Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions

Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

Origin of enhanced photocatalytic activity and photoconduction in high aspect ratio ZnO nanorods

Faceted ZnO nanorods with different aspect ratios were synthesized by a solvothermal method by tuning the reaction time. Increased reaction leads to the formation of high aspect ratio ZnO nanorods largely bound by the prism planes. The high aspect ratio rods showed significantly higher visible light photocatalytic activity when compared to the lower aspect ratio structures. It is proposed that the higher activity is due to better charge separation in the elongated 1D structure. In addition, the fraction of unsaturated Zn2+ sites is higher on the {10 (1) over bar0} facets, leading to better adsorption of oxygen-containing species. These species enhance the production of reactive radicals that are responsible for photodegradation. The photocurrent for these ZnO nanostructures under solar light was measured and a direct correlation between photocurrent and aspect ratio was observed. Since the underlying mechanisms for photodegradation and photocurrent generation are directly related to the efficiency of electron-hole creation and separation, this observation corroborates that the charge separation processes are indeed enhanced in the high aspect ratio structures. The efficiency of photoconduction (electron-hole pair separation) could be further improved by attaching Au nanoparticles on ZnO, which can act as a sink for the electrons. This heterostructure exhibits a high chemisorption of oxygen, which facilitates the production of highly reactive radicals contributing to the high photoreactivity. The suggested mechanisms are applicable to other n-type semiconductor nanostructures with important implications for applications relating to energy and the environment.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Enhanced photocatalytic efficiency of AuPd nanoalloy decorated ZnO-reduced graphene oxide nanocomposites

Inhibition of electron-hole pair recombination is the most desirable solution for stimulating photocatalytic activity in semiconductor nanostructures. To implement this, herein we study the photocatalytic efficiency of elemental Au, Pd and bimetallic AuPd nanoalloy decorated pristine and reduced graphene oxide (RGO) hybridized ZnO nanorods for degrading rhodamine 6G (R6G) dye. Fabrication of Au, Pd and AuPd nanoalloy on pristine and RGO modified ZnO nanorods is simple and more importantly surfactant or polymer free. AuPd nanoalloyed ZnO-RGO nanocomposites exhibit higher photocatalytic activity for degrading dye than both Au and Pd hybridized ones, indicating the promising potential of bimetallic nanoalloys over elemental components. A non-monotonic dependence on the composite composition was found by analyzing photodegradation efficiency of a series of ZnO-RGO-AuPd hybrid nanostructures with different weight percentages of RGO. The hybrid nanostructure ZnO-RGO (5 wt%)-AuPd (1 wt%) exhibits highest photodegradation efficiency (similar to 100% degradation in 20 min) with an improvement in rate constant (k) by a factor of 10 compared to that of the ZnO-RGO nanocomposite. The enhancement of the photocatalytic activity is attributed to the better separation of photogenerated charge carriers in photocatalysts thereby suggesting possible usefulness in a broad range of applications, such as sensing, photocatalysis and solar energy conversion.

Enhanced sunlight photocatalytic activity of Ag3PO4 decorated novel combustion synthesis derived TiO2 nanobelts for dye and bacterial degradation

This study demonstrates the synthesis of TiO2 nanobelts using solution combustion derived TiO2 with enhanced photocatalytic activity for dye degradation and bacterial inactivation. Hydrothermal treatment of combustion synthesized TiO2 resulted in unique partially etched TiO2 nanobelts and Ag3PO4 was decorated using the co-precipitation method. The catalyst particles were characterized using X-ray diffraction analysis, BET surface area analysis, diffuse reflectance and electron microscopy. The photocatalytic properties of the composites of Ag3PO4 with pristine combustion synthesized TiO2 and commercial TiO2 under sunlight were compared. Therefore the studies conducted proved that the novel Ag3PO4/unique combustion synthesis derived TiO2 nanobelt composites exhibited extended light absorption, better charge transfer mechanism and higher generation of hydroxyl and hole radicals. These properties resulted in enhanced photodegradation of dyes and bacteria when compared to the commercial TiO2 nanocomposite. These findings have important implications in designing new photocatalysts for water purification.

Tensile strength properties of polyethylene netting twines under exposure to out-door and artificial UV radiation

Photodegradation of three types of polyethylene twines namely, polyethylene fibrillated tape twine, polyethylene flat tape twine and polyethylene monofilament twines were studied by exposing them to sunlight and artificial UV radiation. The percentage residual strength varied in the samples, the monofilament with the highest residual strength followed by fibrillated tape twine and flat tape twine. A plot of the difference between the breaking strengths of the fibrillated tape twine and the mono filament twines against any given period of exposure exhibited a linear relationship

Photochromic fulgide for holographic recording

(N-4'-methoxy-2-methyl-5-phenyl)-3-pyrryl-ethylidene (isopropylidene) succinic anhydride fulgide, doped in PMMA matrix, exhibits photochromic behavior. The fatigue resistance experiment shows no photodegradation is detected after more than 450 writing-erasing cycles. Study of fulgide material for holographic recording media shows the optimal exposure and the diffraction efficiency is 1047 mJ/cm(2) and 2.26%, respectively, with 10 mum thickness polymer film. Holographic grating with 1680 lines/mm at writing angle theta = 30degrees is also obtained. (C) 2004 Elsevier B.V. All rights reserved.

