Humidity dependence of carbon dioxide generation during photodegradation of biaxially oriented polypropylene in oxygen

UV generation of CO₂ gas from a range of biaxially oriented polypropylene (BOPP) films exposed in oxygen gas has been measured by in situ infrared spectrometry and compared with the development of absorption at 1713 cm⁻¹ due to carbonyl formation in the same films. As in studies of other polyalkene films, the CO₂ measurements, which take only 3 h, correlate well with carbonyl development measurements that require hundreds of hours.Upon UV irradiation of BOPP in dry oxygen an induction time of ∼60 min preceded a linear increase of photogenerated CO₂. In wet oxygen, no noticeable induction time preceded the linear increase of CO₂. The rate of CO₂ increase was greater when the oxygen was humidified. This pattern was observed for four different types of film and for films of different thickness. The increase in the rate of CO₂ photogeneration with increased humidity was greater for thicker films. The correlation between the amount of CO₂ generated and the strength of the carbonyl absorption developed under standard conditions was better for BOPP oxidation in dry than in humidified oxygen. The inclusion of recycled polymer caused an increase in the rate of photodegradation.Although measurements on each subset of films demonstrated a clear increase in the photogeneration of CO₂ at high humidity, the mechanism by which the CO₂ generation from BOPP is enhanced remains unclear and further work is necessary to resolve this puzzle.     

Rapid measurement of polymer photo-degradation by FTIR spectrometry of evolved carbon dioxide

A novel method, allowing simultaneous UV exposure of a polymer sample and IR interrogation of the vapour in a specially constructed cell, has been applied to polyethylene (PE) samples containing TiO₂ pigments with different photoactivities. Measurements of the CO₂ generated by films exposed to ultraviolet irradiation (UV) were completed in 5 h - very much less than conventional accelerated tests. The TiO₂ pigments used included anatase and rutiles with different surface treatments. Anatase pigmented material gave significantly higher CO₂ emission than unpigmented PE whilst rutile-pigmented PEs either gave reduced CO₂ emission or enhanced emission, according to the surface treatment. The ranking of the pigments as protectants or pro-degradants correlated well with the carbonyl index measured after more than 300 h exposure to UVA fluorescent tubes in a QUV machine.The method was then used to probe mechanistic aspects of the photo-oxidation of pigmented polyethylene (PE) film. For unpigmented polymer the photo-degradation was sensitive to changes in the small fraction of incident UV below 300 nm, but for pigmented films this was much less important. This is because unpigmented film degrades by direct photochemical attack whereas, for pigmented film, photocatalysis by TiO₂, which absorbs in the 300-400 nm region, is important. For films whose photo-oxidation was dominated by photocatalysis by the TiO₂ the rate of oxidation was shown to vary as the square root of the UV intensity. By contrast, for unpigmented films the rate of direct photochemical oxidation was linearly proportional to UV intensity. The difference is a consequence of the controlling role of electron-hole recombination in photocatalytic processes. For both unpigmented and pigmented films the rate of oxidation was shown to increase with increasing humidity and oxygen content of the atmosphere.     

IR-study of hydrated surface of oxide photocatalysts

IR spectroscopy combined with thermogravimetry was used to investigate the effect of the pretreatment temperature on the degree of coverage of the surface of oxide photocatalysts, TiO₂, ZnO, CeO₂, and Zn²⁺/TiO₂, with water. At room temperature, the amount of adsorbed water per unit area of photocatalysts in the air decreases in the row: ZnO ≥ CeO₂ > TiO₂, whereas the temperature needed for complete removal of physically adsorbed water from the studied oxides decreases in the reverse order. Water is removed from the ZnO surface by evacuation at room temperature; in the case of CeO₂ and TiO₂, it desorbs at 200 and 300 °С, respectively. The terminal OH groups on the oxide surface are the most strongly bonded with adsorbed water. In the zinc modified TiO₂, the terminal OH groups are firstly replaced by Zn cations, which causes both hydrophobization of the samples under atmospheric conditions and a decrease in the temperature at which physically adsorbed water is released from the surface. Evacuation of ZnO at 350 °C removes the surface oxygen and results in the generation of the surface defect sites. This causes strong absorption in the IR spectra in the region of 1000—4000 cm^–1. The formation of surface defects probably causes the appearance of donor levels in the band gap. The energy of the transition of electrons from these levels to the conduction band corresponds to the energy of the IR radiation. After oxidation of such samples in O₂ at 350 °C, strong absorption in the IR spectra disappears.     

