Kinetic Studies of WO3-Based Photochromism in Polyvinyl Alcohol Film.

Tungsten oxide (WO3) has been extensively studied for various photochromic applications. Blue coloration of WO3 is explained in terms of the intervalence charge transfer (IVCT) transition of electrons between W6+ and W5+. However, various absorption spectra with different shapes have been reported. Herein, a transparent film was prepared by drying aqueous solutions containing polyvinyl alcohol, WO3 nanoparticles and ethylene glycol (EG). For comparison, the photochromic behavior of an aqueous WO3 colloidal solution containing EG was also investigated. Under UV irradiation, a single intense peak was always observed at ca. 777 nm in the colloidal solution, but the absorption spectra of the film changed from a peak at 770 nm to two distinct peaks at 654 and 1003 nm. All absorption spectra observed with the film and the colloidal solution were deconvoluted into five peaks at 540, 640, 775, 984, and 1265 nm. Kinetic studies using the colloidal solution indicated that the coloration rates (r0) estimated at the deconvoluted peaks of 640, 775, and 984 nm followed the same rate law. On the other hand, in the case of the film, r0 evaluated at 640 or 984 nm was independent of the water amounts but increased proportionally to the EG amounts and the light intensity, although r0 at 775 nm significantly increased with the increasing amounts of water and EG. Raman and electron spin resonance spectroscopic observations of the film revealed that the photogenerated electrons migrated toward the terminal W═O moiety to accumulate and then a small anisotropic electron spin resonance signal appeared. Our study demonstrates that the absorption at 775 nm is due to IVCT between W6+ and W5+, which is stabilized with water in the bulk and the absorption peaks at 640 and 984 nm are attributable to IVCT on the WO3 surface.

Photochromism of TiO2 Nanoparticles Doped with Molybdenum Ions: Neutral Color Change from Colorless to Black via Gray.

Transition metal oxide nanoparticles have been extensively studied for the development of smart windows which are expected to be a promising technology to save energy in buildings. However, most of them turn blue under UV irradiation. Since the blue coloration affects the color of objects through the windows, the development of materials with a neutral color which hardly disturbs the view is more beneficial. In this work, we prepared a colorless-transparent TiO2 colloidal solution containing Mo6+ ions (Mo-TiO2), which turns black via gray in a nitrogen atmosphere under UV irradiation. An absorption peak was observed at 535 nm, which increased with an increase in the UV irradiation time and reached a constant value (Absmax). The Absmax value increased linearly with an increase in the Mo doping amount. We demonstrated that the photochromic behavior of the Mo-TiO2 nanoparticles is completely different from that of pure MoO3 or the mixture of MoO3 and TiO2. In addition, we performed a kinetic study to elucidate the mechanism and found that the coloration rate at the initial stage decreased with an increase in Mo doping amount. Based on the kinetic analysis, the following results are obtained: a color center is formed at a deeper energy level than the Mo dopant level; the number of the color center depends on the Mo doping amount, and the color center traps the photogenerated electrons more rapidly when it is isolated. The black color was bleached by purging the air in the solution. In particular, the gray state which is observed as a transient color is promising for the development of smart windows to shield the sunlight while allowing a clear and undistorted view.

Determination of W(V) in WO3 Photochromism Using Localized Surface Plasmon Resonance of Ag Nanoparticles.

A reversible color change of WO3 has been widely studied to develop new energy-saving technologies such as smart windows, rewritable paper, and information displays. A blue coloration arises from the intervalence charge transfer between W(VI) and W(V), which is partially formed by the reduction of WO3 under UV light or an applied voltage. This means that WO3 has a mixed-valence state of W(V) and W(VI) upon the reduction. However, despite many studies for various applications, how many W(V) atoms are formed and contribute to the intervalence charge transfer (IVCT) transition remains unclear because W(V) formed in WO3 cannot be determined quantitatively. We determined the amount of the photogenerated W(V) in an aqueous WO3 colloidal solution containing ethylene glycol (EG) by observing the localized surface plasmon resonance (LSPR) peaks of Ag nanoparticles which were produced by a redox reaction between W(V) and Ag+. EG acted as a hole scavenger to suppress the recombination between the photogenerated holes and electrons. First, we explored the reaction condition where only the IVCT transition was observed under UV irradiation, and then it decreased in response to the increase in the LSPR peak in the dark. Under such a condition, the absorbance at 775 nm (A775) due to the IVCT transition was observed after the UV irradiation for 30 s, and the absorbance at 410 nm (A410) due to the LSPR absorption was obtained when A775 completely disappeared in the dark. Experiments were performed at various UV intensities to confirm a proportional relationship between A775 and A410. Electron spin resonance measurements revealed that A775 was proportional to the amount of W(V). Furthermore, Ag nanoparticles were synthesized by a polyol reduction method to obtain the relationship between the LSPR peak intensity and the Ag+ concentration, which was consumed for the formation of Ag. On the basis of all of these relationships, A775 of 1.669 corresponded to 2.53 × 10-4 mol dm-3 W(V), which was estimated to be only 0.21% of 0.12 mol dm-3 WO3 used in this study, and the molar absorption coefficient for the IVCT transition between W(V) and W(VI) was evaluated to be 6.85 × 103 dm3 mol-1 cm-1.

