Mechanistic studies of the photocatalytic degradation of methyl green: an investigation of products of the decomposition processes

The methyl green (MG) dye dissolves into an alkaline solution when the pH value is too high (pH 9). The cationic MG dye molecules are converted into the colorless carbinol base (CB) and produce crystal violet (CV) dye and ethanol by hydroxide anion. Thirty-three intermediates of the process were separated, identified, and characterized by HPLC-ESI-MS technique in this study and their evolution during the photocatalytic reaction is presented. Moreover, the other intermediates formed in the photocatalytic degradation MG processes were separated and identified by HPLC-PDA technique. The results indicated that the N-de-methylated degradation of CV dye took place in a stepwise manner to yield N-de-methylated CV species, and the N-de-alkylated degradation of CB also took place in a stepwise manner to yield N-de-alkylated CB species generated during the processes. Moreover, the oxidative degradation of the CV dye (or CB) occurs to yield 4-(N,N-dimethylamino)phenol (DAP), 4-(N,N-dimethylamino)-4'-(N',N'-dimethylamino)benzophenone (DDBP) and their N-de-methylated products [or to yield 4-(N-ethyl-N,N-dimethyl)aminophenol (EDAP), DDBP, 4-(N-ethyl-N,N-dimethylamino)-4'-(N',N'-dimethylamino)benzophenone (EDDBP), DAP, and their N-de-alkylated products], which were found for the first time. A proposed degradation pathway of CV and CB is presented, involving mainly the N-de-alkylation and oxidation reaction.     

Modeling of an annular photocatalytic reactor for water purification: oxidation of pesticides

Photocatalytic oxidation (PCO) over titanium dioxide (TiO2) is a "green" sustainable process for the treatment and purification of water and wastewater. However, the application of PCO for wastewater treatment on an industrial scale is currently hindered by a lack of simple mathematical models that can be readily applied to reactor design. Current models are either too simplistic or too rigorous to be useful in photocatalytic reactor design, scale-up, and optimization. In this paper a simple mathematical model is presented for slurry, annular, photocatalytic reactors that still retains the essential elements of a rigorous approach while providing simple solutions. The model extends the applicability of the thin-film model of photocatalytic reactors previously presented to include the case of geometrically thick photoreactors (i.e., those reactors in which the thickness of the annular zone is significant as compared to the outer radius of the reactor). The model uses a novel six-flux absorption-scattering model to represent the radiation field in the reaction space, which assumes that scattered photons follow the route of the six directions of the Cartesian coordinates. The model was successfully validated with experimental results from the photocatalytic oxidation of the pesticide isoproturon in an experimental reactor. The mathematical model presented may be used as a tool for the design, scale-up, and optimization of annular photocatalytic reactors for water treatment and purification.     

Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: an in situ HATR-IR isotope study

The reaction of FeS2 (pyrite) with gaseous H2O, O2, and H2O/O2 was investigated using horizontal attenuated total reflection Fourier transform infrared spectroscopy (HATR-FTIR). Spectra were interpreted with the aid of hybrid molecular orbital/density functional theory calculations of sulfate-iron hydroxide clusters. Reaction of pyrite in gaseous H2O led primarily to the formation of iron hydroxide on pyrite. Exposure of the pyrite to gaseous O2 after exposure to H2O vapor led to the formation of sulfur oxyanions that included SO42-. Isotopic labeling experiments showed that after this exposure sequence the oxygen in the sulfate product was primarily derived from the H2O reactant. If, however, pyrite was exposed to gaseous O2 prior to pure H2O vapor, both SO42- and iron oxyhydroxide became significant products. Isotopic rabeling experiments using the O2-then-H2O sequence showed that the oxygen in the SO42- product was derived from both H2O and O2. The results indicate that H2O and O2 exhibit a competitive adsorption on pyrite, with H2O blocking surface sites for O2 adsorption. The extent of oxygen incorporation from either the H2O or the O2 component into the surface-bound sulfur oxyanion product appears to be a strong function of the relative concentration ratio of the reactant H2O and O2.     

Myoglobin and lipid oxidation interactions: Mechanistic bases and control

Lipid oxidation and myoglobin oxidation in meat lead to off-flavor development and discoloration, respectively. These processes often appear to be linked and the oxidation of one of these leads to the formation of chemical species that can exacerbate oxidation of the other. Several investigators have reported preservation of fresh meat color following the inclusion of antioxidant ingredients. An understanding of the complementary oxidation interaction provides a basis for explaining quality deterioration in meat and also for developing strategies to maintain optimal sensory qualities.     

