Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution

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华北地区紫外与可见光辐射在大气中的传输

根据对华北地区2年观测资料的分析以及实际天气条件下紫外辐射(UV)和可见光辐射(VIS)的经验模式,研究了UV、VIS在大气中的传输,得到了大气中物质成分与不同波段太阳辐射相互作用的不同特征和规律.结果表明,对于UV传输,水汽因子的重要性远大于散射因子;对于VIS传输,散射因子的重要性大于水汽因子.受水汽和散射因子衰减的影响,到达地面的UV、VIS表现出一定的地域特色,华北地区到达地面的UV、VIS均以散射因子的贡献为主,在紫外、可见光波段,散射因子的贡献分别为62.55%、95.76%.经水汽因子衰减到达地面的UV大于VIS,经散射因子衰减到达地面的VIS远远大于UV.整体上,华北地区SD/SQ(散射辐射/总辐射)年均值由南到北逐渐降低,地面UV、VIS由南到北逐渐增加.仅受水汽因子影响,华北地区损失于大气中的UV、VIS能量分别为19.30、16.54W.m-2;仅受散射因子影响,华北地区损失于大气中的UV、VIS能量分别为35.31、311.07W.m-2.华北地区UV和VIS的能量损失季节变化明显,并表现出由南到北减小的趋势.UV、VIS在大气中传输时,一部分能量被大气中的物质成分在化学和光化学反应中吸收和利用,这一能量影响到大气中的各种基本过程,在未来研究中应予以高度重视.利用能量方法并结合对测量数据的分析来研究大气中物质与辐射能量的相互作用,特别是能量在大气中的利用、分配、时空变化等是一种有效、客观的方法.UV对水汽的敏感性远大于VIS对水汽的敏感性,UV和VIS对SD/SQ的敏感性大于对水汽的敏感性.     

Heterogeneous uptake of NO2 on soils under variable temperature and relative humidity conditions

Heterogeneous reactions of nitrogen dioxide (NO₂) on soils collected from Dalian (S1) and Changsha (S2) were investigated over the relative humidity (RH) range of 5%-80% and temperature range of 278-328 K using a horizontal coated-wall flow tube. The initial uptake coefficients of NO₂ on S2 exhibited a decreasing trend from (10 ± 1.3) × 10^-8 to (3.1 ± 0.5) × 10^-8 with the relative humidity increasing from 5% to 80%. In the temperature effect studies, the initial uptake coefficients of S1 and S2 decreased from (10 ± 1.2) × 10^-8 to (3.8 ± 0.5) × 10^-8 and from (16 ± 2.2) × 10^-8 to (3.8 ± 0.4) × 10^-8 when temperature increased from 278 to 288 K for S1 and from 278 to 308 K for S2, respectively. As the temperature continued to increase, the initial uptake coefficients of S1 and S2 returned to (7.9 ± 1.1) × 10^-8 and (20 ± 3.1) × 10^-8 at 313 and 328 K, respectively. This study shows that relative humidity could influence the uptake kinetics of NO₂ on soil and temperature would impact the heterogeneous chemistry of NO₂.     

On the divergence criterion for runaway detection: Application to complex controlled systems

It is well-known that, for certain values of the operative parameters influencing the dynamic behavior of a chemical reactor, a phenomenon known as thermal runaway (that is, a loss of the reactor temperature control) may arise. Such a situation can be really dangerous because above a certain threshold temperature value unwanted side reactions or, worse, decompositions of the reacting mixture may be triggered evolving high amounts of flammable or toxic gases that can cause reactor pressurization and, eventually, its explosion. For this reason, since the beginning of the previous century a number of studies concerning the prediction of the so called runaway boundaries has been carried out. In this work, a modified version of the divergence criterion for runaway detection, originally developed by Zaldívar and co-workers, is presented. Such a modified divergence criterion is capable of treating whatever type of complex controlled reacting system (taking into account not only temperature control but also dosing strategies) and its reliability has been demonstrated for isoperibolic semibatch reactors using literature experimental data concerning the nitration of 4-Chlorobenzotrifluoride in mixed acids and the nitric acid oxidation of 2-octanol to 2-octanone and further carboxylic acids.     

电子束脱除烟道气中硫和氮过程的计算机模拟

电子束干法脱硫脱硝的技术可以同时去除烟道气中的NOx与SO2。根据该处理方法建立脱除NOx和SO2的化学反应机理，并使用计算机模拟的方法，考察体系温度、辐照剂量和氨浓度与去除效率的关系。     

Relevant organic components in ambient particulate matter collected at Svalbard Islands (Norway)

n-Alkanes, polynuclear aromatic hydrocarbons and n-alkanoic acids present in the inhalable fraction of airborne particles have been determined at the Italian scientific base sited in the area of Ny Alesund, Spitzbergen Island, Norway. Both the profiles of n-alkane and polynuclear aromatic congeners among the respective classes showed that anthropogenic sources were responsible for the presence of particulate organics in the atmosphere there, since the monomodal distribution of aliphatics and the fresh-emission shape of PAH fraction were observed. The total contents of n-alkanes and PAH ranged from 19 to 97 ng m⁻³ and from 0.6 to 2.0 ng m⁻³, respectively; n-alkanoic acids reached 6 ng m⁻³. The occurrence of nitrated-PAH of photochemical origin at trace extent (i.e. nitrated-fluoranthenes and nitropyrenes) has been also observed. Since the occurrence of OH radicals is required together with NO_x for the processes leading to the generation of 2-nitrofluoranthene and 2-nitropyrene would start, the detection of these nitrated species revealed the occurrence of photochemical processes in that region.     

Groundwater flow, multicomponent transport and biogeochemistry: development and application of a coupled process model

A research tool for modeling the reactive flow and transport of groundwater contaminants in multiple dimensions is presented. Arbitrarily complex coupled kinetic–equilibrium heterogeneous reaction networks, automatic code generation, transfer-function based solutions, parameter estimation, high-resolution methods for advection, and robust solvers for the mixed kinetic–equilibrium chemistry are some of the features of reactive flow and transport (RAFT) that make it a versatile research tool in the modeling of a wide variety of laboratory and field experiments. The treatment of reactions is quite general so that RAFT can be used to model biological, adsorption/desorption, complexation, and mineral dissolution/precipitation reactions among others. The integrated framework involving automated code generation and parameter estimation allows for the development, characterization, and evaluation of mechanistic process models. The model is described and used to solve a problem in competitive adsorption that illustrates some of these features. The model is also used to study the development of an in situ Fe(II)-zone by encouraging the growth of an iron-reducing bacterium with lactate as the electron donor. Such redox barriers are effective in sequestering groundwater contaminants such as chromate and TCE.     

Fires, explosions and related incidents at work in Great Britain in 1996/97 and 1997/98

Incidents in Great Britain reported to the Health and Safety Executive during 1996/97 and 1997/98 involving fires, explosions, runaway chemical reactions and unignited releases of flammable materials are reviewed. Statistical comparisons are made against previous years based on the materials involved, and a number of common themes and causes are identified.