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.     

Powder preparation and UV absorption properties of selected compositions in the CeO2-Y2O3 system

Several approaches have been investigated to prepare fluorite-type compositions within the (1−x) CeO₂-xYO_1.5 system. The optical properties of the resulting modified-ceria materials have been characterized in order to evaluate their potential abilities as inorganic UV absorbers. Diffuse reflectance analyses reveal a strong optical absorption between 390 and 400 nm for all substituted compositions and the spectral selectivities are estimated suitable for the targeted application. Additionally, time resolved microwave conductivity (TRMC) and phenol photodegradation analyses do not indicate any photocalatytic activity for these compositions. Aqueous colloidal suspensions of the Ce_0.7Y_0.3O_1.85 UV absorber have been carried out.     

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.     

Role of the UV absorber as a matrix in matrix‐assisted laser desorption/ionization mass spectrometric analysis of a mixture of a UV absorber and a stabilizer

A mixture of a UV absorber (Tinuvin 234 or Tinuvin 329) and a UV stabilizer (Tinuvin 770) was analyzed using matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) without any matrix. Fragmentation patterns of the UV absorbers and stabilizer were also investigated. The mass spectra showed the [M+H]⁺ ions and some fragment ions. Tinuvin 234, Tinuvin 329, and Tinuvin 770 generated three (m/z 119, 370, 432), one (m/z 252), and two (m/z 124 and 140) fragment ions, repectively. These fragment ions can be used to identify the chemical structures of the UV absorbers and stabilizer. Since the UV absorber performed a role as the matrix, the ion abundance of the UV stabilizer was enhanced by mixing with the UV absorber. When organic materials extracted from polypropylene (PP) containing the UV absorber and stabilizer were directly analyzed using MALDI‐MS without any matrix, the protonated molecule of the UV stabilizer was detected in abundance but the product ions of the UV absorber were not observed. When 2,5‐dihydroxybenzoic acid was used as a matrix, the protonated molecule of the UV absorber was observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Photocatalytic activity of polyaniline/Fe-doped TiO2 composites by in situ polymerization method

This study was focused on the photocatalytic activity of polyaniline (Pani)/iron doped titanium dioxide (Fe–TiO₂) composites for the degradation of methylene blue as a model dye. TiO₂ nanoparticles were doped with iron ions (Fe) using the wet impregnation method and the doped nanoparticles were further combined with Pani via an in situ polymerization method. For comparison purposes, Pani composites were also synthesized in the presence undoped TiO₂. The photocatalyst and the composites were characterized by standard analytical techniques such as FTIR, XRD, SEM, EDX and UV–Vis spectroscopies. Fe–TiO₂ and its composites exhibited enhanced photocatalytic activity under ultraviolet light irradiation. Improved photocatalytic activity of Fe–TiO₂ was attributed to the dopant Fe ions hindering the recombination of the photoinduced charge carriers. Pani/Fe–TiO₂ composite with 30?wt.% of TiO₂ nanoparticles achieved 28% dye removal and the discoloration rate of methylene blue for the sample was 0.0025?min^?1. FTIR, XRD, SEM, EDX and UV–Vis spectroscopies supported the idea that Fe ions integrated into TiO₂ crystal structure and Pani composites were successfully synthesized in the presence of the photocatalyst nanoparticles. The novelty of this study was to investigate the photocatalytic activity of Pani composites, containing iron doped TiO₂ and to compare their results with that of Pani/TiO₂.     

Effect of UV-absorbing agents on photodegradation of tranilast in oily gels

Tranilast (TL) oily gels containing UV-absorbing agents (UV absorber) were prepared, and the effect of the agents against photodegradation of TL was investigated. When 0.1% TL oily gel without UV absorber was exposed to light, TL was photochemically decomposed to the extent of 74.1% of its initial content at the end of the first hour. Although there were differences in the preventive effect on photodegradation of TL depending on the UV absorbers employed, 2-(2-benzotriazolyl)-p-cresol (BTPC) was the most effective absorber. The addition of UV absorbers to the oily gel did not affect the release of TL from the gel, the skin permeation, or the skin concentration of TL following topical application. UV absorbers added to TL oily gel penetrated into skin; however, their concentration in skin was similar to that following application of commercial sunscreen. These results suggest that the addition of UV absorbers to the oily gel of TL may be useful in preventing photodegradation of TL in the gel.     

