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.     

Gas-phase degradation of CCl<Subscript>4</Subscript>, CHCl<Subscript>3</Subscript> and CH<Subscript>2</Subscript>Cl<Subscript>2</Subscript> over metallic Fe

We studied the hydrolysis of gas-phase carbon tetrachloride (CCl₄), chloroform (CHCl₃), and dichloromethane (CH₂Cl₂) over a metallic Fe surface for its application in combination with air stripping and soil vapour extraction. The effects of chlorocarbon concentration, type and preparation of the iron-containing material, humidity, and temperature on process performance are reported. The hydrolysis of chlorinated methane derivatives is catalysed by metallic iron resulting in a noticeable decrease of the reaction temperature. The reaction kinetics were found to be consistent with the Langmuir-Hinshelwood model.     

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.     

Decolorisation of Acid Blue 74 by ultraviolet/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The photodegradation of Acid blue 74 in aqueous solution employing a H₂O₂/ultraviolet system in a photochemical reactor was investigated. The kinetics of decolorization were studied by application of a kinetic model. The results show that the reaction of decolorization followed pseudo-first order kinetics. We demonstrate that there is an optimum H₂O₂ concentration, at which the rate of the decolorization reaction is maximum. Irradiation at 253.7 nm of the dye solution in the presence of H₂O₂ results in complete discoloration after ten minutes of treatment.     

New insights into mercury removal mechanism on CeO<Subscript>2</Subscript>-based catalysts: A first-principles study

First-principles calculations were performed to investigate the mechanism of Hg⁰ adsorption and oxidation on CeO₂(111). Surface oxygen activated by the reduction of Ce⁴⁺ to Ce³⁺ was vital to Hg⁰ adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO₂(111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO₂(111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO₂ catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O₂ into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg⁰ removal on CeO₂-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg⁰ removal process will help provide guidelines for developing novel CeO₂-based catalysts and enhance the Hg⁰ removal efficiency.

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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.     

Pt/Mg-Ce-O catalyst for NO/H<Subscript>2</Subscript>/O<Subscript>2</Subscript> lean de-No<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reaction

The NO/H₂/O₂ reaction was studied under oxidizing conditions in the 100-400 °C range over 0.1 wt% Pt supported on various metal oxides such as MgO, CeO₂, SiO₂, La₂O₃, CaO, Y₂O₃ and TiO₂. The Pt/MgO and Pt/CeO₂ catalysts showed good catalytic behaviours. Here, we find that the Pt/Mg-Ce-O catalyst, prepared from MgO and CeO₂ by the sol-gel method, is a very active and selective catalyst towards N₂ formation in the whole 100–400 °C range. This catalyst appears to be the most active, selective and stable one ever reported in the literature for the NO/H₂/O₂ reaction, even in the presence of 5%v H₂O or 20 ppmv of SO₂ in the feed stream.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Static and dynamic characteristics of SO<Subscript>2</Subscript>-O<Subscript>2</Subscript> aqueous solution in the microstructure of porous carbon materials

Porous carbon material facilitates the reaction SO₂ + O₂ + H₂O → H₂SO₄ in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H₂O, SO₂ and O₂) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO₂ and O₂ by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H₂O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.

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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     

Near-critical free-surface flows: real fluid flow analysis

An open channel flow with a flow depth close to the critical depth is characterised by a curvilinear streamline flow field that results in steady free surface undulations. Near critical flows of practical relevance encompass the undular hydraulic jump when the flow changes from supercritical (F > 1) to subcritical (F < 1), and the undular weir flow over broad-crested weirs where the flow changes from subcritical (F < 1) to supercritical (F > 1). So far these flows were mainly studied based on ideal fluid flow computations, for which the flow is assumed irrotational and, thus, shear forces are absent. While the approach is accurate for critical flow conditions (F = 1) in weir and flumes, near-critical flows involve long distances reaches, and the effect of friction on the flow properties cannot be neglected. In the present study the characteristics of near-critical free-surface flows are reanalysed based on a model accounting for both the streamline curvature and friction effects. Based on the improved model, some better agreement with experimental results is found, thereby highlighting the main frictional features of the flow profiles.     

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.     

Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

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.     

氯代芳烃催化氢转移脱氯的研究

本文以甲酸钠为氢源,对聚乙烯吡咯烷酮锚定的ＰｄＣｌ２催化氯代芳烃脱氯进行了研究,考察了反应条件对反应的影响,研究了脱氯的选择性。结果表明;该方法具有卓越的脱氯选择性,催化剂用量少,反应条件温和,操作简便。本文并对其脱氯反应机理进行了初步探讨。     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> 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.     

