Efficient photosensitized degradation of 4-chlorophenol over immobilized aluminum tetrasulfophthalocyanine in the presence of hydrogen peroxide

The photosensitized degradation of 4-chlorophenol (4-CP) under visible light (lambda > or = 450 nm) irradiation in an aerated aqueous medium at pH 12 was studied using an immobilized photosensitizer, aluminum tetrasulfophthalocyanine, on a commercial resin Amberlite IRA 400. The catalyst exhibited strong adsorption toward 4-CP, but the adsorption led to an exponential decrease in both the initial rate and the apparent first-order rate constant, as measured by 4-CP loss in the bulk solution. Several intermediates were formed from 4-CP oxidation, including fumaric acid, benzoquinone, and hydroquinone, which were adsorbed strongly on the catalyst and lowered the photosensitized reaction. Addition of H2O2 was found to be an efficient way to eliminate the colored intermediates and consequently recover the catalyst activity. The immobilized sensitizer was stable and could be used repeatedly in the presence of H2O2. The optimal loading of the photosensitizer in the catalyst was about 1.0 wt %.     

Heterogeneous ion-exchange membranes based on sulfonated poly(1,4-phenylene sulfide) and linear polyethylene: preparation, oxidation stability, methanol permeability and electrochemical properties

Poly(1,4-phenylene sulfide) was sulfonated with chlorosulfonic acid in 1,2-dichloroethane. The product (IEC = 2.38 mequiv./g) was ground and sieved (mesh size 63 μm) to obtain small particles. The particles and linear polyethylene were mixed in various ratios and the resulting blends were press-molded at 150 °C to obtain the membranes. Membranes containing up to 66 wt.% of sulfonated particles could be prepared without any problem in mechanical strength. The membranes were characterized by their stability in oxidative environment, ionic conductivity, and diffusive permeability to methanol. The membrane containing 66 wt.% of sulfonated particles was almost as conductive as Nafion 117; it exhibited, however, much lower diffusive permeability to methanol. In a strongly oxidative environment (3% aqueous H₂O₂ at 70 °C), the prepared membranes were less stable than Nafion 117, but much more stable than membranes with sulfonated poly(styrene-co-divinylbenzene) particles. In preliminary laboratory tests with H₂/O₂ and direct methanol fuel cells, the prepared membranes with high concentrations of sulfonated particles performed similarly to Nafion 117.     

采用Nafion粘结剂的PEMFC氧电极研究

研究了聚合物电解质燃料电池（PEMFC）中以Nation溶液取代PTFE乳液作粘结剂的效果．并对催化剂层内Nafion含量进行了优化，同时探讨了气体工作压力和离子交换膜的影响，实验发现：1．使用Nafion溶液后显著提高电池性能，Nafion含量为2mg·cm－2时性能技好；2．气体压力增大改善了电池位能；3．使用Nafion115膜的电池性能优于使用Nafion117膜的电池．要进一步提高电池性能，减小欧姆控制区的斜率是必要的．     

Membrane-derived fluorinated radicals detected by electron spin resonance in UV-irradiated Nafion and Dow ionomers: effect of counterions and H2O2

Electron spin resonance (ESR) spectroscopy was used to detect and identify radicals formed by UV irradiation of Nafion and Dow perfluorinated membranes partially or fully neutralized by Cu(II), Fe(II), and Fe(III). This method allowed the monitoring of ESR signals from the paramagnetic counterions together with the appearance of membrane-derived radical species. The most surprising aspect of this study was the formation of membrane-derived radical species only in the neutralized membranes, and even in the absence of H2O2 in the case of Nafion/Cu(II) and Nafion/Fe(III). In Nafion/Cu(II), ESR spectra from radicals exhibiting hyperfine interactions with three equivalent 19F nuclei (the "quartet") and with four equivalent 19F nuclei (the "quintet") were detected. In Nafion/Fe(II) exposed to H2O2 solutions, the formation of Fe(III) was detected. Upon UV irradiation, strong signals from the chain-end radical ROCF2CF2* were detected first, followed by the appearance, upon annealing above 200 K, of the quartet signal observed in Nafion/Cu(II). In subsequent experiments with Nafion and Dow membranes neutralized by Fe(III), the ROCF2CF2* radicals were formed even in the absence of H2O2, indicating that the role of H2O2 is oxidation of Fe(II) to Fe(III); moreover, in these systems small amounts of the chain-end radicals were detected even without UV irradiation. This result validates the method used to form the radicals: the role of UV irradiation is to accelerate the formation of a signal that is produced, albeit slowly, even in the dark, and possibly during fuel cell operation. The major conclusion is that cations are involved in degradation processes; the point of attack appears to be at or near the pendant chain of the ionomer. Therefore when studying membrane stability, it is important to consider not only the formation of oxygen radicals, such as HO*, HOO*, and O2*-, that can attack the membrane but also the specific reactivity of counterions.     

