Lanthanide Shift Reagents XIV Equilibrium Binding Constants for Europium Shift Reagent with Alkyl and Aryl Esters

Methods have been developed for measuring the equilibrium binding constants (K) for lanthanide shift reagents with donor substrates. Although Infrared Spectroscopy proved useful¹ for determining the binding of substituted anilines to the tris-tetramethylheptanedionate of Ytterbium, it was found that NMR was more sensitive and applicable to a wider range of substrates than simple alcohols and amines^2,3. The NMR procedure of progressive     

Photo fenton like process Fe3+/(NH4)2S2O8/UV for the degradation of Di azo dye congo red using low iron concentration

Degradation of Congo Red (CR) a di azo dye in aqueous solution is investigated by a Photo Fenton like process using Fe³⁺ ions as the catalyst and peroxy disulfate as the oxidant. The influence of various reaction parameters like, concentration of Fe³⁺ ions, concentration of the dye, concentration of ammonium persulfate, pH of the solution and the presence of hydroxyl radical scavenger are studied and optimal conditions are reported. The degradation rate decreased at higher dye concentration and at higher pH. The rate constant (k), catalytic efficiency (k_c) and process efficiency (Φ) are evaluated for different concentration of Fe³⁺ ions. The degradation of CR by the photo Fenton like process leads to the formation of 4-Amino, 3-azo naphthalene sulphonic acid, dihydroxy substituted naphthalene, dihydroxy substituted biphenyl, phenol, quinol etc., as intermediates, based on which probable degradation mechanism is proposed. These results show that a photo Fenton like process could be useful technology for the mineralization of di azo dyes under lower concentration of iron in acidic conditions. The present process is advantageous as it lowers the sludge production resulting from the iron comple      

Chemical oxidative degradation of Polybenzimidazole in simulated environment of fuel cells

The chemical oxidative degradation process of poly [2,2′-(m-phenylene)-5,5′-bibenzimidazole] (PBI) in simulated environment of fuel cells was evaluated. From the mechanical properties and the intrinsic viscosity of PBI, it was observed that the stress at break of PBI membranes decreased and the macromolecular chains of PBI were broken after the treatment in Fenton reagent for 24 h. From the photos of Scanning Electron Microscope, it was identified that there were lots of corroded holes in PBI membranes. By means of FTIR and ¹H NMR analysis, it was shown that during the treatment of PBI in the presence of HO or HOO free radicals the hydrogen atom of N-H bond in imidazole ring was liable to be oxidized, and the phenyl was oxidized with the formation of quinine and dicarboxylic acid structures. In the end, the possible mechanism of the chemical oxidative degradation of PBI was proposed.     

球磨微米硫化零价铁活化双氧水降解有机污染物的研究

报道了机械球磨方法制备的微米硫化零价铁（S-ZVI）可以快速活化H₂O₂降解各类有机污染物.S-ZVI/H₂O₂降解苯酚的单位比表面积反应速率常数是ZVI/H₂O₂的5倍以上,且苯酚的降解不存在初始抑制阶段.探针化合物乙醇的淬灭反应结合电子顺磁共振（EPR）实验证明S-ZVI/H₂O₂体系产生的氧化活性物质为·OH.反应前后S-ZVI颗粒的扫描电子显微镜（SEM）和X射线衍射（XRD）表征结合电化学测试和苯酚降解结果表明S-ZVI中FeS取代ZVI表面的钝化膜（铁氧化物）,加速了电子从Fe⁰传递到H₂O₂,更快地释放Fe²⁺,引发Fenton反应.在这过程中FeS主要作为电子的导体而非Fe²⁺的释放源.     

介孔Fe/SBA-15非均相芬顿氧化水中难降解染料罗丹明B

以介孔二氧化硅SBA-15 为载体, 采用等体积浸渍法制备了Fe/SBA-15. 通过X射线衍射(XRD)、N₂吸附-脱附、扫描电镜(SEM)、透射电镜(TEM)和X射线光电子能谱(XPS)等技术对其进行了表征, 并用于对水溶液中罗丹明B (RhB)的芬顿氧化. 表征结果表明了Fe/SBA-15维持了长程有序的介孔结构, 孔径和比表面积都有所下降, 并呈现棒状体的聚集态, 平均直径为0.6 μm. Fe 以α-Fe₂O₃的形态同时存在于介孔孔道内外. 在Fe/SBA-15 和H₂O₂同时存在条件下RhB的去除是吸附和催化氧化降解的协同作用所致, 并且与Fe/SBA-15 投加量密切相关, 但与初始溶液pH 几乎无关. 当Fe/SBA-15 投加量为0.15 g·L^-1, RhB 初始浓度为10.0 mg·L^-1,H₂O₂/Fe³⁺摩尔比为2000:1,初始溶液pH为5.4和反应温度为21 ℃时, RhB去除率达到了93%. Fe/SBA-15的Langmiur 单分子层饱和吸附量为99.11 mg·g^-1. 此外, 采用H₂O₂浸泡方式对使用过的Fe/SBA-15可进行再生,连续6 次循环使用后仍可维持80%的RhB去除率, 且每次使用后Fe浸出浓度都在0.1 mg·L^-1 (或者0.6% (质量分数))以下. 基于淬灭实验、UV-Vis 光谱和气相色谱-质谱(GC-MS)联用仪分析的结果, 提出了RhB的去除机理. 非均相芬顿催化剂Fe/SBA-15可用于去除像RhB这样的生物难降解有机物.     