Composition and biological effects of goldenberry byproducts: an overview

Goldenberry is a wild fruit that has been widely used for centuries, mainly in folk medicine. Most studies of goldenberry have focused on the fruit, but new research has studied its byproducts, which were considered to be waste until recently. The main objective of our study was to systematize the published information regarding the composition of goldenberry byproducts (calyces, leaves, seeds, and pomace) and their effects on biological systems. Goldenberry byproducts contain minerals, amino acids, withanolides, flavonoids, and essential fatty acids, thus representing good sources of these compounds. Some of their major biological effects include anti-inflammatory, antioxidant, antidiabetic, and antiproliferative effects. Information regarding their toxicity is also presented here. To determine the optimal dosage, further safety studies would be recommended to ensure the best health benefits of these compounds. The available evidence has demonstrated the nutritional value of different byproducts of goldenberry, suggesting them to be potential candidates for use in the cosmetic industry, in the preparation of functional foods, and in phytomedicine for the prevention and adjuvant treatment of some diseases. © 2020 Society of Chemical Industry     

Mesoporous nitrogen-doped TiO2 for the photocatalytic destruction of the cyanobacterial toxin microcystin-LR under visible light irradiation

The presence of the harmful cyanobacterial toxins in water resources worldwide drives the development of an innovative and practical water treatment technology with great urgency. This study deals with two important aspects: the fabrication of mesoporous nitrogen-doped TiO2 (N-TiO2) photocatalysts and their environmental application for the destruction of microcystin-LR (MC-LR) under visible light. In a nanotechnological sol-gel synthesis method, a nitrogen-containing surfactant (dodecylammonium chloride) was introduced as a pore templating material for tailor-designing the structural properties of TiO2 and as a nitrogen dopant for its visible light response. The resulting N-TiO2 exhibited significantly enhanced structural properties including 2-8 nm mesoporous structure (porosity 44%) and high surface area of 150 m2/g. Red shift in light absorbance up to 468 nm, 0.9 eV lower binding energy of electrons in Ti 2p state, and reduced interplanar distance of crystal lattices proved nitrogen doping in the TiO2 lattice. Due to its narrow band gap at 2.65 eV, N-TiO2 efficiently degraded MC-LR under visible spectrum above 420 nm. Acidic condition (pH 3.5) was more favorable for the adsorption and photocatalytic degradation of MC-LR on N-TiO2 due to electrostatic attraction forces between negatively charged MC-LR and +6.5 mV charged N-TiO2. Even under UV light, MC-LR was decomposed 3-4 times faster using N-TiO2 than control TiO2. The degradation pathways and reaction intermediates of MC-LR were not directly related to the energy source for TiO2 activation (UV and visible) and nature of TiO2 (neat and nitrogen-doped). This study implies a strong possibility for the in situ photocatalytic remediation of contaminated water with cyanobacterial toxins and other toxic compounds using solar light, a sustainable source of energy.     

Formation and decomposition of new and unknown polar brominated disinfection byproducts during chlorination

Brominated disinfection byproducts (Br-DBPs) are generally more cytotoxic and genotoxic than their chlorinated analogues. A great portion of total organic bromine in chlorinated drinking water is still unknown and may be ascribed to polar Br-DBPs. In this work, a novel approach, precursor ion scan using ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, was adopted and further developed for selective detection and identification of polar Br-DBPs, which made it possible to reveal the whole picture of the formation and decomposition of polar Br-DBPs during chlorination. Simulated drinking water samples with chlorine contact times from 1 min to 7 d were analyzed. Many new polar aromatic and unsaturated aliphatic Br-DBPs were detected and tentatively proposed with chemical structures, of which 2,4,6-tribromophenol, 3,5-dibromo-4-hydroxybenzoic acid, 2,6-dibromo-1,4-hydroquinone, and 3,3-dibromopropenoic acid were confirmed or identified with authentic standards. It was found that various polar Br-DBPs formed and reached the maximum levels at different chlorine contact times; high molecular weight Br-DBPs might undergo decomposition to relatively low molecular weight Br-DBPs or even finally to haloacetic acids and trihalomethanes. The decomposition of newly detected intermediate Br-DBPs (including molecular ion cluster m/z 345/347/349/351, 2,4,6-tribromophenol, and 3,5-dibromo-4-hydroxybenzoic acid) during chlorination was investigated in detail. The "black box" from the input of "humic substances + bromide + chlorine" through the output of "haloacetic acids + trihalomethanes" was opened to a significant extent.     

