钴改性Fe3O4-MnO2催化转化生物质合成气制备液体燃料

本文制备了用于费托合成反应的钴改性Fe₃O₄-MnO₂双功能催化剂,并探究了钴负载量对Fe-Co协同效应的影响以及Fe₁Co_xMn₁催化剂的费托合成反应性能. 实验发现,在Fe₃O₄-Mn催化剂中加入Co可促进铁氧化物的还原、增加反应过程中铁位点的活性. 此外,Co的加入可增强Fe-Co金属间的电子转移,加强两者的协同作用,提高催化性能. Co负载较高的Fe₁Co_xMn₁催化剂可进一步促进加氢反应能力,使产品分布向短链烃方向转移. 在280 ^°C、2.0 MPa和3000 h^-1的最佳工况条件下,Fe₁Co₁Mn₁催化剂的液体燃料收率最高.     

焙烧温度对SiO2负载的Co3O4纳米粒子表面氧缺陷浓度和CO氧化催化性能的影响

以传统的浸渍法,在不同焙烧温度下制备了用于CO氧化反应的Co₃O₄/SiO₂催化剂．通过激光拉曼光谱(Raman)、X射线光电子能谱(XPS)、X射线衍射(XRD)、程序升温还原(TPR)和X射线吸收精细结构谱(XAFS)表征了该系列催化剂的结构．在所有的催化剂中,XRD和Raman光谱都只检测到了Co₃O₄晶相的存在．与Co₃O₄体相相比,XPS结果表明在200 oC焙烧的(Co₃O₄(200)/SiO₂)催化剂中Co₃O₄表面上存在着过量的Co²⁺．与XPS的结果一致,TPR结果表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄表面上存在氧缺陷, 并且XAFS结果也表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄具有更多的Co²⁺．提高焙烧温度使得过量的Co²⁺进一步氧化为Co³⁺,同时降低了表面氧缺陷浓度,从而得到计量比的Co₃O₄4/SiO₂催化剂．在所有的负载催化剂中Co₃O₄(200)/SiO₂催化剂表现出了最好的CO氧化催化性能,表明过量Co²⁺和表面氧缺陷的存在能够促进Co₃O₄催化CO氧化反应的活性.     

基于从头算势能面对S-(2P)+H2(1Σ+g)→SH-(1Σ)+H(2S)反应的量子含时波包计算

本文基于离子分子SH₂^-基态势能面,应用含时波包方法研究了反应S^-(²P)+H₂(¹Σ⁺_g)→SH^-(¹Σ)+H(²S)的动力学行为. 给出了反应几率和积分截面随碰撞能的变化关系,结果表明,在讨论的所有碰撞能量范围内二者均存在显著的振荡结构. 当初始转动量子数j=0,2,4,6,8,10和振动量子数v=0,1,2,3,4时,从总反应几率数值计算中可以看出,双原子H₂的振动激发和转动激发显著提高了反应活性. 同时积分散射截面的理论值与前人的实验值相符合.     

锰氧化物团簇正离子与硫化氢反应的实验与理论研究 (cited: 2)

采用激光溅射法制备了同位素标记的氧化锰团簇正离子Mn_m¹⁸O_n⁺,并研究了其在快速流动反应管中与硫化氢在热碰撞条件下的反应,氧化锰团簇正离子与硫化氢反应前后的质量分布与强度变化由飞行时间质谱仪检测．实验表明,绝大多数氧化锰团簇正离子可与硫化氢发生氧-硫交换反应产生水分子,反应通式为：Mn_m¹⁸O_n⁺+H₂S→Mn_m¹⁸O_n-1S⁺+H₂¹⁸O．通过密度泛函理论计算了氧化锰团簇正离Mn₂O₂⁺、Mn₂O₃⁺和Mn₂O₄⁺与H₂S反应的机理,结果显示,在这些反应体系中氧-硫交换反应通道同时具有热力学和动力学优势,印证了实验中观察到的现象．气相团簇研究发现的氧-硫交换反应与相关凝聚相体系反应结果一致     

一维锰氧化物纳米棒在以O2为氧源的苯甲醇氧化反应中的催化性能

采用水热法合成MnOOH一维纳米线,通过MnOOH在不同气氛和温度中煅烧得到尺寸和形貌相似的不同锰氧化物,并用于以O₂为氧源的苯甲醇液相氧化反应. 结果表明,MnO₂对苯甲醇氧化反应具有较高的催化活性. 通过XPS、SEM、TEM和H₂-TPR等手段对催化剂的形貌和结构进行了表征,并讨论了可能影响反应活性的一些因素. MnO₂的良好催化性能可能与其晶格氧具有较高的迁移率以及氧化还原能力有关. 通过简单的焙烧处理,可以使MnO₂催化剂在苯甲醇氧化反应中具有良好的重复使用性.     

Al2O3Hx(x=1—3)分子团簇的结构与光谱研究

用密度泛函理论(DFT)的B3lyp方法在6-311++g(d,p)水平上对Al₂O₃H_x(x=1—3)分子的几何构型, 电子结构, 振动频率等性质进行了系统研究. 并给出了它们可能基态结构的总能量(E_T), 零点能(E_z), 摩尔热容(C_v), 标准熵(S), 原子化能(ΔE_m), 垂直电离能(IP)及垂直电子亲和能(E_A). Al₂O₃H和Al₂O₃H₂分子可能的基态的几何构型都为平面结构. Al₂O₃H₃的两个可能为基态的几何构型都是在立体Al₂O₃(D_3h)的几何结构基础上加三个氢原子构成. 这三个分子的能量最低结构为Al₂O₃H(²A′)C_s, Al₂O₃H₂(¹A′) C_s, Al₂O₃H₃ (²A) C₁.     

