Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Photocatalytic degradation of the herbicide cinosulfuron in aqueous TiO<Subscript>2</Subscript> suspension

The photocatalytic degradation of a sulfonylurea herbicide, cinosulfuron, has been studied in TiO₂ aqueous suspensions. A first order kinetic law was found. The influence of the initial concentration of cinosulfuron and of the initial radiant flux on the kinetics were evaluated. The identification of the intermediate products was based on high performance liquid chromatography coupled with mass spectrometry analyses (HPLC-MS). The mineralization of cinosulfuron was traced using ion chromatography and total organic carbon (TOC) measurements. These results indicate that the photocatalytic degradation of cinosulfuron leads to CO₂, NO₃ ⁻ and SO₄ ²⁻ as final products, and in addition cyanuric acid (C₃H₃O₃N₃), confirming previous results on triazinic ring-containing compounds. Electronic Publication     

Photocatalytic oxidation of humic substances with TiO<Subscript>2</Subscript>-coated glass micro-spheres

The photocatalytic oxidation of humic substances in aqueous solutions and natural waters with TiO₂ attached to buoyant, hollow glass micro-spheres was studied. A maximum oxidation efficiency of 3.6 mg W^–1 h^–1 was achieved in neutral or alkaline media at a plane surface concentration of the catalyst attached to the micro-spheres of 25 g m^–2. Proceeding by different mechanisms in acidic and alkaline media, the photocatalytic oxidation efficiency did not benefit from an excessive presence of hydroxyl radical promoters, hydrogen peroxide and alkali.     

Effective degradation of tetracycline by mesoporous Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> under visible light irradiation

Bi₂WO₆ was synthesized with a hydrothermal method at different pHs and used for the degradation of tetracycline (TC) in water. The mesoporous Bi₂WO₆ prepared at pH 1 (BWO-1) displayed the highest adsorption and degradation capacity to TC due to its large surface area and more efficient capacity to separate photogenerated electrons and holes. 97% of TC at 20 mg·L^?1 was removed by BWO-1 at 0.5 g·L^?1 after 120 min irradiation under simulated solar light. Only 31% of the total organic carbon (TOC) was removed after 360 min irradiation although the TC removal reached 100%, suggesting that TC was mainly transformed to intermediate products rather than completely mineralized. The intermediates were identified by high-performance liquid chromatography-time of flight-mass spectrometry (HPLC-TOF-MS) and possible photodegradation pathways were proposed.     

Preparation of effective TiO<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalysts for water treatment

Photocatalytic oxidation using semiconductors is one of the advanced oxidation processes for degradation of organic pollutants in water and air. TiO₂ is an excellent photocatalyst that can mineralize a large range of organic pollutants such as pesticides and dyes. The main challenge is to improve the efficiency of the TiO₂ photocatalyst and to extend TiO₂ light absorption spectra to the visible region. A potential solution is to couple TiO₂ with a narrow band gap semiconductor possessing a higher conduction band such as bismuth oxide. Therefore, here we prepared Bi₂O₃/TiO₂ heterojunctions by the impregnation method with different Bi/Ti ratio. The prepared composites have been characterized by UV–Vis diffused reflectance spectra and X-ray diffraction. The photocatalytic activity of the heterojunction has been determined from the degradation of orange II under visible and UV light. Results show that Bi₂O₃/TiO₂ heterojunctions are more effective than pure TiO₂-anatase under UV-A irradiation, with an optimum for the Bi/Ti ratio of 5 %, for the photocatalytic degradation of Orange II. However, the photocatalytic activity under irradiation at λ higher than 420 nm is not much improved. Under UV–visible radiation, the two semiconductors are activated. We propose a mechanism explaining why our products are more effective under UV–visible irradiation. In this case the charge separation is enhanced because a part of photogenerated electrons from the conduction band of TiO₂ will go to the conduction band of bismuth oxide. In this composite, titanium dioxide is the main photocatalyst, while bismuth oxide acts as adsorbent photosensitizer under visible light.     

Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication     

Photocatalytic degradation of organic dyes by Er<Superscript>3+</Superscript>:YAlO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> composite under solar light

In this work, Er³⁺:YAlO₃/TiO₂ composite was synthesized by a ultrasonic dispersion and liquid boil method. The Er³⁺:YAlO₃/TiO₂ composite and pure TiO₂ powder were characterized by XRD. The degradation of different organic dyes was used to evaluate the photocatalytic activity of the Er³⁺:YAlO₃/TiO₂ composite. It is found that the photocatalytic activity of Er³⁺:YAlO₃/TiO₂ composite is much higher than that for the similar system with only TiO₂. Moreover, this Er³⁺:YAlO₃/TiO₂ composite provides a new way to take advantage of TiO₂ in sewage treatment aspects using solar light.     

Efficient photocatalytic degradation of Rhodamine B dye using ZnO/graphitic C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanocomposites synthesized by microwave

Semiconductor photocatalysis is a solution to issues of environmental pollution and energy shortage because photocatalysis can use solar energy to degrade pollutants. The photocatalytic activity can be improved by using composites of ZnO and other semiconductors. Here, composites of ZnO and polymeric graphite-like C₃N₄ (g-C₃N₄) with high photocatalytic activities were prepared by microwave synthesis. Products were characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible and Fourier transform infrared spectroscopy. The photocatalytic degradation of Rhodamine B was tested under irradiation from a Xe lamp. Results show that adding graphite-like C₃N₄ promotes the photocatalytic activity of ZnO. Composites with 1.0 wt% g-C₃N₄ showed the best photodegradation efficiency, and the reaction average energy was approximately 33.71 kJ mol^?1.     

Unexpected release of HNO<Subscript>3</Subscript> and related species from UV-illuminated TiO<Subscript>2</Subscript> surface into air in photocatalytic oxidation of NO<Subscript>2</Subscript>

We have discovered that HNO₃ and related species are released from the TiO₂ surface into air in the TiO₂ photocatalytic oxidation of NO₂ (1 ppm) under continuous UV light illumination (1 mW cm⁻²) by dehumidifying the outlet gas of the reaction and analyzing the recovered condensate liquid by ion chromatography. The origin of the HNO₃ recovered in the dehumidifier could not be explained by a simple desorption of HNO₃ overproduced on the TiO₂ surface. The produced HNO₃ must be activated on the TiO₂ surface and causing the unidentified reaction.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO<Subscript>2</Subscript> composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

Fabrication and photocatalytic ability of an Au/TiO<Subscript>2</Subscript>/reduced graphene oxide nanocomposite

A new type of Au/TiO₂/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO₂ on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO₂ and RGO. Au/TiO₂/RGO had a better photocatalytic activity than Au/ TiO₂ for the degradation of phenol. Electrochemical measurements indicated that Au/TiO₂/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO₂/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO₂/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO₂ to effectively reduce photogenerated charge recombination.

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Rapid photocatalytic degradation of the recalcitrant dye amaranth by highly active N-WO<Subscript>3</Subscript>

Dye wastewater is a major source of toxic aromatic amines released into the environment. Semiconductor photocatalysis is a clean, solar-driven process for the treatment of dye wastewater. To enhance applicability of semiconductor photocatalysis, the catalyst used should be visible light active. Here we report a facile synthesis of a highly visible-light-active nitrogen-doped tungsten oxide, N-WO₃, by thermal decomposition of peroxotungstic acid–urea complex. The structure and properties of N-WO₃ are characterized by X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy. The photodegradation of amaranth catalyzed by N-WO₃ is evaluated in a batch system under visible and ultraviolet A (UVA) light. Our results show successful doping of N in both interstitial and substitutional sites and the presence of N₂-like species. The N doping surprisingly expands the usable portion of the solar spectrum up to the near-infrared region and enhances the photocatalytic activity. At typical experimental conditions such as 25 mg/L of amaranth, 1 g/L of N-WO₃, and pH 7, 100 % degradation of amaranth is achieved within 2 h under both visible and UVA light. The photocatalytic activity of N-WO₃ is maintained in repeated cycles, indicating its exceptional photostability. To the best of our knowledge, this is the first time that a reusable, highly visible-light-active N-WO₃ can be obtained through thermal decomposition of peroxotungstic acid–urea complex.     