Crystal Facet Engineering and Hydrogen Spillover-Assisted Synthesis of Defective Pt/TiO2-x Nanorods with Enhanced Visible Light-Driven Photocatalytic Activity.

Hydrogen spillover can assist the introduction of defects such as Ti3+ and concomitant oxygen vacancies (VO) in a TiO2 crystal, thereby inducing a new level below the conduction band to improve the conductivity of photogenerated electrons and the visible light absorption property of TiO2. Meanwhile, crystal facet engineering offers a promising approach to achieve improved activity by influencing the recombination step of the photogenerated electrons and holes. In this study, with the aim of achieving enhanced visible light-driven photocatalytic activity, rutile TiO2 nanorods with different aspect ratios were synthesized by crystal facet engineering, and Pt-deposited TiO2-x nanorods (Pt/TNR) were then obtained via reduction treatment assisted by hydrogen spillover. The reduction treatment at 200 °C induced the formation of surface Ti3+ exclusively, whereas surface Ti3+ and VO were formed by performing the reduction at 600 °C. The Pt/TNR with a higher aspect ratio reduced at 200 °C exhibited the highest activity in photocatalytic H2 production under visible light irradiation owing to the synergistic effect of the introduction of Ti3+ defects and the spatial charge carrier separation induced by crystal facet engineering.

One-Pot Synthesis of Long Rutile TiO2 Nanorods and Their Photocatalytic Activity for O2 Evolution: Comparison with Near-Spherical Nanoparticles.

Rutile TiO2 nanorods with lengths greater than 600 nm and aspect ratios greater than ca. 16 were synthesized through a one-pot hydrothermal method using lactic acid (LA) as a structure-directing agent. Under the hydrothermal treatment at 200 °C, the LA concentration higher than 1.6 mol dm-3 and the hydrothermal time of 72 h were needed to obtain 100% rutile nanorods. The length and the width of the nanorods increased with the increasing LA concentration. The photocatalytic activity of the synthesized nanorods was evaluated for the oxygen evolution in aqueous AgNO3 solutions under ultraviolet irradiation. Calcination of the synthesized nanorods at 400 °C was required to decompose residual organic compounds on the surface and improve the oxygen evolution. The highest oxygen evolution rate was obtained with the nanorods after being calcined at 800 °C. It is worth noting that the nanorods retained their shape (aspect ratio of 8.8) at 800 °C. Selected area electron diffraction patterns indicated that the side or the end surface of the nanorods was attributable to the {110} or {111} facet, respectively. Deposition of Pt or PbO2 on the nanorods revealed that the {110} or {111} facet acted as reductive or oxidative sites. For comparison, near-spherical TiO2 nanoparticles were synthesized by a sol-gel method. Furthermore, using glycolic acid as the structure-directing agent, we synthesized small rutile TiO2 nanorods (aspect ratio of 9) and changed the shape to near-spherical (aspect ratio of 1.3) by calcining at 800 °C. Time-resolved diffuse reflectance spectra were measured to determine the lifetime of the photogenerated electrons. The photocatalytic activity of the nanorods was much lower than that of the near-spherical TiO2 nanoparticles. However, the nanorods synthesized with LA are useful as catalyst support or platforms for various applications because of their unique morphology and high heat resistance.

Visible light responsive TiO2 photocatalysts for degradation of indoor acetaldehyde.