Effect of surface hydration on the photocatalytic activity of oxide catalysts in the CO oxidation

The effect of the state of hydrated surface of the bulk oxide photocatalysts, TiO₂, CeO₂, and ZnO on the rate of UV-induced oxidation of CO with atmospheric oxygen was studied. The activity of dehydroxylated catalyst samples evacuated at temperatures of >350 °C toward CO photooxidation decreases in the series CeO₂ > ZnO ≈ TiO₂, while that of partially hydrated samples after pretreatment at 20 °C changes in the order TiO₂ > ZnO ≥ CeO₂ ≈ 0. According to the results, the difference in the photocatalytic activity toward CO oxidation on the dehydrated ZnO, TiO₂, and CeO₂ catalysts is attributable to different concentrations of oxygen vacancies, which are formed more readily after high-temperature treatment on ZnO and CeO₂ and thus promote higher rate of CO photooxidation. Using a new technique for recording transmittance IR spectra, it was found that photoirradiation in the presence of adsorbed water and O₂ gives peroxides and hydroperoxides, with their concentrations decreasing in the series TiO₂ >> ZnO >> CeO₂. Most likely, these species are active intermediates of CO photooxidation with oxygen in the presence of adsorbed water. The hydrophobization effect was detected upon TiO₂ modification with zinc, resulting in removal of surface acid sites capable of adsorbing water. The TiO₂ modification with zinc increases the activity of CO photooxidation with respect to the oxidation catalyzed by samples pretreated at low temperatures (20—60 °C).     

High photocatalytic degradation activity of polyethylene containing polyacrylamide grafted TiO2

A novel photocatalytic polyacrylamide grafted TiO₂ (PAM-g-TiO₂) nanocomposite was prepared and embedded into a low density polyethylene (LDPE) plastic. Photocatalytic degradation of the LDPE/PAM-g-TiO₂ composite film was carried out under ambient conditions under ultraviolet light irradiation. The properties of composite film were compared with those of the pure LDPE film by measuring the changes in weight loss, carbonyl index, molecular weight, tensile strength and elongation at break. PAM-g-TiO₂ embedded LDPE showed highly enhanced photocatalytic degradation. Irradiating the LDPE/PAM-g-TiO₂ composite film for 520 h under UV light reduced its weight by 39.85% and average molecular weight (M_w) by 94.60%, while that of pure LDPE film was only 1.03% and 69.59%, respectively. The addition of PAM-g-TiO₂ brought about the good dispersion of TiO₂ in LDPE matrix and improved the hydrophilicity of composite film, which were able to facilitate the degradation of LDPE. The photocatalytic degradation mechanism of the films is briefly discussed.     

Synthesis and Characterization of TiO2 Doped ZnO Microtubes

The TiO₂-doped ZnO microtubes have been successfully fabricated via a wet chemicalmethod, using zinc chloride and titanium sulphate as the starting materials. The as-synthesized products were characterized by X-ray diffraction, field emission scanning electronmicroscopy and room temperature photoluminescence measurement. The photocatalytic ac-tivity in degrading methyl orange was measured with a UV-Vis spectrophotometer. The pure ZnO microtubes exhibit an exact hexangular hollow structure with a diameter of about 700 nm, a length of 3 μm and a wall thickness of about 40 nm. The TiO₂-doped ZnO microtubes with TiO₂/ZnO ratio less than 5% have the same dimension with the pure ZnO microtubes, a smooth column shape, not a hexangular structure. The growth of ZnO may be inhibited by the more Ti⁴⁺ doped into ZnO structure to achieve a small dimension or a multiphase. The crystallinity of ZnO microtubes decreases with increasing TiO₂ content, and then a multiphase containing ZnO, Ti₃O₅ and TiO occur when the TiO₂/ZnO ratio is more than 5%. The UV emission intensity of the TiO₂-doped ZnO obviously increases and then tends to decrease with TiO₂/ZnO ratio increasing. The photocatalytic properties of the TiO₂-doped ZnO microtubes are very effcient in degrading organic dyes of methyl orange and are well identical with its PL properties and the crystallinity.     