Metal-free oxidation of aldehydes to acids using the 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl adduct

Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na₂SO₄·2H₂O₂·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H₂O₂, with inexpensive sodium sulphate, Na₂SO₄, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.     

Promotion of transition metal oxides on the NH<Subscript>3</Subscript>-SCR performance of ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> catalyst

Chromium oxide and manganese oxide promoted ZrO₂-CeO₂ catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NO _x with NH₃. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H₂ temperatureprogrammed reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH₃-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO₂-CeO₂ binary oxide for the low temperature NH₃-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO₂ and H₂O. Cr-Zr-Ce mixed oxide exhibited>80% NO _x conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr^{6 +}. The present mixed oxide can be a candidate for the low temperature abatement of NO _x .

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Semiconducting oxide photocatalysts for reduction of CO<Subscript>2</Subscript> to methanol

The explosive growth in anthropogenic energy consumption, coupled with the consequent environmental pollution, have been acknowledged as two impending challenges confronting humanity. Photocatalytic CO₂ reduction to produce value-added hydrocarbon fuels, by using abundant solar energy and redundant atmospheric CO₂, is an innovative way to satisfy global energy requirements whilst simultaneously reducing atmospheric CO₂ levels. Although this notion is several decades old, it has unfortunately been lingering in a state of infancy due to inherently poor CO₂-to-fuel conversion efficiencies, and the generation of low-value products (e.g., CO, HCHO). These pitfalls hamper this process from any potential commercial breakthrough and are primarily fuelled by the lack of progress in developing high-performance photocatalytic materials. Fortunately, the advent of nanotechnology has recently introduced many promising novel materials for this purpose. Here, we review photocatalysts with proven potential for converting CO₂ into methanol, a high-value, energy-dense hydrocarbon fuel that is easily transported using existing pipeline infrastructure. Methanol possesses multifarious applications in the automobile, industrial and petrochemical sector. In addition, the development of direct methanol fuel cells (DMFCs) has introduced the tantalizing prospect of using methanol as a medium for storing solar energy that is easily converted to electricity via DMFCs. As such, methanol is an ideal fuel, with numerous advantages over its counterparts. This article reviews several photocatalysts that have been reported for this environmentally sustainable process of converting CO₂ into methanol by photocatalysis. Specifically, the performance enhancement effected by adding dopant atoms, forming heterostructured composites and nanostructures, is investigated in terms of four key areas: (1) enhanced visible light sensitivity, (2) improved adsorption of reactants on the catalytic surface, (3) lowered electron–hole recombination and (4) increased CO₂ reduction kinetics. The trends deduced therein are invaluable for researchers developing novel photocatalytic materials, which will utilize sunlight to convert CO₂ into methanol with enhanced efficiency, thus ushering in the era of a green methanol-based economy.     

Environmental impact of CO<Subscript>2</Subscript>, Rn,Hg degassing from the rupture zones produced by Wenchuan <Emphasis Type="Italic">M</Emphasis><Subscript>s</Subscript> 8.0 earthquake in western Sichuan,China

The concentrations and flux of CO₂, ²²²Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M _s 8.0 earthquake in order to assess the environmental impact of degassing of CO₂, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO₂, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO₂, Rn and Hg concentration in soil gas showed that (1) the concentration of CO₂ in the epicenter of Wenchuan M _s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I _geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO₂, Rn and Hg degassing rate indicated that (1) the CO₂ in soil gas was characterized by a mean \(\updelta^{13}C_{CO2}\) of ?20.4 ‰ and by a mean CO₂ flux of 88.1 g m^?2 day^?1, which were in the range of the typical values for biologic CO₂ degassing. The maximum of soil CO₂ flux reached values of 399 g m^?2 day^?1 in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m^?2 s^?1; (3) the soil Hg flux was lower, ranging from ?2.5 to 18.7 n g m^?2 h^?1 and increased from south to north. The mean flux over the all profiles was 4.2 n g m^?2 h^?1. The total output of CO₂ and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km² were approximately 0.57 Mt year^?1 and 688.19 g year^?1. It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO₂ and Rn, were needed in some houses.     