The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment

In this study, conventional TiO2 powder was heated in hydrogen (H-2) gas at a high temperature as pretreatment. The photoactivity of the treated TiO2 samples was evaluated in the photodegradation of sulfosalicylic acid (SSA) in aqueous suspension. The experimental results demonstrated that the photodegradation rates of SSA were significantly enhanced by using the H-2-treated TiO2 catalysts and an optimum temperature for the H-2 treatment was found to be of 500-600 degreesC. The in situ electron paramagnetic resonance (EPR) signal intensity of oxygen vacancies (OV) and trivalent titanium (Ti3+) associated with the photocatalytic activity was studied. The results proved the presence of OV and Ti3+ in the lattice of the H2-treated TiO2 and indicated that both were contributed to the enhancement of photocatalytic activity. Moreover, the experimental results presented that the EPR signal intensity of OV and Ti3+ in the H-2-treated TiO2 samples after 10 months storage was still significant higher than that in the untreated TiO2 catalyst. The experiment also demonstrated that the significant enhancement occurred in the photodegradation of phenol using the H-2-treated TiO2. (C) 2002 Elsevier Science Ltd. All rights reserved.

Hydrothermal Synthesis and High Photocatalytic Activity of 3D Wurtzite ZnSe Hierarchical Nanostructures

Novel 3D wurtzite ZnSe hierarchical nanostructures have been synthesized by a mild hydrothermal treatment. The as-prepared flowerlike nanostructures efficiently catalyze the photodegradation of methylene blue and ethyl violet present in aqueous solutions under UV light irradiation, exhibiting higher photocatalytic activity than the commercially available photocatalysts P25 and ZnSe microspheres. We also demonstrate that flowerlike morphology is important for the excellent photocatalytic activity.

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles has been developed. The core-shell nanostructures with NH4Cl as core and TiO2 center dot xH(2)O-NH4Cl as shell were prepared in nonaqueous system by the deposition on the surface of the aggregated NH4Cl crystals, which could be transformed into mesoporous anatase nanoparticles or hollow nanospheres by calcination at 500A degrees C or extraction with methanol, respectively. The hierarchical mesoporous nanostructures benefited the photocatalytic activities of the resultant titania nanomaterials, demonstrated by the UV light photodegradation of Methyl Orange.

Degradation of polyimide induced by nitrogen laser irradiation

The degradation behavior of polyimide (PMDA-ODA) induced by nitrogen laser irradiation was studied. The changes in the surface morphology and the composition of the irradiated polyimide films were examined by scanning electron microscopy, X-ray photoelectron spectroscopy and FT-IR spectroscopy. The initial reaction was achieved by photochemical degradation of polyimide in the highly electronic excited state by the absorption of a second 337 nm photon. Atmospheric oxygen sequentially reacted with the produced radicals to form a highly oxidized layer. The formation of carbonyl group was enhanced by the heat remaining on the irradiated polyimide film surfaces. (C) 2000 Elsevier Science B.V. All rights reserved.

Effect of surface state properties of TiO2 nanoparticle film on its photocatalytic activity

TiO2 nanoparticle film catalysts with different thicknesses were prepared by plasma-enhanced chemical vapor deposition(PECVD) method and the surfaces were subsequently treated by TiCl4 or O-2 plasma. Two kinds of TiO2 films with different surface properties were obtained. Their surface microstructures and energy levels of surface states were tested by AFM, XRD, SPS, The photocatalytic activities of the catalysts were determined via photodegradation experiments of phenol. The results demonstrated that photocatalytic activities of samples whose surface was treated by O-2 plasma were greater than those treated by TiCl4 plasma. Moreover, photodegradation ratio of phenol during the first hour catalyzed by 0. 17 mu m thickness TiO2 nanoparticle film was greater than other samples. Especially, the difference of photocatalytic activities of TiO2 nanoparticle films treated by TiCl4 or O-2 plasma was respectively explained by energy band theory.