Infrared study of UV-irradiated tungsten trioxide powders containing adsorbed dimethyl methyl phosphonate and trimethyl phosphate

The photodecomposition of dimethyl methylphosphonate (DMMP) and trimethyl phosphate (TMP) adsorbed on monoclinic WO₃ powders when irradiated by ultraviolet light (UV) in air, oxygen, and under evacuation was investigated using infrared spectroscopy (IR). The IR spectra show that DMMP decomposes into methyl phosphonate upon exposure to 254 nm UV for 2 h at room temperature in air. The same decomposition of DMMP occurs only at temperatures above 300°C without UV illumination. TMP differs from DMMP in that the photodecomposition product is not the same as the decomposition product obtained by heating above 300°C. Thermal decomposition leads to formation of a phosphate on the surface, whereas photodecomposition leads to the same adsorbed methyl phosphonate as found for the thermal or photodecomposition of DMMP. Since TMP does not contain a P-CH₃ bond, the formation of a methyl phosphonate on the surface after UV illumination involves a mechanism where CH₃ groups migrate from the methoxy group to the phosphorous central atom. No decomposition is observed at room temperature when DMMP or TMP adsorbed on WO₃ is irradiated under vacuum or in nitrogen atmosphere. Therefore, the photodecomposition of either DMMP or TMP adsorbed on WO₃ at room temperature does not involve a reaction with the lattice oxygen but rather a reaction with the oxygen radicals produced by the decomposition of ozone.     

Characterization of CO2 Plasma and Interactions with Polypropylene Film

The interactions between CO₂ plasma, less degrading than O₂ plasma, and polymeric surfaces are studied. CO₂ discharge and the relationships between the density of plasma reactive species are analyzed by optical emission spectroscopy and mass spectrometry. The optical emission spectrum was identified and five principal systems of carbon monoxide were assigned: the 4th and 3rd positive systems, Angstrom and 3A systems. Other systems dealing with ionized species CO⁺ ₂ and CO⁺ were also found. Mass spectrometry showed that the carbon monoxide and atomic oxygen were created through CO₂ dissociation by electronic impact. The detected molecular oxygen coming from the atomic oxygen recombination was associated with the power. The study of plasma/polymer interface showed the consumption of ionized species, the appearance of atomic hydrogen due to methyl groups transformation into exomethylene groups onto the polypropylene surface, and a degradation mechanism dependent on atomic oxygen density in the plasma phase.     

Effects of temperature on the weathering lifetime of coated polycarbonate

The lifetime of polycarbonate (PC) coated with silicone hardcoats containing UV absorber is shorter at elevated temperatures. The activation energy (E_a) for delamination was found to be 18 ± 2 kJ/mol (4.3 ± 0.5 kcal/mol) at the 95% confidence level in this study. This E_a is the consequence of the sensitivity of the substrate and the UV absorber to temperature. The E_a for PC photodegradation was previously found to be 17-21 kJ/mol (4-5 kcal/mol). The E_a for loss of absorbance in the second-generation silicone hardcoat was found to be 28.5 ± 5.4 kJ/mol (6.8 ± 1.3 kcal/mol) at the 95% confidence level. Results are consistent with experimental findings when these activation energies are used in published predictive models. Since the E_a for coating delamination depends on the E_a of UV absorber loss, coating systems different from the one in this study will need to be investigated separately.     