Titania supported copper catalysts for methanol synthesis from carbon dioxide

The effect of co-catalyst (ZnO or ZrO₂) has been tested for hydrogenation of CO₂ on CuO/TiO₂ and CuO/Al₂O₃. CuO−ZnO/TiO₂ catalyst showed the highest activity for methanol synthesis. Kinetic parameters were also determined.     

TiO2-, ZnO-, and CdS-photocatalyzed oxidation of ethylene-propylene thermoplastic elastomers

The ZnO-, TiO₂-, and CdS-photocatalyzed oxidations of an amorphous ethylene-propylene copolymer ( EP copolymer) containing 75% w/w of ethylene are described. In solid films exposed under polychromatic (λ > 300 nm) or monochromatic (λ = 365 nm) UV light, it is observed that the introduction of pigment (0.5–5% w/w) strongly modified the course of the photooxidation of a transparent sample. Ketonic and lactonic groups accumulate in the polymer matrix without being converted photochemically into acidic, ester, and vinyl groups. In the kinetic study it is pointed out that the variations of the rate of formation of carbonyl groups depend on the nature of the pigment. With highly photoactive pigments (ZnO and untreated TiO₂ RL11A), the rate is at first a decreasing function of the pigment percent, then an increasing function. With poorly photoactive pigments (treated TiO₂ RL90 and CdS), the rate of formation of carbonyl groups is a decreasing function of the pigment content. It is therefore emphasized that, at a low pigment content, the inner filter effect prevails over the photocatalytic influence with any pigment. It is also observed that the rate of formation of vinyl groups, photoproducts formed from the excited ketones, is a monotonously decreasing function of the pigment content. The complete inhibition of the ketone photochemistries is observed with ZnO in conditions in which the light is not absorbed by the pigment, suggesting that the carbonyl groups formed are adsorbed on the pigment.     

Nucleation Activation and Spherical Crystals Morphology of LLDPE/LDPE/TiO2 Nanocomposites Prepared by Non-Isothermal Crystallization

The nucleation activation of TiO₂ nanoparticles in the linear low-density polyethylene (LLDPE)/low-density polyethylene (LDPE)/TiO₂ nanocomposites prepared by non-isothermal crystallization, the spherical crystals morphology of the etched LLDPE/LDPE and LLDPE/LDPE/TiO₂ composites were investigated by differential scanning calorimetry (DSC) and field-emission scanning electron microscopy (FE-SEM), respectively. The results showed that the heterogeneous nucleation activation of TiO₂ nanoparticles was accelerated by the fast cooling rate. The spherical crystals in the LLDPE/LDPE and LLDPE/LDPE/TiO₂ composites were ascribed to the same crystal structure. It was worth to note that there was distinct difference between the morphology of the cocrystallization LLDPE/LDPE crystals and that of the independent crystallization LLDPE/LDPE crystals.     

Selectivity in the Ligand Functionalization of Photocatalytic Metal Oxide Nanoparticles for Phase Transfer and Self-Assembly Applications

The functionalization of photocatalytic metal oxide nanoparticles of TiO₂, ZnO, WO₃ and CuO with amine-terminated (oleylamine) and thiol-terminated (dodecane-1-thiol) alkyl-chain ligands was studied under ambient conditions. A high selectivity was observed in the binding specificity of a ligand towards nanoparticles of these different oxides. It was observed that oleylamine binds stably to only TiO₂ and WO₃, whereas dodecane-1-thiol binds stably only to ZnO and CuO. Similarly, polar-to-nonpolar solvent phase transfer of TiO₂ and WO₃ nanoparticles could be achieved by using oleylamine, but not dodecane-1-thiol, whereas the opposite holds for ZnO and CuO. The surface chemistry of ligand-functionalized nanoparticles was probed by attenuated total reflectance (ATR)-FTIR spectroscopy, which enabled the occupation of the ligands at the active sites to be elucidated. The photostability of the ligands on the nanoparticle surface was determined by the photocatalytic self-cleaning properties of the material. Although TiO₂ and WO₃ degrade the ligands within 24 h under both UV and visible light, ligands on ZnO and CuO remain unaffected. The gathered insights are also highly relevant from an application point of view. As an example, because the ligand-functionalized nanoparticles are hydrophobic in nature, they can be self-assembled at the air-water interface to give nanoparticle films with demonstrated photocatalytic as well as anti-fogging properties.     