Photocatalysis is a promising technique for developing sustainable and environmentally friendly materials to improve indoor air quality. Visible-light-responsive TiO2 has been widely investigated but there are inconsistent results because photocatalytic properties depend strongly on synthetic methods. Herein, we synthesize TiO2 doped with 10 different metal ions (M-TiO2) by conducting a dialysis in a sol-gel method to obtain the best photocatalyst for the degradation of acetaldehyde under LED irradiation. Purification of a sol by dialysis enables us to discuss pure effects of dopants on the photocatalytic activity because impurities such as counter ions of metal salts are removed before sintering. Only Cr-, Pt-, V-, and Fe-TiO2 show photocatalytic activity and the optimal doping amounts are 0.50-1.7, 0.10, 1.0, and 0.10 atom%, respectively. Such differences in the optimal amounts can be explained in terms of the dopant ions having different valence states, suggesting the formation of oxygen vacancies. The Cr-TiO2 powder exhibits high activity even at the doping amount of 4.2 atom%. We also demonstrate that the Cr-TiO2 film prepared on a glass substrate can be used to degrade acetaldehyde by changing the film thickness and the LED intensity depending on the degree of the indoor contamination.

Effect of Dispersants on Photochromic Behavior of Tungsten Oxide Nanoparticles in Methylcellulose.

Tungsten oxide-based photochromic films that change reversibly in air between colorless-transparent in the dark and dark blue under UV irradiation were prepared by using methylcellulose as a film matrix and various dispersants. Alpha-hydroxyl acid such as glycolic acid (GA) or glyceric acid (GlyA) is the best dispersant because it can make the film transparent by adding a small quantity much less than that of 3-hydroxypropionic acid or ethylene glycol. Fourier-transform infrared spectra and Raman spectra indicate that a strong interaction exists between WO3 and GA or GlyA. The coloration and bleaching processes of the prepared films were investigated to clarify the effect of the dispersants and the moisture contents. The bleaching rate remarkably decreased in the films containing GA or GlyA but accelerated by increasing the contact with O2. Measurements of electron-spin resonance reveals that GA and GlyA as dispersants stabilize the W5+ state. This paper shows that the coloring rate and the period for keeping the blue-colored state are tunable by changing the dispersants. The photochromic films containing α-hydroxyl acid as the dispersant have the potential for application as rewritable film on which information displayed with blue-colored state can be clearly readable for longer times compared with other dispersants.

Effect of Mixed Valence States of Platinum Ion Dopants on the Photocatalytic Activity of Titanium Dioxide under Visible Light Irradiation.

Titanium dioxide doped with the Pt ion (Pt-TiO2) was synthesized by a sol-gel method using only water as the solvent and conducting dialysis. The photocatalytic activity for the degradation of 4-chlorophenol (4-CP) on Pt-TiO2 was not affected by the Brunauer-Emmett-Teller specific surface area under visible light (VL) irradiation. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure measurements revealed that only the Pt(IV) ion existed in the TiO2 bulk and both Pt(II) and Pt(IV) were present near the Pt-TiO2 surface. Pt(IV) is most likely substituted in the Ti(IV) site of the TiO2 lattice because of their similar ionic sizes. Quantitative analysis of Pt(II) was performed in the XPS measurements, indicating that the amount of Pt(II) on the surface increased with an increase in the doping amount from 0.2 to 1.0 atom %. We synthesized 0.5 atom % Pt-TiO2 with various Pt(II)/Pt(IV) ratios by changing the Ti(OC3H7)4 concentration used in the sol-gel synthesis. The 4-CP conversion on Pt-TiO2 increased linearly with an increase in the Pt(II)/Pt(IV) ratios. A similar relationship was obtained with Pt-TiO2, which was prepared by a conventional sol-gel method in ethanol-water mixed solvent. Therefore, the Pt(II)/Pt(IV) ratio is a key factor affecting the photocatalytic activity of Pt-TiO2 under VL irradiation. Our results indicate that controlling the mixed valence states of the doped metal ions is a new strategy to developing highly active metal-ion-doped TiO2 under VL irradiation.

Kinetics of Coloration in Photochromic Tungsten(VI) Oxide/Silicon Oxycarbide/Silica Hybrid Xerogel: Insight into Cation Self-diffusion Mechanisms.