A Microwave-Assisted Boudouard Reaction: A Highly Effective Reduction of the Greenhouse Gas CO2 to Useful CO Feedstock with Semi-Coke

The conversion of CO₂ into more synthetically flexible CO is an effective and potential method for CO₂ remediation, utilization and carbon emission reduction. In this paper, the reaction of carbon-carbon dioxide (the Boudouard reaction) was performed in a microwave fixed bed reactor using semi-coke (SC) as both the microwave absorber and reactant and was systematically compared with that heated in a conventional thermal field. The effects of the heating source, SC particle size, CO₂ flow rate and additives on CO₂ conversion and CO output were investigated. By microwave heating (MWH), CO₂ conversion reached more than 99% while by conventional heating (CH), the maximum conversion of CO₂ was approximately 29% at 900 °C. Meanwhile, for the reaction with 5 wt% barium carbonate added as a promoter, the reaction temperature was significantly reduced to 750 °C with an almost quantitative conversion of CO₂. Further kinetic calculations showed that the apparent activation energy of the reaction under microwave heating was 46.3 kJ/mol, which was only one-third of that observed under conventional heating. The microwave-assisted Boudouard reaction with catalytic barium carbonate is a promising method for carbon dioxide utilization.     

Sorption equilibria of CO2 on silica-gels in the presence of water

The sorption equilibria of carbon dioxide on three types of silica gel (SG) with different pore size distributions in the presence of water were studied experimentally using a volumetric method at 275?K with pressures from 0 to 3.7?MPa. Both the pore size distribution of the silica gel and the quantity of pre-sorbed water impact the formation of the CO₂ hydrates. For wet silicon gel A(SG-A) with water loading ratio of 0.75, the highest CO₂ sorption was about 2.5?mmol of CO₂ per gram of dry sorbent at 275?K. Similarly, the highest sorption was about 2.7?mmol for wet SG-B with R _w =0.81. However, CO₂ hydrate did not form on the wet surface of SG-C due to its large pore sizes.     

Synthesis and Sintering-wet Carbonation of Nano-sized Carbonated Hydroxyapatite

Synthetic carbonated apatite ceramics are considered as promising alternative to auto- and allograft materials for bone substitute. In this study, Carbonated hydroxyapatite (CHA) was synthesized by nanoemulsion method. The powder produced was B-type CHA in nano-sized and had 8.25% carbonate content. The CHA samples were made into pellets and were sintered to 800 °C. Upon cooling down to 150, 200, 250 and 300 °C, carbonation with wet CO₂ was performed on the CHA in a desiccator to re-compensate the carbonate loss due to sintering and improve densification. The aim of this study was to investigate and compare the effect of cooled down temperatures on dense CHA with two kind of wet CO₂ atmospheres: direct wet CO₂ and dry CO₂ through water. Sintered CHA carbonated by using dry CO₂ through water had overall higher amount of carbonate content as compared to carbonation from wet CO₂ directly from tank. D200, sample undergone carbonation by carbonated by dry CO₂ through water at 200 °C had the highest carbonate content (3.35%).     

Controlled Synthesis of a Vacancy-Defect Single-Atom Catalyst for Boosting CO2 Electroreduction

The reaction of precursors containing both nitrogen and oxygen atoms with Ni^II under 500 °C can generate a N/O mixing coordinated Ni-N₃O single-atom catalyst (SAC) in which the oxygen atom can be gradually removed under high temperature due to the weaker Ni−O interaction, resulting in a vacancy-defect Ni-N₃-V SAC at Ni site under 800 °C. For the reaction of Ni^II with the precursor simply containing nitrogen atoms, only a no-vacancy-defect Ni-N₄ SAC was obtained. Experimental and DFT calculations reveal that the presence of a vacancy-defect in Ni-N₃-V SAC can dramatically boost the electrocatalytic activity for CO₂ reduction, with extremely high CO₂ reduction current density of 65 mA cm⁻² and high Faradaic efficiency over 90 % at −0.9 V vs. RHE, as well as a record high turnover frequency of 1.35×10⁵ h⁻¹, much higher than those of Ni-N₄ SAC, and being one of the best reported electrocatalysts for CO₂-to-CO conversion to date.     