Magnetically agitated photocatalytic reactor for photocatalytic oxidation of aqueous phase organic pollutants

A magnetically agitated photocatalytic reactor (MAPR) has been developed and assessed for oxidation of phenol. The MAPR uses a titanium dioxide composite photocatalyst with a ferromagnetic barium ferrite core. The catalyst motion was controlled with a dual-component magnetic field. First, a permanent magnet above the reactor provided a static magnetic field to counteract the force of gravity, hence increasing catalyst exposure to UV. Second, an alternating magnetic field generated by a solenoid was used to agitate the catalyst, thus increasing mass transfer between pollutants and byproducts to the catalyst. Optimal performance of the MAPR was achieved with the permanent magnet present and 1 A of alternating current to the solenoid between 20 and 80 Hz. Operating with a 60-Hz signal at 1 A with the permanent magnet present and 100 mg of catalyst, the system reduced an 11 mg/L phenol concentration by97% and decreased nonpurgeable dissolved organic carbon by 93% in 7 h using three 8-W 365-nm peak UV lamps.     

Hydrogen abstraction and decomposition of bromopicrin and other trihalogenated disinfection byproducts by GC/MS

Tribromonitromethane (bromopicrin), dibromochloronitromethane, bromodichloronitromethane, and trichloronitromethane (chloropicrin) have been identified as drinking water disinfection byproducts (DBPs). They are thermally unstable and decompose under commonly used injection port temperatures (200-250 degrees C) during gas chromatography (GC) or GC/mass spectrometry (GC/MS) analysis. The major decomposition products are haloforms (such as bromoform), which result from the abstraction of a hydrogen atom from the solvent bythermally generated trihalomethyl radicals. A number of other products formed by radical reactions with the solvent and other radicals were also detected. The trihalonitromethanes also decompose in the hot GC/MS transfer line, and the mass spectra obtained are mixed spectra of the undecomposed parent compound and decomposition products. This can complicate the identification of these compounds by GC/MS. Trihalomethyl compounds that do not have a nitro group, such as tribromoacetonitrile, carbon tetrabromide, methyl tribromoacetate, and tribromoacetaldehyde, do not decompose or only slightly decompose in the GC injection port and GC/MS transfer line. The brominated trihalomethyl compounds studied also showed H/Br exchange by some of their fragment ions. This H/Br exchange also makes the identification of these compounds in drinking water more difficult. The extent of H/Br exchange was found to depend on the mass spectrometer ion source temperature, and it is proposed that the internal surface of the ion source is involved in this process.     

Evaluation of the intrinsic photocatalytic oxidation kinetics of indoor air pollutants

This paper presents a methodology for the evaluation of the intrinsic photocatalytic oxidation (PCO) kinetics of indoor air pollutants. It combines computational fluid dynamics (CFD) modeling of the fluid flow in the reactor with radiation field modeling and photocatalytic reaction kinetics to yield a rigorous model of a flat-plate, single-pass, flow-through photocatalytic reactor for indoor air purification. This method was applied to model the PCO of trichloroethylene (TCE) in humidified air and to derive kinetic parameters directly from kinetic data in an integral flow reactor. Steady-state PCO experiments of TCE over irradiated TiO2 (Degussa P25) thin films immobilized on glass supports were carried out at different radiation intensities, flow rates, and inlet substrate concentrations. The oxidation rate of TCE was found to be first-order on the incident photon flux and to follow a Langmuir-Hinshelwood type reaction kinetics rate law. Mass transfer resistances were observed at Reynolds numbers less than 46. Apparent quantum yields were found to be up to 0.97 mol Einstein(-1). A comparison of the model prediction with the experimental results in an integral reactor yielded pollutant-specific kinetic rate parameters which were independent of reactor geometry, radiation field, and fluid-dynamics. The kinetic parameters would,therefore, be more universally applicable to the design and scale-up of photocatalytic reactors for indoor air purification.     

Effect of process variables and natural organic matter on removal of microcystin-LR by PAC-UF

The release of cyanobacterial toxins, such as microcystin-LR, in drinking water supplies is of increasing concern. In this study, we investigated the use of ultrafiltration (UF) combined with adsorption on powdered activated carbon (PAC) for the removal of microcystin-LR from drinking water. Process variables examined included PAC type, PAC dosage, membrane characteristics (material and pore size), and the presence of natural organic matter (NOM). Due to greater mesopore volume, wood-based activated carbon was up to 4-times more effective at removing microcystin-LR than coconut-based carbon, depending on contact time. Cellulose acetate (CA) membranes with a molecular weight cutoff (MWCO) of 20,000 Da did not reject or adsorb microcystin-LR. Membranes composed of polyethersulfone (PES) of similar pore size, on the other hand, adsorbed microcystin-LR presumably through hydrophobic interactions. A PES membrane with a MWCO of 5000 Da sorbed microcystin-LR, and also rejected 8.4% of the toxin through a size exclusion mechanism. When PAC was coupled to UF using PES membranes, greater removal of microcystin-LR occurred compared to when CA membranes were used due to sorption of the toxin to the PES membrane surface. The presence of Suwannee River fulvic acid (SRFA) reduced microcystin-LR removal by PAC-UF, primarily due to competition between SRFA and microcystin-LR for sites on the PAC surface.     