In situ preparation of polymeric cobalt phthalocyanine–decorated TiO2 nanorods for efficient photocatalytic CO2 reduction

The integration of photosensitizers with low-cost and non-toxic metal oxides is a promising strategy to design heterogeneous photocatalysts for CO₂ reduction. Herein, p–n heterojunction photocatalysts (T-CoPPcs) consisting of p-type polymeric cobalt phthalocyanines (CoPPcs) as a photosensitizer coupled with n-type TiO₂ nanorods were fabricated through a facile, eco-friendly, one-pot hydrothermal reaction. In this process, CoPPcs were grown on n-type TiO₂ nanorods, whereas protonated titanate nanorods began converting to the highly crystalline anatase phase with small crystals on the TiO₂ surfaces. The introduction of CoPPcs not only improved the solar light utilization but also accelerated the separation and migration of charge carriers via the p–n heterojunction with the strong interfacial contact Ti–O–Co bond. The increases in crystallinity and surface area of TiO₂ nanorods also contributed to the enhanced photoactivities of T-CoPPcs. The CO₂ photoreduction of the synthesized materials was evaluated in CO₂-saturated MeCN/water using [Co(bpy)₃]²⁺ as a cocatalyst and triethanolamine as a hole scavenger. The optimized nanocomposite exhibited a remarkable CO generation rate of 4.42 mmol/h/g with a high selectivity of 85.3% and outstanding catalytic stability. The influences of cocatalyst concentration, water content, catalyst loading, and hole scavenger concentration were optimized for efficient CO₂ reduction. The photocatalytic CO₂ conversion efficiency of the present system is found to be higher than that of TiO₂-based materials reported in the literature. We believe that this research into a heterostructural design strategy and photocatalytic system may be an inspiration for the development of photocatalytic CO₂-to-CO conversion.     

Modelization of photocatalyzed oxidation of polyolefins. II. ZnO and TiO2 photocatalyzed decomposition of tert-butyl hydroperoxide and atactic polypropylene hydroperoxides

Direct evidence of the TiO₂ and ZnO photocatalytic decomposition of tert-butyl hydroperoxide and atactic polypropylene hydroperoxides in solution is reported. Molecular and macromolecular hydroperoxides behaved similarly. Untreated TiO₂ in the rutile form was a far more efficient photocatalyst than ZnO in solution; the photoactivities of both pigments were limited on preferential absorption sites. In the solid state no preferential reaction sites were observed. When added to preoxidized atactic polypropylene both pigments were photocatalysts of the formation of macromolecular hydroperoxides and of their decomposition. The photoreactivities of untreated TiO₂ and ZnO varied less than in solution.     

Controlled oxidation of benzyl ethers on irradiated semiconductor powders

Irradiation of a suspension of powdered TiO₂, a photoactive semiconductor, in oxygen saturated acetonitrile leads to mild selective oxidation of substrates containing a benzylic methylene by conversion of that carbon to a carbonyl group. The method is shown to be synthetically useful for the preparation of esters from ethers and ketones from hydrocarbons. A critical analysis of the products and of the possible intermediates results in a plausible mechanistic pathway for these photooxidations.     

Synthesis of camphorquinoxaline and quinoxaline derivatives over metal oxides as catalyst

Under solvent-free conditions, the synthesis of camphorquinoxaline and quinoxaline derivatives catalyzed by various solid metal oxides (ZnO, TiO₂, ZrO₂, MgO, acidic and basic Al₂O₃, and CaO) and salts (K₂CO₃, CaCO₃) is described. In the cases of ZnO, TiO₂, and ZrO₂, the catalysts can be recovered and reused several times without losing activity.     