Degradation of 4-Chlorophenol using a Gas–Liquid Gliding Arc Discharge Plasma Reactor

The gas–liquid gliding arc discharge plasma is used directly to study degradation and dechlorination of 4-Chlorophenol (4-CP) in solution. The typical AC waveforms of discharge voltage and current revealed that the discharge behavior was not definitely periodic. The chemical oxygen demand (COD) abatement of 4-CP solution with stainless steel electrode is higher than that with aluminum or brass electrode; When air was used as carrier gas the COD abated from 1,679.2 to 190 mg/L (i.e., 88.68% abatement) after 76 min plasma treatment; Increasing gas–liquid mixing rate could also increase the degradation of 4-CP; adding appropriate amounts of Fe²⁺ or iron chips to the solution were found to be favorable for 4-CP degradation. The main intermediates of 4-CP degradation are p-benzoquinone, hydroquinone, 4-chlorocatechol, p-chloronitrobenzene, and ring cleavage products (acetic acid, glycol, propanone, and others). Furthermore, possible pathways of 4-CP degradation in solution are proposed.     

Kinetics of liquid phase semiconductor photoassisted reactions: supporting observations for a pseudo-steady-state model

The kinetics of liquid phase semiconductor photocatalytic and photoassisted reactions are an area of some debate, reignited recently by an article by Ollis(1) in which he proposed a simple pseudo-steady-state model to interpret the Langmuir-Hinshelwood type kinetics, commonly observed in such systems. In the current article, support for this model, over other models, is provided by a reinterpretation of the results of a study, reported initially in 1999,(2) of the photoassisted mineralization of 4-chlorophenol, 4-CP, by titania films and dispersions as a function of incident light intensity, I. On the basis of this model, these results indicate that 4-CP is adsorbed more strongly on P25 TiO2 when it is in a dispersed, rather than a film form, due to a higher rate constant for adsorption, k(1). In addition, the kinetics of 4-CP removal appear to depend on I(beta), where beta = 1 or 0.6 for when the TiO2 is in a film or a dispersed form, respectively. These findings are discussed both in terms of the pseudo-steady-state model and other popular kinetic models.     

纳米孔碳负载Fe3O4催化剂上苯直接羟基化制苯酚

Fe3O4/CMK-3 was prepared by impregnation and used as a catalyst for the direct hydroxylation of benzene to phenol with hydro-gen peroxide. The iron species in the prepared catalyst was Fe3O4 because of the partial reduction of iron(III) to iron(II) on the surface of CMK-3. The high catalytic activity of the catalyst arises from the formation of Fe3O4 on the surface of CMK-3 and the high selectivity for phenol is attributed to the consumption of excess hydroxyl radicals by CMK-3. The effect of temperature,re...     

Suzuki Reaction of Aryl Bromides Using a Phosphine-Free Magnetic Nanoparticle-Supported Palladium Catalyst

A palladium catalyst immobilized on superparaganetic nanoparticles was prepared with a palladium loading of 0.30 mmol/g. The catalyst was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, atomic absorption spectrophotometry, and nitrogen adsorption. The immobilized palladium catalyst was an efficient catalyst without added phosphine ligands for the Suzuki cross-coupling reaction of several aryl bromides with phenylboronic acid. The recovery of catalyst was simply by magnetic decantation in the presence of a magnet. The immobilized palladium catalyst can be reused many times without significant degradation in catalytic activity. No leaching of active palladium species into the reaction solution was detected.     

Improvement of Fe/MgO catalysts by calcination for the growth of single- and double-walled carbon nanotubes

Calcination at 900-1000 degrees C for 8-12 h of an Fe/MgO catalyst prepared by impregnation was found to result in a uniform MgFe2O4/MgO solid solution that showed a successful settling of well-dispersed iron species into the MgO lattice. During methane reduction, many iron-containing particles with a diameter of about 4 nm were formed on the catalyst surface to provide numerous active sites for the growth of single- and double-walled carbon nanotubes. There was a significant improvement of the Fe/MgO catalyst that resulted in a high yield of impurity-free nanotubes. Using C2H4 cracking at 600 degrees C and transmission electron microscope observations, the Fe species distribution in the catalysts and microscope images of nanotube growth were described in detail. H2 reduction of the calcined Fe/MgO catalyst was found to cause the formation of iron layers on the catalyst surface, which resulted in the growth of only carbon layers. The results are useful for understanding changes in the metal species distribution in the catalysts and the nanotube growth mechanism, and they provide a simple method to improve Fe/MgO catalysts.     

Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane

Sulfonated poly(ether ether ketone) (PEEK) was prepared by sulfonation of commercial Victrex^@ PEEK and degree of sulfonation was found to be about 44.5% by ¹H NMR. Sulfonated PEEK/polyaniline composite membranes, in order to prevent methanol crossover, were prepared by chemical polymerization of a thin layer of polyaniline (PANI) in the presence of a high oxidant concentration on a single face modification. FTIR and PANI coating density studies confirmed the loading of PANI in sulfonated PEEK membrane matrix. PANI composite membranes with different polymerization time were prepared and subjected to thermogravimetric analysis as well as electrochemical and methanol permeability study to compare with sulfonated PEEK and Nafion 117 membrane. Ion-exchange capacity, water uptake, proton transport numbers and proton conductivities for different PANI composite sulfonated PEEK (SPEEK) membranes were found to be dependent on the coating density of the PANI in the membrane matrix and were slightly lower than that of Nafion 117 membrane. Methanol permeability of these membranes (especially SPEEK/PANI-1.5) was about four times lower than Nafion 117 membrane. Among the all SPEEK membranes synthesized in this study, SPEEK-1.5 appears to be more suitable for direct methanol fuel cell (DMFC) application considering optimum physicochemical and electrochemical properties, thermal stability as well as very low methanol permeability. Above all, the cost-effective and simple fabrication technique involved in the synthesis of such composite membranes makes their applicability quite attractive.     

质子交换膜对钒氧化还原液流电池性能的影响

采用溶液接枝聚合法制备了一种新型的质子交换膜PVDF-g-PSSA, 测定了PVDF-g-PSSA膜、Nafion 117 膜和PE01均相膜的离子交换能力和电导率, 并分别研究了以这3种膜为隔膜的钒电池的电化学性能. 实验结果表明, PVDF-g-PSSA膜具有优良的质子电导率和离子交换能力, 室温下其离子交换能力和质子电导率分别为1.13 mmol/g和3.22×10-2 S/cm, 在不同的充放电电流密度下, 以PVDF-g-PSSA膜为隔膜的钒电池的库仑效率和能量效率明显高于Nafion 117膜和PE01均相膜为隔膜的钒电池; PVDF-g-PSSA膜阻钒离子的渗透性能与PE01均相膜基本一致, 都明显优于Nafion 117膜的阻钒离子渗透能力.     

Radiation deterioration in mechanical properties and ion exchange capacity of Nafion N117 swelling in water

The base form Nafion N117 samples swelling in the oxygen-saturated distilled water were irradiated with γ-rays or with electron beams at various doses up to 1600 kGy at room temperature or at 343 K to obtain detailed information on the effect of oxygen on the radiation deterioration in the Nafion mechanical properties and in the ion exchange capacity. The contribution of the radical reactions where oxygen molecules did not participate was dominant for the radiation deterioration in the mechanical properties of the Nafion N117 membrane swelling in the oxygen-saturated distilled water at room temperature. The effect of oxygen molecules was not significant due to the little oxygen concentration in the distilled water even though oxygen was saturated in the water. The Nafion N117 membrane irradiated with γ-rays at 343 K became a weak and brittle material, since the rise of the temperature activated the reactions. Oxygen molecules, in contrast, have negligible part in the reactions at 343 K due to their lower solubility in the water. We observed the negligible effect of the radiation sources as well as of the dose rate below 10 kGy/h on the radiation deterioration in Nafion N117 mechanical properties at room temperature. The irradiation of the Nafion membrane with γ-rays or with electron beams is one of the acceleration tests of the Nafion degradation. We made clear that the dissolved fluorine measured using a fluoride ion meter is a hopeful index for the in situ judging of the Nafion mechanical deterioration. The ion exchange capacity of the membrane irradiated up to 1600 kGy was the 20% decrease of the initial capacity at room temperature. Nafion side chains terminating with –SO₃⁻ M⁺ groups were radiation-durable compared with the backbone.     

聚偏氟乙烯-Nafion共混膜的制备及阻醇质子导电性能研究

直接甲醇燃料电池 (Ｄｉｒｅｃｔｍｅｔｈａｎｏｌｆｕｅｌｃｅｌｌ,ＭＤＦＣ)以高效、清洁和燃料储运方便等优点成为一类极具发展潜力的新型动力源 .但目前ＤＭＦＣ中普通使用的全氟磺酸膜 (如ＮａｆｉｏｎＴＭ 系列膜 )阻醇性能太差 ,导致大量甲醇从阳极穿过膜直接透到阴极 ,造成燃料的浪费和电池整体性能的下降 .据文献报道 ,即使甲醇浓度低到 1ｍｏｌ Ｌ ,也有近40 %的醇透过膜 .缺乏高性能的阻醇质子导电聚合物电解质膜是制约ＤＭＦＣ发展的瓶颈之一 .已有一些研究人员致力于新型膜材料的开发 ,如有人研制了聚苯并咪唑膜[1] 及各种掺杂…     

Gamma radiation-induced catalytic degradation of 4-chlorophenol using SiO2, TiO2, and Al2O3

To study radiocatalytic processes, solutions of 4-chlorophenol (4-CP) were irradiated with gamma radiation, and results indicate that degradation of 4-CP is increased when commercial SiO_2, TiO₂, or Al₂O₃ is added.     