Turbulence and aeration in hydraulic jumps: free-surface fluctuation and integral turbulent scale measurements

In an open channel, a change from a supercritical to subcritical flow is a strong dissipative process called a hydraulic jump. Herein some new measurements of free-surface fluctuations of the impingement perimeter and integral turbulent time and length scales in the roller are presented with a focus on turbulence in hydraulic jumps with a marked roller. The observations highlighted the fluctuating nature of the impingement perimeter in terms of both longitudinal and transverse locations. The results showed further the close link between the production and detachment of large eddies in jump shear layer, and the longitudinal fluctuations of the jump toe. They highlighted the importance of the impingement perimeter as the origin of the developing shear layer and a source of vorticity. The air–water flow measurements emphasised the intense flow aeration. The turbulent velocity distributions presented a shape similar to a wall jet solution with a marked shear layer downstream of the impingement point. The integral turbulent length scale distributions exhibited a monotonic increase with increasing vertical elevation within 0.2 < L_z/d₁ < 0.8 in the shear layer, where L_z is the integral turbulent length scale and d₁ the inflow depth, while the integral turbulent time scales were about two orders of magnitude smaller than the period of impingement position longitudinal oscillations.     

Effects of Pd doping on N<Subscript>2</Subscript>O formation over Pt/BaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> during NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> storage and reduction process

N₂O is a powerful greenhouse gas and plays an important role in destructing the ozone layer. This present work investigated the effects of Pd doping on N₂O formation over Pt/BaO/Al₂O₃ catalyst. Three types of catalysts, Pt/BaO/Al₂O₃, Pt/Pd mechanical mixing catalyst (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) and Pt-Pd co-impregnation catalyst (Pt-Pd/BaO/Al₂O₃) were prepared by incipient wetness impregnation method. These catalysts were first evaluated in NSR activity tests using H₂/CO as reductants and then carefully characterized by BET, CO chemisorption, CO-DRIFTs and H2-TPR techniques. In addition, temperature programmed reactions of NO with H2/CO were conducted to obtain further information about N₂O formation mechanism. Compared with Pt/BaO/Al₂O₃, (Pt/BaO/ Al₂O₃ + Pd/Al₂O₃) produced less N₂O and more NH3 during NO _x storage and reduction process, while an opposite trend was found over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃). Temperature programmed reactions of NO with H₂/CO results showed that Pd/Al₂O₃ component in (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) played an important role in NO reduction to NH₃, and the formed NH3 could reduce NO _x to N₂ leading to a decrease in N₂O formation. Most of N₂O formed over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃) was originated from Pd/BaO/Al₂O₃ component. H₂-TPR results indicated Pd-Ba interaction resulted in more difficultto- reduce PdOx species over Pd/BaO/Al₂O₃, which inhibits the NO dissociation and thus drives the selectivity to N₂O in NO reduction.

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废水处理新技术中的超临界水氧化法

超临界水氧化法是一种有效处理有机废水的方法,本文在总结超临界水的特点和优点的基础上,着重介绍了超临界水氧化的基本原理,工艺流程及应用状况,探讨该项技术的前景与发展趋势。、     

Enhanced dechlorination of chlorobenzene by microwave-induced zero-valent iron: particle effects and activation energy

Organic compounds such as chlorobenzene cannot be effectively decomposed with currently available biological and chemical treatment methods. Preliminary studies show that nano-scale zero-valent iron particles irradiated by microwave is effective in decomposing chemically refractive organic compounds such as chlorobenzene. In this study, microwave is applied to enhance chlorobenzene removal using micron-scale iron particles and nano-scale zero-valent iron particles suspended in the chlorobenzene solution as the dielectric media. The results show that better chlorobenzene removal can be achieved when the chlorobenzene solution is irradiated with 250 W microwave for 150 s than without microwave irradiation. The microwave radiation increases iron reaction rate and surface activity, thus enhancing the chlorobenzene removal. The microwave-induced iron particles cause the chlorobenzene activation energy to drop 34.0% for micron-scale iron and 16.1% for nano-scale zero-valent iron. They can remove 13.6 times more chlorobenzene for micro iron, and 3.6 times more chlorobenzene for nano iron. We have demonstrated that the microwave-induced nano-scale iron particles are effective in treating toxic organic substances as demonstrated in this laboratory study.     

Effects of SO<Subscript>2</Subscript> contamination on rising CO<Subscript>2</Subscript> drops under high pressure

Although the flow dynamics of pure liquid drops in other liquids has been well researched, little attention has been paid to the impacts of impurities. Hence, most of research is not directly applicable to the real world. To address this gap, we conducted numerical experiments simulating the rise of pure and contaminated drops. It was selected to study liquid CO₂ drops contaminated with SO₂ under high pressure because such mixtures mimic potential scenarios in which drops may leak from carbon capture and storage (CCS) facilities or pipelines. First, numerical simulation experiments were performed to validate our method by comparing our results with previous research on pure drops. Second, the validated numerical approach was applied to simulations of contaminated drops to investigate how contaminants affect rising drops. The results show that the SO₂ contamination caused changes in deformation, breakup phenomena, rising velocities, surrounding flow fields and drag coefficients. Most importantly, the contamination resulted in the formation of smaller “child drops”; such breakup is not observed in pure CO₂ drops. The formation of child drops in turn affects the streamlines, patterns and areas of wakes behind the contaminated drops. The addition of contaminants also enhances the dissolution rate, which is affected by the contaminant concentration and by the flow dynamics of the rising drop. Our results would improve understanding the rise of impure CO₂ drops, such as drops potentially leaked by future CCS operations.