Methane generated during photocatalytic redox reaction of alcohols on TiO2 suspension in aqueous solutions

Studies on the photo-catalytic redox reaction of C1–C3 alcohols such as methanol, ethanol and 2-propanol were carried out in aqueous solution containing TiO₂ photocatalyst (0.1% w/v) as suspension using 350 nm light. Other hydrocarbons such as ethane and ethene in the case of ethanol, and propene in the case of 2-propanol with low yields were produced along with the major photolytic products methane and carbon dioxide. The yields of methane and CO₂ were found to be dependent on the light exposure time and ambient conditions. Methane yields were higher in 2-propanol and ethanol systems than in methanol system, showing their better hole-scavenging properties. In the aerated condition, methane was produced during photolysis of all alcohols in the presence of TiO₂ and the yield was comparable to those observed in the corresponding CO₂-saturated systems. The overall results reveal that the surface adsorbed, as well as in-situ-generated CO₂ from photo-oxidation of alcohols are equally responsible for methane formation through photo-reduction in presence of TiO₂. In the O₂-saturated system, the methane yield was lower as compared to that in aerated system, in contrast to the CO₂ yield. In N₂O-and N₂-purged systems, the yield of methane was observed to be low, inferring that the methane generation has not taken place through photodecomposition/photodissociation of alcohols. Again, photolysis of alcohols without TiO₂ did not generate any methane.     

Selective oxidation of propylene over gold deposited on titanium-based oxides

Gold supported on titanium-based metal oxides can assist the selective partial oxidation of propylene at temperatures from 313 K to 573 K in a gas containing both H₂ and O₂. The preparation method was found to be crucial in controlling the selectivities. In general, impregnation and chemical vapor deposition methods do not produce selective catalysts. Only the deposition-precipitation method makes gold selective to propylene oxide or propanal, suggesting that a strong contact between the gold particles and the titanium ion sites on the support is important. The effect of changing the support was also dramatic; the use of the anatase form of TiO₂ and Ti-MCM-41 results in propylene oxide production, while the rutile structure of TiO₂ caused complete oxidation to CO₂. Microporous crystalline titanium silicates such as TS-1, TS-2, and Ti-β zeolite make gold relatively selective to propanal and of the three TS-1 gives the highest selectivity. These results indicate that the oxidation of propylene in the copresence of H₂ must involve the surface of the supports and that the reaction takes place at the interface perimeter around the gold particles.     

CdS‐Encapsulated TiO2 Nanotube Arrays Lidded with ZnO Nanorod Layers and Their Photoelectrocatalytic Applications

A novel TiO₂ nanotube array/CdS nanoparticle/ZnO nanorod (TiO₂ NT/CdS/ZnO NR) photocatalyst was constructed which exhibited a wide‐absorption (200–535 nm) response in the UV/Vis region and was applied for the photoelectrocatalytic (PEC) degradation of dye wastewater. This was achieved by chemically assembling CdS into the TiO₂ NTs and then constructing a ZnO NR layer on the TiO₂ NT/CdS surface. Scanning electron microscopy (SEM) results showed that a new structure had been obtained. The TiO₂ NTs looked like many “empty bottles” and the ZnO NR layer served as a big lid. Meanwhile the CdS NPs were encapsulated between them with good protection. After being sensitized by the CdS NPs, the absorption‐band edge of the obtained photocatalyst was obviously red‐shifted to the visible region, and the band gap was reduced from its original 3.20 eV to 2.32 eV. Photoelectric‐property tests indicated that the TiO₂ NT/CdS/ZnO NR material maintained a very high PEC activity in both the ultraviolet (UV) and the visible region. The maximum photoelectric conversion efficiencies of TiO₂ NT/CdS/ZnO NR were 31.8 and 5.98 % under UV light (365 nm) and visible light (420–800 nm), respectively. In the PEC oxidation, TiO₂ NT/CdS/ZnO NR exhibited a higher removal ability for methyl orange (MO) and a high stability. The kinetic constants were 1.77×10^?4 s^?1 under UV light, which was almost 5.9 and 2.6 times of those on pure TiO₂ NTs and TiO₂ NT/ZnO NR, and 2.5×10^?4 s^?1 under visible light, 2.4 times those on TiO₂ NT/CdS.     