Silicon oxycarbide/silica composites with well-dispersed tungsten(VI) oxide (WO3) nanoparticles were obtained as transparent hybrid xerogels via an acid-catalyzed sol-gel process (hydrolysis/condensation polymerization) of 3-(triethoxysilyl)propyl methacrylate (TESPMA) and tetraethoxysilane (TEOS). The self-diffusion mechanism of alkali-metal cations and the kinetics of the photochromic coloration process in the WO3/TESPMA/TEOS hybrid xerogel systems have been systematically investigated. Under continuous UV illumination, a gradual color change (colorless → blue) corresponding to the reduction of W(6+) into W(5+) states in WO3 nanoparticles can be confirmed from the WO3/TESPMA/TEOS hybrid xerogels containing alkali-metal sulfates, although no coloration of the hybrid xerogel without alkali-metal sulfate was observed. The coloration behavior depended exclusively on a variety of alkali-metal cations present in the hybrid xerogel system. Furthermore, a detailed analysis of the self-diffusion mechanism confirmed that the alkali-metal cations electrostatically interact with a layer of unreacted silanol groups on the TESPMA/TEOS matrix surface, and subsequently pass through the interconnected pore network of the hybrid xerogel. More interestingly, in the context of an Arrhenius analysis, we found a good coincidence between the activation energies for alkali-metal cation self-diffusion and UV-induced coloration in the WO3/TESPMA/TEOS hybrid xerogel system containing the corresponding alkali-metal sulfate. It is experimentally obvious that the photochromic properties are dominated by the diffusion process of alkali-metal cations in the WO3/TESPMA/TEOS hybrid xerogel system. Such hybrid materials with cation-controlled photochromic properties will show promising prospects in applications demanding energy-efficient "smart windows" and "smart glasses".

Photochromic Properties of Tungsten Oxide/Methylcellulose Composite Film Containing Dispersing Agents.

Tungsten oxide-based photochromic films which changed reversibly in air between colorless- transparent in the dark and dark blue under UV irradiation were prepared by using methylcellulose as a film matrix and polyols such as ethylene glycol (EG), propylene glycol (PG), and glycerin (Gly) as dispersing agents. Influence of the dispersing agents and water in the films on the photochromic behavior was systematically studied. Under UV irradiation, absorption bands around 640 and 980 nm increased and the coloring rate was the following order: Gly > EG > PG. An increase in the amounts of dispersing agents or water accelerated the coloring rate. By increasing the water content of the film, a new absorption peak appeared at ca. 775 nm and the Raman spectra indicated a shift of W-O-W stretching vibration to lower wavenumber which was due to the formation of hydrogen bonding. All absorption spectra were fit by three Lorentz functions, whose bands were ascribed to various packing of WO6 octahedra. After the light was turned off, the formation of W(5+) was stopped and bleaching occurred by the reaction with O2 in air to recover its original transparent state. We anticipate that the biodegradable photochromic films developed in this study can be applied in recyclable display medium and especially in detachable films for glass windows whose light transmission properties are changed by sunlight, i.e., for usage as an alternative of smart windows without applying voltage.

Mechanism of peripheral substituent effects on adsorption-aggregation behaviors of cationic porphyrin dyes on tungsten(VI) oxide nanocolloid particles.

The adsorption and aggregation behaviors of the cationic porphyrin derivatives such as 5,10,15,20-tetrakis(4-pyridyl)porphyrin [TPyP], 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin [TMPyP], 5,10,15,20-tetrakis(N-ethyl-4-pyridyl)porphyrin [TEPyP], and 5,10,15,20-tetrakis(N-n-propyl-4-pyridyl)porphyrin [TPPyP] (hereafter called "TPyP derivatives") in the tungsten(VI) oxide (WO3) colloid aqueous solution at weak acidic pH were studied by UV-vis spectroscopy. The TPyP derivatives were strongly adsorbed as monolayer onto the WO3 surface via the electrostatic interaction between their peripheral cationic substituents and negatively surface-charged WO3 colloid particles, and most of the ones adsorbed eventually formed J-type dimers aligned in the head-to-tail fashion. These different dimerization states were effectively analyzed by the change of ratios among the intensities of exciton split Soret bands (H- and J-bands). Judging from the exciton coupling theory and adsorption measurements, we concluded that the J-dimer geometry of the TPyP derivatives adsorbed on the WO3 colloid particle surface is strongly dependent on the presence and difference of peripheral substituents. The results described here indicate a new and promising way of designing surface supramolecular structures combination of two principles, the self-association of organic dyes, and the steric repulsive interaction between the peripheral substituents and the inorganic semiconductor surfaces.

