Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (eaq-),hydroxyl radicals (·OH),and sulfate anion radicals (SO4·-) were investigated using nanosecond pulse radiolysis techniques.The spectra of these ionic liquids on reaction with eaq-all exhibited a similar peak at about 320 nm,and a typical peak for eaq-in aqueous ionic liquid solutions.The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6) with eaq-were deduced to be 10 10 L mol-1s-1,however the values were lower for trisubstituted ionic liquids.For example,the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4) was 5.5×10 9 L mol-1s-1.Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts,and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4).Moreover,imidazolium cations were also oxidized by SO4·-to produce bivalent cation radicals,which exhibit a peak at 320 nm,and these rate constants are of the same order of magnitude,i.e.,10 9 L mol-1s-1,except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO4·-(k=2.8×10 8 L mol-1 s-1).Theoretical calculations were carried out to estimate the structures of the products of reduction by eaq- and the results were related to the experimental data.     

Interaction of aloe-emodin with human serum albumin

The presence of several high affinity binding sites on human serum albumin (HSA) makes it a possible target for many drugs. This study is designed to examine the effect of aloe-emodin on HSA by fluo-rescence, CD spectroscopy and molecular modeling. The results of fluorescence measurements sug-gested that the hydrophobic interaction was the predominant intermolecular force stabilizing the AE-HSA complex, which was in good agreement with the result of molecular modeling study. And the enthalpy change ΔH0 and the entropy change ΔS0 were calculated to be -7.041 kJ·mol-1 and 76.619 J·mol-1·K-1 according to the Van't Hoff equation. The alterations of protein secondary structure in the presence of AE in aqueous solution were quantitatively calculated from CD spectra, and the content of α-helices obviously increased.     

Fe3O4@C nanoparticles as high-performance Fenton-like catalyst for dye decoloration

Water pollution has become serious environmental problem nowadays. Advanced oxidation processes(AOP) have been widely applied in water treatment.However, traditional Fenton reaction based on Fe2﹢-H2O2 system has obvious drawbacks, which limit its applications In this study, magnetic Fe3O4core-C shell nanoparticles(Fe3O4@C NPs) were prepared for the decoloration of methylene blue(MB) via the co-precipitation followed by the hydrothermal dehydrogenation of glucose. Fe3O4@C NPs showed high catalytic activity of the decoloration of MB through the decomposition of H2O2 in Fenton-like reactions. Fe3O4@C NPs had much higher activity than bare Fe3O4 cores, suggesting the coating of carbon enhanced the catalytic activity. The performance of Fe3O4@C NPs was better at lower pH and higher temperature, but was significantly inhibited in the presence of radical scavenger tertiary butanol. Fe3O4@C NPs could be magnetic separated and regenerated, and maintained with very good catalytic activity. The implication for the applications of Fe3O4@C NP-catalyzed Fenton-like reactions in water treatment was discussed.     

Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

Effects of Influencing Factors on Fenton Oxidation of Antibiotic Pharmaceutical Wastewater by a Statistical Design Approach

A series of batch-scale experiments were completed to investigate the effects of operational parameters on chemical oxygen demand (COD) removal by Fenton reagent for antibiotic pharmaceutical wastewater (APW). The significance of five operational factors including the mass ratio of H2O2/COD (g/g), the mole ratio of H2O2/Fe2+ (mol/mol), initial pH, oxidation temperature T, and reaction time t were evaluated statistically by Box-Behnken design (BBD). It was found that the five parameters were all significant to the COD removal efficiency by t-test, as well as the interactions between mass ratio/reaction time and oxidation temperature/reaction. The optimal COD removal efficiency (89.50%) was achieved when the mass ratio of H2O2/COD and the mole ratio of H2O2/Fe2+ were 3.00 and 5.00 respectively, with pH value of 3.68 at 298K for 72min reaction. A quadratic regression model with 0.9907 regression coefficient (R2) was developed which had good agreement to the experimental data.     