纤维负载炭黑金属酞菁轴向配合物仿酶高效催化降解水体中有机污染物

天然血红素基过氧化氢酶具有高选择催化性, 但易失活变性. 为提高其活性和稳定性, 以性能稳定的十六氯铁酞菁(FePcCl₁₆)为活性中心, 四氨基吡啶为配体, 炭黑(CB)为载体, 合成了仿酶催化剂炭黑十六氯铁酞菁轴向配合物(FePcCl₁₆-Py-CB); 通过热黏合法将其负载于低熔点皮芯聚酯纤维(LMPET)上, 生成易与水体分离的纤维负载型仿酶催化剂FePcCl₁₆-Py-CB@LMPET, 并以H₂O₂为氧化剂, 地赛米松(DXMS)为底物, 构筑仿酶催化体系. 研究了该催化体系在温和条件下的催化性能及循环使用性能, 探讨了催化体系的催化机理及DXMS的降解历程. 结果表明, 异裂H₂O₂产生的高价铁氧[Fe(Ⅳ)=O]为催化体系中的主要活性物种, 体系呈现出优异的催化性能和稳定性能. 该催化体系在120 min内降解的最终产物均为小分子酸.     

Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene,Methyl Methacrylate,and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling

Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R₃TACN) ligands. Two types of structures were confirmed by crystallography: “[(R₃TACN)FeX₂]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R₃TACN)Fe(μ‐X)₃Fe(R₃TACN)]⁺ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R₃TACN)FeX₂]_n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)₃TACN}FeBr₂] ( 4 b ) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined.     

IR laser photodeposition of a-Fe/Si films developing nanograins of ferrisilicate, iron disilicide and rare hexagonal iron upon annealing

IR laser-induced gas-phase photolysis of Fe(CO)(5)-SiH(4) mixtures occurs as SiH(4)-photosensitized decomposition of Fe(CO)(5) is accelerated by products of this decomposition and it results in deposition of amorphous Si/Fe nanocomposite films. Analyses of the deposited and subsequently annealed solid films were made by FTIR, Raman and X-ray photoelectron spectroscopy, X-ray diffraction and electron microscopy. The deposited films are amorphous, contain crystalline nanostructures of iron silicide FeSi(2) and undergo atmospheric oxidation in topmost layers to iron oxide and hydrogenated silicon oxide. Upon annealing they develop nanocrystalline structures of ferrisilicate, Fe(1.6)SiO(4), carbon-encaged iron disilicide, FeSi(2), and very rare hexagonal (high-pressure) Fe surviving at ambient conditions. The mechanism of formation of these nanostructures is discussed in terms of gas-phase and solid-phase reactions.     

全钒氧化还原液流电池Nafion/SiO_2复合膜的研究

采用溶胶-凝胶法制备Nafion117/SiO2复合膜.工艺研究表明:复合膜制备过程中,加入的MeOH与TEOS比例基本不影响复合膜的阻钒性能.但如以水解时间10 min,水解完成后自然晾干24 h制备的复合膜,则其VO2+的渗透率最低,为4.27×10-9cm2/s,比Nafion117膜的渗透率降低了52倍.SEM测试表明,经自然晾干的复合膜,其中SiO2晶粒长大,并填充了Nafion膜中大部分的孔洞.以其作隔膜组装全钒氧化还原液流电池(单电池),测试表明膜掺杂后电池的电力效率提高2.7%.     

直接甲醇燃料电池新型聚合物膜的研究

通过溶液共混方法 ,制备了聚偏氟乙烯与聚苯乙烯磺酸 (PVDF_PSSA)、聚偏氟乙烯与Nafion(PVDF_Nafion)两种共混膜 .研究了膜组成对膜电导率和甲醇透过率的影响 .与Nafion 1 1 7膜相比 ,PVDF_Nafion共混膜在Nafion含量为 2 5wt%时 ,电导率σ下降 2个数量级 ,而甲醇透过率P却降低 3个数量级 .若以 (σ/P)为综合指标 ,则PVDF_Nafion共混膜和PVDF_PSSA共混膜的综合性能分别比Nafion 1 1 7膜高约 4 0倍、1 6倍