Effect of humic acids,nitrate and oxygen on the photodegradation of the flubendiamide insecticide: identification of products

Flubendiamide is a ryanodine insecticide that shows a strong insecticidal activity and is relatively safe for non-target organisms. Actually only flubendiamide and its product desiodo-flubendiamide have been studied during catalytic degradation using TiO₂ and ZnO. Therefore, here we tested the photocatalytic removal of flubendiamide in the presence of nitrates or humic acids. Degradation kinetics were monitored using high-performance liquid chromatography ultraviolet–visible detector. Product identification was done using a high-resolution time-of-flight mass spectrometer coupled to a gas chromatograph (GC-HRMS). Results show that the addition of humic acids at 10 mg l^?1 increased the removal of flubendiamide more than five times. The addition of nitrate ions at 10 mg l^?1 had no influence. The removal of flubendiamide was more than ten times faster in experiments with oxygen purging. Fourteen degradation products were identified, which can be classified into three groups: phthalimide and related phthalic acid derivatives, fluorinated species related to the second amide moiety, and advanced transformation products.     

TiO2 photocatalyzed degradation of diazinon in an aqueous medium

The photocatalytic degradation of diazinon was studied over TiO₂ catalysts. The kinetics obtained demonstrated that powder titania (t_1/2 = 9.7 min) was more efficient compared to pure titania thin film catalysts (t_1/2 = 29.4 min). Mineralization of organic carbon to CO₂ after 360 min of irradiation was found to be 75% while heteroatoms (P, S, N) were mineralized into phosphate, sulfate and nitrate ions, respectively. A microtox test was performed to evaluate the toxicity of solutions treated by catalysts. Illumination of diazinon in the presence of TiO₂ gave rise to several intermediates that have been identified by means of solid phase extraction and gas chromatography-mass spectrometry, while a simple degradation pathway is proposed.     

Characteristics of PM<Subscript>2.5</Subscript>, CO<Subscript>2</Subscript> and particle-number concentration in mass transit railway carriages in Hong Kong

Fine particulate matter (PM_2.5) levels, carbon dioxide (CO₂) levels and particle-number concentrations (PNC) were monitored in train carriages on seven routes of the mass transit railway in Hong Kong between March and May 2014, using real-time monitoring instruments. The 8-h average PM_2.5 levels in carriages on the seven routes ranged from 24.1 to 49.8 µg/m³, higher than levels in Finland and similar to those in New York, and in most cases exceeding the standard set by the World Health Organisation (25 µg/m³). The CO₂ concentration ranged from 714 to 1801 ppm on four of the routes, generally exceeding indoor air quality guidelines (1000 ppm over 8 h) and reaching levels as high as those in Beijing. PNC ranged from 1506 to 11,570 particles/cm³, lower than readings in Sydney and higher than readings in Taipei. Correlation analysis indicated that the number of passengers in a given carriage did not affect the PM_2.5 concentration or PNC in the carriage. However, a significant positive correlation (p < 0.001, R ² = 0.834) was observed between passenger numbers and CO₂ levels, with each passenger contributing approximately 7.7–9.8 ppm of CO₂. The real-time measurements of PM_2.5 and PNC varied considerably, rising when carriage doors opened on arrival at a station and when passengers inside the carriage were more active. This suggests that air pollutants outside the train and passenger movements may contribute to PM_2.5 levels and PNC. Assessment of the risk associated with PM_2.5 exposure revealed that children are most severely affected by PM_2.5 pollution, followed in order by juveniles, adults and the elderly. In addition, females were found to be more vulnerable to PM_2.5 pollution than males (p < 0.001), and different subway lines were associated with different levels of risk.     

Preparation of CuO/SiO<Subscript>2</Subscript> and photocatalytic activity by degradation of methylene blue

A photocatalyst based on CuO/SiO₂ was prepared, and evaluated for the degradation of methylene blue in aqueous medium. The photocatalyst was obtained by calcination method of copper salt, in the presence of silica. The characterization by XRD, FTIR, and TPR techniques confirmed the formation of CuO as active phase. SEM studies showed CuO deposited on the surface of SiO₂. By ESI-MS, it was demonstrated that the degradation of methylene blue occurs through successive hydroxylations. Photodegradation assays showed that CuO/SiO₂ was efficient for degradation, and that the material worked better in the presence of UV light.