Plasma surface modified TiO2 nanoparticles: improved photocatalytic oxidation of gaseous m-xylene

Titanium dioxide (TiO(2)) is a preferred catalyst for photocatalytic oxidation of many air pollutants. In an effort to enhance its photocatalytic activity, TiO(2) was modified by pulsed plasma treatment. In this work, TiO(2) nanoparticles, coated on a glass plate, were treated with a plasma discharge of hexafluoropropylene oxide (HFPO) gas. By appropriate adjustment of discharge conditions, it was discovered that the TiO(2) particles can be either directly fluorinated (Ti-F) or coated with thin perfluorocarbon films (C-F). Specifically, under relatively high power input, the plasma deposition process favored direct surface fluorination. The extent of Ti-F formation increased with increasing power input. In contrast, at lower average power inputs, perfluorocarbon films are deposited on the surface of the TiO(2) particles. The plasma surface modified TiO(2) nanoparticles were subsequently employed as catalysts in the photocatalytic oxidation of m-xylene in air, as carried out inside a batch reactor with closed loop constant gas circulation. Both types of modified TiO(2) were significantly more catalytically active than that of the unmodified particles. For example, the rate constant of m-xylene degradation was increased from 0.012 min(-1) with untreated TiO(2) to 0.074 min(-1) with fluorinated TiO(2). Although it is not possible to provide unequivocal reasons for this increased photocatalytic activity, it is noted that the plasma surface treatment converted the TiO(2) from hydrophilic to highly hydrophobic, which would provide more facile catalyst adsorption of the xylene from the flowing air. Also, based on literature reports, the use of fluorinated TiO(2) reduces electron-hole recombination rates, thus increasing the photocatalytic activity.     

Effects of TiO2 surface modifications on photocatalytic oxidation of arsenite: the role of superoxides

Using TiO2 photocatalyst, arsenite [As(III)] can be rapidly oxidized to arsenate [As(V)], which is less toxic and less mobile in the aquatic environment. Superoxides have been recently proposed as a main photocatalytic oxidant of As(III) whereas OH radicals are dominant oxidants in most TiO2 photocatalytic oxidation (PCO) reactions. This study confirms that superoxides are mainly responsible for the As(III) PCO by investigating PCO kinetics in pure and modified TiO2 systems. The rate of As(III) oxidation drastically increased on Pt-TiO2, which could be ascribed to the enhanced superoxide generation through an efficient interfacial electron transfer from the conduction band (CB) to O2. Since the addition of tert-butyl alcohol (OH radical scavenger) had little effect on the PCO rate in both naked and Pt-TiO2 suspensions, OH radicals do not seem to be involved. The addition of polyoxometalates (POMs) as an electron shuttle between TiO2 CB and 02 highly promoted the PCO rate whereas the POM alone was not effective at all in oxidizing As(III). Fluorinated TiO2 that had a markedly reduced adsorptive capacity for As(III) did not show a reduced PCO rate, which indicates that the direct hole transfer path is not important. The arsenite oxidation proceeded under visible light with a similar rate to the case of Pt-TiO2/UV when dye-sensitized Pt-TiO2 was used. Since only superoxides can be generated as a photooxidant in this visible light system, their role as a main oxidant of As(III) is confirmed. In addition, the PCO rate was significantly reduced in the presence of superoxide dismutase.     