Studies of Several Systems with Air Electrode Electro-Synthesizing H2O2 on the Spot for Degrading Aniline in Aqueous

A gas diffusion electrode (air electrode) with a high current efficiency of electro-synthesizing H2O2 using O2 in air was prepared. The several systems with air electrode as cathode of electro-synthesizing H2O2 on the reaction spot for degrading aniline in aqueous--electro-Fenton system, photo-excitation electro-H2O2 system and photo-electro-Fenton system, were developed. The rates of decomposition of H2O2 and mineralization of aniline were experimentally measured respectively under different conditions, and the results indicated there has an excellent parallel relation between decomposition rate of H2O2 and mineralization rate of aniline. Especially, photo-electro-Fenton system, where H2O2 is decomposed the fastest, is the best system of oxidizing and degrading organic toxicants. Compared photo-electro-Fenton system with photo-Fenton system, important role is revealed in the interface of air electrode. In this paper, the mineralization mechanism of aniline in the photo-electro-Fenton system was also discussed.     

新型除草剂(ZJ0777)与牛血清蛋白结合作用的荧光光谱研究

该实验用荧光猝灭光谱和同步荧光光谱研究了在不同温度下,新型除草剂N-(2-溴苯基)-2-(4,6-二甲氧基-2-嘧啶氧基)苄胺[ZJ0777][C19H18BrN3O3]与牛血清蛋白(BSA)结合反应的光谱行为.发现BSA与ZJ0777发生反应生成了新的复合物,属于静态荧光猝灭,由Lineweaver-Burk双倒数方程求出了不同温度下反应时复合物的形成常数KLB(287 K:1.955×103 L·mol-1;298 K:2.441×103L·mol-1;308 K:3.041×103 L·mol-1)及对应温度下结合反应的热力学参数(△H=15.566 kJ·mol-1;△S=117.24,117.08,117.22 J·K-1;△G=-18.082,-19.325,-20.537 kJ·mol-1),证明二者主要靠疏水作用力结合,结合点位为1.同时利用同步荧光光谱,考察了ZJ0777对BSA构象的影响.     

Nitrogenation Process of Nd(Fe,Mo)12 Compound

The reaction kinetics between nitrogen gas and Nd(Fe, Mo)₁₂ intermetallic compound has been studied. The relationship between the reaction temperature, the reaction time with average mass fraction of N in samples have been measured. The activation energy of first step reaction, E_f,(18.2 kJ/mol), is smaller than E_s (64.6 kJ/mol) of the second step during which nitrogen diffusion in the range 400~550℃ can be represented by an activated interstitial diffusion process. Heating above 550℃ leads to disproportion of the compound into NdN and α-Fe and the permanent properties will be damaged greatly.     

Effect of bromization on the propertises of a series of substituted 1,8,15,22—tetra（2,4—ditertbutylphenoxy） phthalocyanines

A series of 1,8,15,22-tetra(2,4-ditertbutylphen-oxy) phthalocyanines [α-（oAr）4PcM,M1=(H)2,M2=Pd,M3=Cu,M4=Zn,M5=Pb] were synthesized in this study.Each compound was bromized in two kinds of solvent.One is the solvent mixture of 1,1,2-trichloroethane and water,the other is 1,1,2-trichloroethane alone.The effects of solvent,bromine excess added and reaction duration on the bromization reaction were studied.The shift of maximum absorbance wave-length both is solution and in solid thin film was investigated comparatively,discovering that both were bathochromism but the former was more.TG data showed that the temperature of thermal decomposition decreased continuously with the increase of numbers of bromine.Finally,the fragments produced during the bromization of (OAr)4PcPb in 1,1,2-trichloroethane were characterized by GC/MS.Based on the electronic structure,the possible mechanism of decomposition of these compounds was presented and discussed.     

Assessment of the apparent activation energies for gas/solid reactions-carbonate decomposition

The guidelines for assessing the apparent activation energies of gas/solid reactions have been proposed based on the experimental results from literatures. In CO₂ free inlet gas flow, CaCO₃ decomposition between 950 and 1250 K with thin sample layer could be controlled by the interracial chemical reaction with apparent activation energy E = (215±10) kJ/mol and E = (200±10)kJ/mol at T = 813 to 1020 K, respectively. With relatively thick sample layer between 793 and 1273 K, the CaCO₃ decomposition could be controlled by one or more steps involving self-cooling, nucleation, intrinsic diffusion and heat transfer of gases, and E could vary between 147 and l90 kJ/mol. In CO₂ containing inlet gas flow (5%-100% of CO₂), E was determined to be varied from 949 to 2897 kJ/mol. For SrCO₃ and BaCO₃ decompositions controlled by the interfacial chemical reaction, E was (213±15) kJ/mol (1000-1350 K) and (305+15) kJ/mol (1260-1400 K), respectively.     