Crosslinking of polyimides via spirodilactone unit in polymer backbone

A new approach for the crosslinking of polyimides via the lactamization of spirodilactone unit in polyimide backbone was studied by two means: model reaction and the comparison of the properties of the polyimide precursors to those of the crosslinking polymers. Polyimides 4 and 5 were soluble in N,N'dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), N'-methylpyrrolidone (NMP), and other common organic solvents, whereas their corresponding crosslinking polymers were insoluble in these solvents. The glass transition temperatures for polyimide 5 and its crosslinking polymer were 262 degrees C and 291 degrees C, whereas those for polyimide 4 and its crosslinking polymer were 265 degrees C and 360 degrees C. The weight-loss rate of the crosslinling polymers was apparently slower than that of the precursors when the temperature was >400 degrees C. The 10% weight-loss temperature for the polyimides 4 and 5 was <500 degrees C, whereas that for the crosslinking polymers was close to or above 600 degrees C. The results indicate that this type of crosslinking polymer has good thermal properties. The temperature for the formation of lactam was above 180 degrees C. (C) 1999 John Wiley & Sons, Inc.

Large-area nanopatterning of self-assembled monolayers of alkanethiolates by interferometric lithography.

We demonstrate that interferometric lithography provides a fast, simple approach to the production of patterns in self-assembled monolayers (SAMs) with high resolution over square centimeter areas. As a proof of principle, two-beam interference patterns, formed using light from a frequency-doubled argon ion laser (244 nm), were used to pattern methyl-terminated SAMs on gold, facilitating the introduction of hydroxyl-terminated adsorbates and yielding patterns of surface free energy with a pitch of ca. 200 nm. The photopatterning of SAMs on Pd has been demonstrated for the first time, with interferometric exposure yielding patterns of surface free energy with similar features sizes to those obtained on gold. Gold nanostructures were formed by exposing SAMs to UV interference patterns and then immersing the samples in an ethanolic solution of mercaptoethylamine, which etched the metal substrate in exposed areas while unoxidized thiols acted as a resist and protected the metal from dissolution. Macroscopically extended gold nanowires were fabricated using single exposures and arrays of 66 nm gold dots at 180 nm centers were formed using orthogonal exposures in a fast, simple process. Exposure of oligo(ethylene glycol)-terminated SAMs to UV light caused photodegradation of the protein-resistant tail groups in a substrate-independent process. In contrast to many protein patterning methods, which utilize multiple steps to control surface binding, this single step process introduced aldehyde functional groups to the SAM surface at exposures as low as 0.3 J cm(-2), significantly less than the exposure required for oxidation of the thiol headgroup. Although interferometric methods rely upon a continuous gradient of exposure, it was possible to fabricate well-defined protein nanostructures by the introduction of aldehyde groups and removal of protein resistance in nanoscopic regions. Macroscopically extended, nanostructured assemblies of streptavidin were formed. Retention of functionality in the patterned materials was demonstrated by binding of biotinylated proteins.

HPLC-ESI-MS method development for the elucidation of nicardipine degradation products

Purpose: Nicardipine is a member of a family of calcium channel blockers named dihydropiridines that are known to be photolabile and may cause phototoxicity. It is therefore vital to develop analytical method which can study the photodegradation of nicardipine. Method: Forced acid degradation of nicardipine was conducted by heating 12 ml of 1 mg/ml nicardipine with 3 ml of 2.5 M HCl for two hours. A gradient HPLC medthod was developed using Agilent Technologies 1200 series quaternary system. Separation was achieved with a Hichrome (250 x 4.6 mm) 5 μm C18 reversed phase column and mobile phase composition of 70% A(100%v/v water) and 30% B(99%v/v acetonitrile + 1%v/v formic acid) at time zero, composition of A and B was then charged to 60%v/v A;40%v/v B at 10minutes, 50%v/v A; 50%v/v B at 30minutes and 70%v/v A; 30%v/v B at 35minutes. 20μl of 0.8mg/ml of nicardipine degradation was injected at room temperature (25oC). The gradient method was transferred onto a HPLC-ESI-MS system (HP 1050 series - AQUAMAX mass detector) and analysis conducted with an acid degradation concentration of 0.25mg/ml and 20μl injection volume. ESI spectra were acquired in positive ionisation mode with MRM 0-600 m/z. Results: Eleven nicardipine degradation products were detected in the HPLC analysis and the resolution (RS) between the respective degradants where 1.0, 1.2, 6.0, 0.4, 1.7, 3.7, 1.8, 1.0, and 1.7 respectively. Nine degradation products were identified in the ESI spectra with the respective m/z ratio; 171.0, 166.1, 441.2, 423.2, 455.2, 455.2, 331.1, 273.1, and 290.1. The possible molecular formulae for each degradants were ambiguously determined. Conclusion: A sensitive and specific method was developed for the analysis of nicardipine degradants. Method enables detection and quantification of nicardipine degradation products that can be used for the study of the kinetics of nicardipine degradation processes.