阴离子改性甘油溶液中TiO2纳米管阵列的制备和表征

本文采用电化学阳极氧化法以含氟的甘油和水混合溶液为电解液在纯钛表面制备了一层排列规整的TiO2纳米管阵列,研究了电解液中额外添加3种2价阴离子、不同的电解时间及不同的添加物浓度等因素对所获得的TiO2纳米管阵列形貌的影响。结果表明,在改性电解液中制备的TiO2纳米管阵列的长度均超过了未改性的电解液中制备的,并随着氧化时间的增长,纳米管管口直径增大,管壁变薄;同时添加的(NH4)2TiF6浓度在0.025~0.1 mol.L-1范围内均可获得管长更长且形貌较好的TiO2纳米管阵列。     

Surface species and gas phase products in the preferential oxidation of CO on TiO2-supported Au-Rh bimetallic catalysts

The oxidation of CO in the presence of hydrogen (PROX process) was investigated on bimetallic Au-Rh catalysts at 300–373 K by Fourier transform infrared spectroscopy and mass spectroscopy. The effects of catalyst composition, reaction temperature and composition of the reacting gas mixtures have been studied. The IR studies revealed the formation of bi- and monodentate carbonates, bicarbonates and hydrocarbonates on the catalysts surfaces; these surface species proved to be not involved in the surface reactions. The formation of adsorbed formaldehyde was observed on all surfaces, except 1% (0.25Au+0.75Rh)/TiO₂. Adsorbed CO₂ (as the surface product of CO oxidation) was not detected on any surface. The presence of both O₂ and H₂ reduced the surface concentration of CO adsorbed on the metallic sites. Mass spectroscopic analysis of the gas phase showed that gaseous CO₂ was formed in the highest amount in the CO+O₂ mixture, the presence of H₂ suppressed the amount of CO₂ produced. This negative effect of H₂ was the lowest on the 1% Rh/TiO₂ and 1% (0.25Au+0.75Rh)/TiO₂ catalysts.     

Formation of different products during photo-catalytic reaction on TiO<Subscript>2</Subscript> suspension in water with and without 2-propanol under diverse ambient conditions

Studies on photo-catalytic reduction of CO₂ using TiO₂ photo-catalyst (0.1%, w/v) as a suspension in water was carried out at 350 nm light. CO₂ from both commercially available source, as well as generated in situ through 2-propanol oxidation, was used for this study. The photolytic products such as hydrogen (H₂), carbon monoxide (CO) andmethane (CH₄) generated were monitored in TiO₂ suspended aqueous solution with and without a hole scavenger, viz., 2-propanol. Similar photolytic experiments were also carried out with varying ambient such as air, O₂, N₂ and N₂O. The yields of CO and CH₄ in all these systems under the present experimental conditions were found to be increasing with light exposure time. H₂ yield in N₂-purged systems containing 2-propanol was found to be more as compared to the without 2-propanol system. The rate of H₂ production in N₂-purged aqueous solutions containing 0.1% TiO₂ suspension were evaluated to be 0.226 and 5.8 μl/h, without and with 0.5 M 2-propanol, respectively. This confirmed that 2-propanol was an efficient hole scavenger and it scavenged photo-generated holes (h⁺), allowing its counter ion, viz., e⁻, to react with water molecule/H⁺ to yield more H₂. The formation of both CO and CH₄ in the photolysis of CO₂-purged aqueous solutions containing suspended TiO₂ in absence of 2-propanol reveal that the generation of CH₄ is taking place mainly through CO intermediate. In presence of air/O₂, the yield of H₂ in the system without 2-propanol was observed to be negligible as compared to the system containing 2-propanol in which low yield of H₂ was obtained with a formation rate of approx. 0.5 μl/h.