Surface-enhanced photochromic phenomena of phenylalanine adsorbed on tungsten oxide nanoparticles: a novel approach for "label-free" colorimetric sensing.

The enhanced photochromic behaviors of the L-phenylalanine (Phe)-tungsten(VI) oxide (WO3) colloid binary aqueous solution have been investigated by means of UV-vis absorption spectrometry. The phenomena provided a potential use of the WO3 nanoparticles as a colorimetric probe for sensitive "label-free" detection of Phe.

Photocatalytic degradation of chlorinated ethanes in the gas phase on the porous TiO(2) pellets: effect of surface acidity.

The photocatalytic degradation of chlorinated ethanes was studied in a tubular photoreactor packed with TiO(2) pellets prepared by sol-gel method. The steady-state condition was not obtained, but the deterioration in the photocatalytic activity was observed during the irradiation. Effects of mole fractions of water vapor, O(2), and C(2)H(5)Cl or C(2)H(4)Cl(2) and reaction temperature on the photodegradation of C(2)H(5)Cl or C(2)H(4)Cl(2) were examined, and these data were compared with those obtained by the photodegradation of chlorinated ethylenes. On the basis of the products detected with and without oxygen in the reactant's gas stream, we proposed the degradation mechanism. Measurement of diffuse reflectance infrared Fourier transform spectroscopy of pyridine adsorbed on the catalysts showed that decrease in the conversion for the photodegradation of C(2)H(5)Cl was attributable to the formation of Brønsted acid sites. Comparison of the data obtained with the TiO(2) and the sulfated TiO(2) (SO(4)(2-)/TiO(2)) pellets indicated that the photodegradation of C(2)H(5)Cl was suppressed by the presence of the Brønsted sites, but that of trichloroethylene was not affected. Such a difference is attributable to the adsorption process of these reactants on the acid sites on the catalyst surface.

Controllable adsorption and ideal H-aggregation behaviors of phenothiazine dyes on the tungsten oxide nanocolloid surface.

The monomer-aggregate equilibrium of four phenothiazine (PN) dyes, containing thionine (TH), methylene blue (MB), new methylene blue (NMB), and 1,9-dimethylmethylene blue (DMB), in the tungsten(VI) oxide (WO(3)) nanocolloid solution has been investigated by means of UV-vis spectroscopy. Addition of PN dye into the WO(3) nanocolloid solution brought about significant changes in the absorption spectrum, suggesting the formation of H-type (face-to-face fashion) trimer on the WO(3) nanocolloid surface. The adsorptivity of PN dyes onto the WO(3) nanocolloid surface was diminished by the raising the ionic strength, indicating the evidence of the electrostatic interaction between cationic PN dye and negatively charged WO(3) nanocolloids. The detail analysis of each spectral data provided insight into the effect of molecular structure of PN dyes on the adsorption and aggregation behaviors on the WO(3) nanocolloid surface. Moreover, in situ measurement of PN dye aggregation using the centrifugal liquid membrane (CLM) technique revealed that the aggregation of PN dyes on the WO(3) nanocolloid surface proceeded in a two-step three-stage (monomer --> dimer --> trimer) formation. The aggregation mechanism of PN dyes on the WO(3) nanocolloid surface was discussed on the basis of Kasha's exciton theory.

Enhanced photodegradation of organic dyes adsorbed on a clay.

The interaction of three photoactive organic dyes, Rhodamine B, Rhodamine 6G and a stilbazolium derivative 4'-dimethylamino-N-methyl-4-stilbazolium with synthetic sodium-saponite has been examined by UV-visible absorption spectroscopy. In all cases, bathochromic shifts and the reduction of peak absorbance for the dyes were observed in the absorption spectra at a low dye concentration (25% adsorption of the cation exchange capacity (CEC) of the clay), although the shape and the width of their absorption bands were similar to those in aqueous solution. This absorption behavior indicates that the organic dye molecules adsorbed onto the surface of the negatively charged clay particles and the adsorbed molecules were well dispersed. The photodegradation of the organic dyes in aqueous solution and in the clay suspension has been also examined by the irradiation of a laser beam at a wavelength of 532 nm. We have found that the hybridization of the organic dyes with the exfoliated clay particles largely enhanced a photodegradation. The clay particles acted as a catalyst even at a high concentration such as approximately 300% of CEC.