Decolorization of C.I. Reactive Red 2 by ozonation catalyzed by Fe(II) and UV

This work evaluated the effects of pH on decolorization of C.I. Reactive Red 2 by O₃, O₃/Fe(II), UV/O₃ and UV/O₃/Fe(II) systems. At pH 4, the decolorization rate constants of O₃, O₃/Fe(II), UV/O₃ and UV/O₃/Fe(II) systems were 1.78, 3.11, 2.04 and 3.18 hr⁻¹, respectively. The decolorization rates and effective energy consumption constants of all systems were higher under basic conditions than under acidic conditions.     

"Decoking" of a "coked" zeolite catalyst in a glow discharge

'Decoking' of a 'coked' zeolite catalyst in a glow discharge in oxygen is investigated. The 'decoking' process involves reactions of atomic oxygen (O atoms) with 'coke' and yields gases such as CO, CO₂ as well as other gaseous products that could be easily pumped out.Three different modes of discharge were investigated including a static mode, a flowing-gas mode, and a periodic-purge mode where the oxygen and other gaseous products of the discharge were replaced by fresh O₂ gas after short but regular intervals of time. In some cases, additional heating was also used to provide base temperatures of the order of 100 °C to facilitate penetration of oxygen atoms into the inner layers and cages of the zeolite catalyst.This paper presents some results of spectroscopic analytical techniques used to monitor the atomization of oxygen, oxidation of 'coke', and to confirm the process of 'decoking'. More specifically, radiation emission on the 3 s ⁵S– 3p ⁵P transitions of O around 777.2–777.5 nm were selected for monitoring the atomization of O₂. On the other hand, X-ray photo-electron spectroscopy (XPS) was used to determine the amount of residual carbon and extent of 'decoking'. Furthermore, evolution of CO and CO₂ gases as a function of time was systematically monitored in real time. For CO, the 451.1 nm band head belonging to the B¹ - A¹ bands of the Angstrom system of the CO spectrum was used, while for CO₂, the band head at 353.4 nm belonging to the CO₂⁺ spectrum was used. The rates of evolution of CO and CO₂ were related to the rate of 'decoking' of the catalyst. It is noted that in the periodic-purge mode, about 63% of the total yield of CO from a given sample of the catalyst appears in the first 3-min exposure to discharge whereas it takes up to 15 min to remove nearly 94% of the removable carbon under our experimental conditions.     

Optical sensor for carbon dioxide combining colorimetric change of a pH indicator and a reference luminescent dye

A new optical CO₂ sensor based on the luminescence intensity change of the europium(III) complex tris(thenoyltrifluoroacetonato) europium(III) dihydrate ([Eu(tta)₃]) caused by the absorption change of various pH indicators—thymol blue, phenol red, or cresol red—with CO₂ was developed and its CO₂ sensing properties were investigated. For all the CO₂ sensors using pH indicators the observed luminescence intensity from [Eu(tta)₃] at 613 nm increased with increasing CO₂ concentration. The linear calibration method based on the plot of (I₁₀₀–I₀)/(I–I₀) versus the inverse of CO₂ concentration was suggested, where I₀ and I₁₀₀ were luminescence intensities at 613 nm of the CO₂ sensor film in 100% nitrogen and 100% gaseous CO₂. In all cases the plots showed good linearity and the correlation factors of the plots, r², were 0.991 for thymol blue, 0.990 for phenol red, and 0.998 for cresol red. The slopes of the plots (A/B) for thymol blue, phenol red, and cresol red were 2.2, 5.2, and 9.0%, respectively. The response times of the CO₂ sensor film were 4.0 s for thymol blue, 4.4 s for phenol red, and 8.8 s for cresol red for switching from nitrogen to CO₂, and the recovery times of films were 36 s for thymol blue, 39.2 s for phenol red, and 56.6 s for cresol red for switching from CO₂ to nitrogen. The signal changes were fully reversible and hysteresis was not observed during the measurements. The highly sensitive CO₂ sensor was developed using thymol blue as an indicator for the CO₂-sensing probe.     

