of 47 nm. The emission decay measurements and quantitative evaluation of the emission intensity demonstrate that blue light emission is induced by sequential processes, which consist of a triplet-triplet (T-T) energy transfer reaction from Ru(dmb)32+ to DPA and T-T annihilation of DPA molecules. From thermogravimetry and Fourier transform infrared spectra measurements, we observe that the cointercalated alkylammonium acts as a waterproof agent to prevent quenching of the molecules in the excited triplet states by H2O. Finally, we demonstrate a photocatalytic decomposition of Rhodamine B dissolved in H2O-containing MMT-DMDOA+-DPA-Ru(dmb)32+ and Pt-deposited WO3 photocatalyst, where wavelength of incident light (λ > 440 nm) is longer than the absorption edge of WO3 photocatalyst. The mechanism of photocatalytic decomposition is the following: (i) the incident long wavelength light is upconverted to 400-450 nm light by MMT-DMDOA+-DPA-Ru(dmb)32+, and then, (ii) WO3 photocatalyst is excited by the generated 400-450 nm light, and finally, (iii) Rhodamine B is decomposed on the Pt cocatalyst induced by the holes in a valence band of WO3.

Determination and perturbation of the electronic potentials of solid catalysts for innovative catalysis.

Concerns about energy and the environment are motivating a reexamination of catalytic processes, aiming to achieve more efficient and improved catalysis compatible with sustainability. Designing an active site for such heterogeneous catalytic processes remains a challenge leading to a next level breakthrough. Herein, we discuss a fundamental aspect of heterogeneous catalysis: the chemical potential of electrons in solid catalysts during thermal catalysis, which directly reflects the consequent catalytic reaction rate. The use of electrochemical tools during thermal catalysis allows for the quantitative determination of the ill-defined chemical potentials of solids in operando, whereby the potential-rate relationship can be established. Furthermore, the electrochemical means can also introduce the direct perturbation of catalyst potentials, in turn, perturbing the coverage of adsorbates functioning as poison, promoters, or reactants. We collect selected publications on these aspects, and provide a viewpoint bridging the fields of thermal- and electro-catalysis.

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.

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.

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-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.

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.