Effect of Yb2O3 doping on the grain boundary of NiFe2O4–10NiO-based cermets after sintering

xYb2O3–15(20Ni–Cu)/(85?x)(NiFe2O4–10NiO) (x=0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0) cermets for aluminum electrolysis were prepared to investigate the effect of Yb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), and electron probe microanalysis (EPMA), YbFeO3 was produced along the grain boundary. The YbFeO3 was concluded to not only have formed from the interaction between the NiFe2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiFe2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the pro-duction of YbFeO3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.     

Effect of Yb_2O_3 doping on the grain boundary of NiFe_2O_4–10NiO-based cermets after sintering

xY b2O3–15(20Ni–Cu)/(85- x)(NiF e2O4–10NiO)(x = 0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0) cermets for aluminum electrolysis were prepared to investigate the effect of Yb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction(XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy(SEM/EDX), and electron probe microanalysis(EPMA), YbF eO 3 was produced along the grain boundary. The YbF eO 3 was concluded to not only have formed from the interaction between the NiF e2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiF e2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the production of YbF eO 3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.     

Characterization of Inverse Spinel LiNiVO_4 Cathode Materials Prepared by the Sol-gel and Polymer Precursor Method

1 Results Due to the high cell voltage of LiNiVO4,the compound properties have been continuously studied as the potential cathode material for Li-ion batteries.LiNiVO4 cathode product has been known to exhibit high cell voltage of 4.8 V[1].LiCH3COO.2H2O (Sigma),Ni(CH3COO)2.4H2O (Aldrich) and NH4VO3(Ajax Finechem) were used as the starting reactants. In this work,LiNiVO4 was prepared by the sol gel method.This method was used to replace the conventional solid state reaction method in terms of the sample preparation as well as enhancing the conductivity of the composite material by adding citric acid[2].Citric acid behaves not only as a chelating reagent but also as a carbon source[3].The product was characterized using TGA and XRD.The TGA result shows that the minimum temperature to sinter the precursor was around 600 ℃.The initial weight loss was 3.61% before 100 ℃ due to the evaporation of water.The decomposition process stops at temperature above 600 ℃.The prepared powder was sintered at various temperatures ranging from 500 ℃ to 700 ℃ for 3 h.The mechanism for the synthesis of LiNiVO4 was determined by analyzing the TGA spectra.This work also includes the several suggested reaction steps involved in the preparation of LiNiVO4.     

Degradation of the antibiotic sulfamonomethoxine sodium in aqueous solution by photo-Fenton oxidation

In this study, photo-Fenton oxidation was applied to degradation of sulfamonomethoxine sodium (SMMS) in aqueous solution. The operation parameters of pH, temperature, and concentrations of H2O2, Fe2+ and SMMS were investigated. The optimum conditions for the photo-Fenton process were determined as follows: [SMMS]=4.53 mg/L, pH 4.0, [H2O2]=0.49 mmol/L, [Fe2+]= 19.51 μmol/L and T=25°C. Under these conditions 98.5% of the SMMS degraded. The kinetics were also studied, and degradation of SMMS by the photo-Fenton process could be described by first-order kinetics. The apparent activation energy was calculated as 23.95 kJ/mol. Mineralization of the process was investigated by measuring the chemical oxygen demand (COD), and the COD decreased by 99% after 120 min. This process could be used as a pretreatment method for wastewater containing sulfamonomethoxine sodium.     

Removal of TOC and Color in Bleaching Effluents from Straw Pulp and Paper Mill by Fe^0- H2O2 Process

TOC and color in the bleaching effluent from straw pulp paper process could not reach draining standard after its treatment by a biochemical process. In this study, advanced treatment by integrated micro-electrolysis （Fe^0） method and Fenton-like process was investigated under various conditions, i.e. pH, Fe/C ratio, initial I-I2O2 concentration and carrier gas. Results showed that Fe/C ratio（V/V = 1.5）, larger H2O2 dosage around 50 rag/L, lower pH（pH= 3） turned out to be particularly efficient. Temperature was a key parameter, remarkably increasing reaction rates. Carrier air not only improved reaction efficiency, but also saved H2O2 dosage. Chlorinated organic compounds could be reductive dechlorinated by Fe^0 reaction and oxidated by OH produced from Fenton process. The combination of Fe^0 and H2O2 reactions had been proved to be highly effective for the advanced treatment of such a type of wastewaters, and important advantages concerning the application in the study.     