Controlled Synthesis of a Vacancy‐Defect Single‐Atom Catalyst for Boosting CO2 Electroreduction

The reaction of precursors containing both nitrogen and oxygen atoms with Ni^II under 500 °C can generate a N/O mixing coordinated Ni‐N₃O single‐atom catalyst (SAC) in which the oxygen atom can be gradually removed under high temperature due to the weaker Ni?O interaction, resulting in a vacancy‐defect Ni‐N₃‐V SAC at Ni site under 800 °C. For the reaction of Ni^II with the precursor simply containing nitrogen atoms, only a no‐vacancy‐defect Ni‐N₄ SAC was obtained. Experimental and DFT calculations reveal that the presence of a vacancy‐defect in Ni‐N₃‐V SAC can dramatically boost the electrocatalytic activity for CO₂ reduction, with extremely high CO₂ reduction current density of 65 mA cm^?2 and high Faradaic efficiency over 90 % at ?0.9 V vs. RHE, as well as a record high turnover frequency of 1.35×10⁵ h^?1, much higher than those of Ni‐N₄ SAC, and being one of the best reported electrocatalysts for CO₂‐to‐CO conversion to date.     

Sonocatalytic degradation of C.I. Reactive Red 198 in H2O2-based Systems

This study elucidated the effects of pH on the decolorization of C.I. Reactive Red 198 (RR198) in US, UV/H₂O₂, US/H₂O₂ and UV/US/H₂O₂ systems. The synergistic effects in US/H₂O₂ and UV/US/H₂O₂ systems were also evaluated. At pH 4, 7 and 10, the decolorization rates of RR198 followed the order UV/US/H₂O₂ > UV/H₂O₂ > US > US/H₂O₂.     

镍基钙钛矿型催化剂的结构调控及其在甲烷干重整反应中的应用

钙钛矿材料在催化领域具有广泛的应用,其微观结构的调控对催化性能有显著的影响.我们采用柠檬酸配合法、溶胶凝胶法、燃烧法和浸渍法一系列不同的制备过程对镍基钙钛矿材料的结构进行调控,并将其应用于甲烷干重整反应,研究了制备方法对活性组分Ni的化学形态、Ni与基底的相互作用以及活性氧物种的调控,进而影响其催化活性和抗积碳能力.结果表明,燃烧法可以显著提高催化剂的结晶度,从而提高Ni与基底的相互作用以及表面氧物种的含量,使其具有较强的抗积碳能力.燃烧法合成的Ni基钙钛矿催化剂在CH4∶CO2=1.25∶1,800℃的条件下反应300 h后,积碳量仅为1.0%,而在同样条件下浸渍法合成的催化剂积碳量则高达14.6%.     

Capture of CO2 from high humidity flue gas by vacuum swing adsorption with zeolite 13X

Capture of CO₂ from flue gas streams using adsorption processes must deal with the prospect of high humidity streams containing bulk CO₂ as well as other impurities such as SO _x , NO _x , etc. Most studies to date have ignored this aspect of CO₂ capture. In this study, we have experimentally examined the capture of CO₂ from a 12% synthetic flue gas stream at a relative humidity of 95% at 30 °C. A 13X adsorbent was used and the migration of the water and its subsequent impact on capture performance was evaluated. Binary breakthrough of CO₂/water vapor was performed and indicated a significant effect of water on CO₂ adsorption capacity, as expected. Cyclic experiments indicate that the water zone migrates a quarter of the way into the column and stabilizes its position so that CO₂ capture is still possible although decreased. The formation of a water zone creates a “cold spot” which has implications for the system performance. The recovery of CO₂ dropped from 78.5% to 60% when moving from dry to wet flue gas while the productivity dropped by 22%. Although the concentration of water leaving the bed under vacuum was 27%(vol), the low vacuum pressure prevented condensation of water in this stream. However, the vacuum pump acted as a condenser and separator to remove bulk water. An important consequence of the presence of a water zone was to elevate the vacuum level thereby reducing CO₂ working capacity. Thus although there is a detrimental effect of water on CO₂ capture, long term recovery of CO₂ is still possible in a single VSA process. Pre-drying of the flue gas steam is not required. However, careful consideration of the impact of water and accommodation thereof must be made particularly when the feed stream temperature increases resulting in higher feed water concentration.