光催化条件下棉织物的蓝晒工艺印相

针对蓝晒工艺在太阳光下曝光过程中存在诸多不定性影响因素的问题,采用具有稳定条件的光催化反应仪作为新曝光方式,探讨了感光剂浓度、棉织物种类、灯管功率、曝光时间对蓝晒图像效果的影响,从而得出优化印相条件;借助扫描电子显微镜、万能试验拉伸机等对棉织物的形貌与性能进行表征。结果表明:面密度为180 g/m²的棉织物在600 W灯光下曝光30 min的蓝晒图像效果最佳,极大提高了成品效率;灯管功率与曝光时间成正比关系,是影响蓝晒图像效果的主要因素;优化印相条件下制得的素染织物(无图案)、印相织物(有图案)与原棉织物相比,质量增加率分别达到了7.26%、5.57%,拉伸断裂强力分别提升了66.89 、46.78 N;织物载体的性能随普鲁士蓝色素沉淀量的不同而有所改变。     

Efficient photocatalytic decomposition of perfluorooctanoic acid by indium oxide and its mechanism

Perfluorooctanoic acid (C(7)F(15)COOH, PFOA) has increasingly attracted worldwide concerns due to its global occurrence and resistance to most conventional treatment processes. Though TiO(2)-based photocatalysis is strong enough to decompose most organics, it is not effective for PFOA decomposition. We first find that indium oxide (In(2)O(3)) possesses significant activity for PFOA decomposition under UV irradiation, with the rate constant about 8.4 times higher than that by TiO(2). The major intermediates of PFOA were C(2)-C(7) shorter-chain perfluorocarboxylic acids, implying that the reaction proceeded in a stepwise manner. By using diffuse reflectance infrared Fourier transform spectroscopy, (19)F magic angle spinning nuclear magnetic resonance, and electron spin resonance, we demonstrate that the terminal carboxylate group of PFOA molecule tightly coordinates to the In(2)O(3) surface in a bidentate or bridging configuration, which is beneficial for PFOA to be directly decomposed by photogenerated holes of In(2)O(3) under UV irradiation, while PFOA coordinates to TiO(2) in a monodentate mode, and photogenerated holes of TiO(2) preferentially transform to hydroxyl radicals, which are inert to react with PFOA. PFOA decomposition in wastewater was inhibited by bicarbonate and other organic matters; however, their adverse impacts can be mostly avoided via pH adjustment and ozone addition.     

酒精废水处理工艺中氧化沟污泥的微生物菌群分析

该实验分析了酒精废水处理过程的主要指标变化,并基于Illumina MiSeq测序方法研究了氧化沟活性污泥的微生物菌群,分析污泥中微生物种类、丰度和功能。 结果表明,在酒精废水处理过程中,pH的变化较小,总磷（TP）浓度不断减小,NH4+-N浓度呈先升高后降低的趋势,化学需氧量（COD）、生化需氧量（BOD）呈先快速减小后缓慢减小的趋势。 氧化沟活性污泥中生丝微菌属（Tetrasphaera）对废水中磷元素的去除起重要的作用;陶厄氏菌属（Thauera）对废水中氮元素的去除起重要的作用;球形杆菌属（Sphaerobacter）、陶厄氏菌属（Thauera）、沙雷氏菌属（Serratia）能够降解或转化结构复杂的有机物;热单胞菌属（Caldimonas）在污泥中丰度高,但其特性和功能尚不清晰,有待更加深入地研究。     

Photocatalytic oxidation of tabun simulant-diethyl cyanophosphate: FTIR in situ investigation

Gas phase photocatalytic oxidation of diethyl cyanophosphate vapor in a static reactor using TiO2 and modified TiO2 as the photocatalyst was studied with the FTIR in situ method. The transition metals Pt, Au, and Ag were used for TiO2 modification by the chemical and photochemical deposition methods as well as the mechanical mixture of TiO2 with manganese oxide to improve its adsorption and catalytic activity. Photocatalytic oxidation of diethyl cyanophosphate in a static reactor results in its complete mineralization with carbon dioxide, phosphoric and nitric acids, and water as the major final products. HCN was demonstrated to be the only toxic gaseous intermediate of diethyl cyanophosphate photocatalytic oxidation, formed as a result of diethyl cyanophosphate hydrolysis. Diethylphosphate and acetic and formic acids were registered as the surface intermediates. It was found that cyanhydric acid is oxidized slowly with the use of unmodified TiO2. The formation of surface cyanide complexes with Ag and Au ions could be responsible for the fast removal of HCN from the gas phase and its further photooxidation in the case of using TiO2 with deposited Au and Ag.     

猪油控制氧化的工艺研究

通过正交实验和单因素实验对以制备肉味香精为目的的猪油控制氧化工艺进行了优化,并对猪油控制氧化的规律进行了探讨.实验结果表明,猪油控制氧化的较优化工艺条件是:反应温度130℃,反应时间4 h,空气流速0.012 m3/(h·100g猪油);较合适的氧化状态为:POV 270～400meq/kg,p-AV大于200,AV小于4.0 mgKOH/g,在此状态下氧化猪油经热反应可获得肉香前体物和肉香风味.