Synthesis, structure and property of serial p-carboxylphenoxyacetate-lanthanide coordination polymers

Four novel lanthanide-based coordination polymers, [Ln（PBDC）（HPBDC）（H2O）3] （H=PBDC=p-carboxylphenoxyacetate; Ln = La （1）, Pr （2）, Nd （3）） and [La=（PBDC）3（H2O）4] （4）, have been prepared through hydrothermal synthetic methods. Compounds 1-3 are isomorphous and exhibit one-dimensional （1D） chain-like motifs, while compound 4 features a complicated three-dimensional （3D） architecture, which is designed and synthesized based on the inspiration from the structure characterization of compound 1. Under the similar reaction conditions, the carboxyl in compound 1 may be further deprotonated by adding the organic base of 2,2′-bipyridine. This subtle change caused a significant difference in the structures, from 1D chain of 1 to a 3D structure of 4. In addition, IR, UV-Vis, TGA and magenetic properties are also investigated in this paper.     

Effects of baria on propane oxidation activity of Pd/Al2O3 catalyst: Pd–BaO interactio n and reaction routes

The BaO-modified Pd/Al2O3exhibits much better catalytic activity than Pd/Al2O3for C3H8 oxidation both before and after the hydrothermal aging treatment. Further studies ascribe its good activity to the influence of BaO species on the physicochemical characteristics of the catalyst and the reaction routes. Firstly, the BaO species inhibits the phase transformation of alumina, resulting in higher surface area of the catalysts and hereby a better dispersion of Pd. Secondly, the basic nature and electron-withdrawing effect of barium oxide maintain palladium at high oxidation state, which leads to a higher PdO content on surface of the BaO-modified catalyst. Finally, the formation/decomposition of carbonate/bicarbonate species can be promoted by the addition of BaO, which provide extra reaction routes and are important for the deep oxidation of C3H8.     

The influence of molar ratios of Ce/Zr on the selective catalytic reduction of NOx with NH3 over Fe2O3-WO3/CexZrl-xO2 （0 〈 x 〈 1） monolith catalyst

A series of CexZrl_xO2 （0 ≤ x ≤ 1） with dif- ferent molar ratios of Ce/Zr were syhthesized via coprecip- itation method, and Fe2O3-WO3/CexZrl-xO2 monolithic catalysts were prepared, for selective catalytic reduction of nitrogen oxides by ammonia （NH3-SCR）. The structural properties and redox behavior of the catalysts were com- prehensively characterized by N2 physisorption, X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, H2-temperature programmed reduction （H2-TPR） and activity measurement for NH3-SCR. The results showed that the NH3-SCR activities of the catalysts were gradually enhanced by increasing the molar ratios of Ce/Zr, especially the low- temperature catalytic activity and the reaction temperature window. Fe2O3-WO3/Ceo.68Zro.3202 monolithic catalyst presented the best NH3-SCR activity among the investigated catalysts, more than 90 % NOx could be removed in the temperature range of 247-454 ℃ on the catalyst under the gas hourly space velocities of 30,000 h- 1. And it always held more than 99 % N2 selectivity and less than 20 ppm （1 ppm =10-6 L/L ） N20 generation concentration between 200 and 500 ℃, the catalyst also displayed its strong resistance of H20 and SO2. Good textural and structural properties, more surface Fe, Ce and active oxygen were together contributed to the excellent NH3-SCR performance of Fe2O3-WO3/ Ce0.68Zr0.32O2 catalyst.     

光谱法研究加替沙星与牛血清白蛋白的相互作用

采用荧光光谱和紫外吸收光谱法研究牛血清白蛋白与加替沙星的相互作用机制.由荧光光谱可知加替沙星对牛血清白蛋白有猝灭作用;用Stern-Volmer方程求得在17℃和25℃温度下它们的结合常数分别为1.14×107L·mol-1和6.30×106L·mol-1,结合位点数分别为1.46和1.44;用热力学方程处理实验数据得到结合反应的相关参数(25℃):△H=53.46 kJ·mol-1,△G=-38.79 kJ·mol-1,△S=49.24 J·K-1·mol-1;并用三维荧光光谱和同步荧光光谱探讨加替沙星对牛血清白蛋白构象的影响.实验结果表明,加替沙星对牛血清白蛋白的猝灭方式为静态猝灭,它们间的主要作用力为静电作用.