Degradation of chlortetracycline in wastewater sludge by ultrasonication,Fenton oxidation,and ferro-sonication

Residual emerging contaminants in wastewater sludge remain an obstacle for its wide and safe applications such as landfilling and bio-fertilizer. In this study, the feasibility of individual ultrasonication (UlS) and Fenton oxidation (FO) and combined, Ferro-sonication processes (FO) on the degradation of chlortetracycline (CTC) in wastewater sludge was investigated. UlS parameters such as amplitude and sonication time were optimized by response surface methodology (RSM) for further optimization of FS process. Generation of highly reactive hydroxyl radicals in FO and FS processes were compared to evaluate the degradation efficiency of CTC. Increasing in the ratio of hydrogen peroxide and iron concentration showed increased CTC degradation in FO process; whereas in FS, an increase in iron concentration did not show any significant effect (p > 0.05) on CTC degradation in sludge. The estimated iron concentration in sludge (115 mg/kg) was enough to degrade CTC without the addition of external iron. The only adjustment of sludge pH to 3 was enough to generate in-situ hydroxyl radicals by utilizing iron which is already present in the sludge. This observation was further supported by hydroxyl radical estimation with adjustment of water pH to 3 and with and without the addition of iron. The optimum operating UlS conditions were found to be 60% amplitude for 106 min by using RSM. Compared to standalone UlS and FO at 1:1 ratio, FS showed 15% and 8% increased CTC degradation respectively. In addition, UlS of sludge increased estrogenic activity 1.5 times higher compared to FO. FS treated samples did not show any estrogenic activity.     

The role of bulk micro-nanobubbles in reagent desorption and potential implication in flotation separation of highly hydrophobized minerals

Micro-nanobubbles (MNBs) generated during hydrodynamic cavitation (HC) have been extensively studied in mineral processing field in the past two decades. Many researchers have claimed that MNBs can effectively promote the collection of fine particles in flotation, while studies on MNBs assisted mineral separation are rare. In this study, the role of bulk MNBs in desorbing flotation reagent was investigated, with the aim of illustrating the potential effects of MNBs on minerals separation. The results showed that bulk MNBs could efficiently remove the sodium oleate (NaOl) from diaspore surfaces, reducing the residual concentration of NaOl on solids, which was more significant when the amount of NaOl pre-adsorbed was relatively small. Furthermore, lower residual concentration of NaOl on solids caused by MNBs cleaning made the particles less hydrophobic and flocs more friable. Given that gangue entrapment in flocs was one of the main limits for high-selective flotation, the roles of MNBs in enhancing reagent desorption and associated flocs breakup and reorganization probably contribute to higher separation efficiency of different minerals, which was confirmed by the flotation results of diaspore/kaolinite mixture.     

Green synthesis and application of nanoscale zero-valent iron/rectorite composite material for P-chlorophenol degradation via heterogeneous Fenton reaction

A zero-valent iron/rectorite nanocomposite (NZVI/rectorite) was developed as a heterogeneous H₂O₂ catalyst for P-chlorophenol degradation. The physicochemical properties of NZVI/rectorite were characterized by various techniques including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller analysis. Results showed that NZVI sphere nanoparticles were successfully loaded on the rectorite surface with less aggregation and good dispersion. Moreover, compared with acid-leached rectorite (30.91 m²/g), the NZVI/rectorite appeared to have larger surface area (50.75 m²/g). In addition, the effects of pH, reaction time, initial P-chlorophenol concentration, catalyst amount, and H₂O₂ dosage on the P-chlorophenol degradation were systematically investigated. Results showed that NZVI/rectorite presents better properties for the degradation and mineralization of P-chlorophenol compared with pristine NZVI due to the large surface area, low aggregation, and good dispersion of the former. The degradation mechanisms of P-chlorophenol by NZVI/rectorite were adsorption and reduction coupled with a Fenton-like reaction. Four successive runs of the stability and regeneration study also showed that the NZVI/rectorite were unchanged even after 100% of P-chlorophenol degradation ratio. This study has extended the application of NZVI/rectorite as environment function material for the removal of P-chlorophenol from the environment.     

The role of transition metals in oxidative degradation of cellulose

The role of transition metals in oxidative degradation of cellulose has been studied. Degradation experiments with model papers and studies of hydroxyl radical production in solution have been performed with Fe, Cu, Mn, Co, Cr, Ni, and Zn. Rates of production of hydroxyl radicals in solution have been estimated using the radical scavenger N,N′-(5-nitro-1,3-phenylene)bisglutaramide in the pH interval 7-9. Hydroxyl radical production during degradation of Cu-containing cellulose has been studied. To gain a better insight into chemistry behind degradation processes, chemiluminometric experiments were also performed.The experiments provide strong evidence that the role of transition metals during the oxidative degradation of cellulose is catalytic. A correlation between the behaviour of transition metals in solution and in paper was established at low contents of transition metal in paper.