Cr2O3催化合成气转化至甲醇的微观动力学研究

Cr₂O₃是双功能催化合成气转化的重要氧化物组分,其可将合成气转化为重要的中间物种甲醇. 结合密度泛函理论计算和微观动力学模拟,本文系统研究了干净Cr₂O₃(001)和(012)表面,以及氢覆盖或含有氧空位的还原(012)表面的结构及催化合成气转化至甲醇的活性. 本文探讨了合成气转化为甲醇的分步或协同反应路径,并确定CO或CHO氢化是决速步骤. 微观动力学分析表明,Cr₂O₃(001)表面难以催化合成气转化为甲醇,在673 K 时,两个还原性(012)表面的反应速率(25∽28 s^-1)比干净的(012)表面(4.3 s^-1)高出约五倍. 计算结果表明了Cr₂O₃表面还原性对催化活性的重要性,或许可以为双功能催化体系中氧化物组分的设计提供参考.     

分级多孔Cafe2O4/C的合成及其微波催化活性

以天然木棉为模板,利用造孔及纳米颗粒自组装两步法合成了分级多孔的Cafe₂O₄/C复合催化剂. Cafe₂O₄/C复合催化剂保留了木棉模板的中空纤维形貌,且该中空纤维是由碳及均匀分布在碳表面的Cafe₂O₄纳米颗粒组成. 该复合催化剂具有较强的甲基紫微波催化降解活性. 研究了Cafe₂O₄负载量、微波功率、催化剂用量、甲基紫的初始浓度和pH值对微波诱导甲基紫降解的影响. 结果表明,Cafe₂O₄/C微波降解甲基紫的催化反应具有较高的反应速率和较短的反应时间. 其降解反应符合一级动力学模型. Cafe₂O₄/C 高的催化活性得益于催化反应和吸附特性之间的协同作用.     

O2分子吸附的金属表面的O2(1Δg)猝灭

建立了一套流动装置测量单重态氧O₂(¹Δ_g)在O₂分子吸附的金属Cu、Cr、Ni和Ag表面的猝灭几率. 随实验时间和O₂(¹Δ_g)浓度增加,猝灭几率增加. 当上述金属样品在几帕斯卡的真空度下暴露数小时后猝灭几率会回到原先水平. 提出了一种基于表面吸附位上弱化学吸附的表面吸附氧分子O₂(¹∑_{g相似文献}   

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

The effects of hydrogen peroxide on the sonochemical degradation of phenol and bisphenol A

This report describes the effects of H₂O₂ concentration (0.01, 0.1, 1, and 10 mM) on the sonochemical degradation of phenol and bisphenol A (BPA) using an ultrasonic source of 35 kHz and 0.08 W/mL. The concentration of the target pollutants (phenol or BPA), total organic carbon (TOC), and H₂O₂ were monitored for each input concentration of H₂O₂. The effects of H₂O₂ on the sonochemical degradation of phenol was more significant than that of BPA because phenol has a high solubility and low octanol–water partition coefficient (K_ow) value and is subsequently very likely to remain in the aqueous phase, giving it a greater probability of reacting with H₂O₂. The removal of TOC was also enhanced by the addition of H₂O₂. Some intermediates of BPA have a high K_ow value and subsequently have a greater probability of pyrolyzing by the high temperatures and pressures inside of cavitation bubbles. Thus the removal efficiency of TOC in BPA was higher than that of phenol. The removal efficiencies of TOC were lower than the degradation efficiencies of phenol and BPA. This result is due to the fact that some intermediates cannot readily degrade during the sonochemical reaction. The H₂O₂ concentration decreased but was not completely consumed during the sonochemical degradation of pollutants. The initial H₂O₂ concentration and the physical/chemical characteristics of pollutants were considered to be important factors in determining the formation rate of the H₂O₂. When high concentration of H₂O₂ was added to the solution, the formation rates were relatively low compared to when low concentrations of H₂O₂ were used.     

Fluorophotometric Determination of Hydrogen Peroxide with Fluorescin in the Presence of Cobalt (II) and Reaction Against Other Reactive Oxygen Species

A fluorophotometric method for the determination of hydrogen peroxide (H₂O₂) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent lactoid fluorescein, by H₂O₂ to give highly fluorescein fluorescence emission. In the determination of H₂O₂, the calibration curve exhibited linearity over the H₂O₂ concentration range of 1.5–310 ng mL⁻¹ at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL⁻¹, 30.8 ng mL⁻¹, and for 308 ng mL⁻¹ of H₂O₂, respectively. The detection limit for H₂O₂ was 1.9 ng mL⁻¹ six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such as singlet oxygen (¹O₂), hydroxyl radical (^•OH), peroxynitrite (ONOO⁻) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery tests of H₂O₂ in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory.     

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

pH‐dependent surface‐enhanced Raman scattering observation of sulfanilamide on the silver surface

Monolayers of sulfanilamide on metallic surface can serve as an ideal model for understanding the interaction mechanism between the metal and the sulfanilamide molecule. In the present paper, the surface‐enhanced Raman scattering (SERS) technique was employed to obtain the SERS spectra of sulfanilamide monolayers formed on the silver surface under different pH values. Assignments of the spectra were carried out with the aid of density functional theory (DFT) calculations (BLYP/6‐311G). It can be found that the adsorption function of sulfanilamide on the silver surface was influenced by the pH value. The fully protonated sulfanilamide molecule adsorbed on the silver surface through N¹³H₂ group and the benzene ring anchored in a relatively perpendicular manner leading to N⁷H₂ and S¹⁰O₂ groups near the surface, while the completely deprotonated sulfanilamide molecule attached on the silver surface via N⁷H₂ and the benzene ring was perpendicular to, and the N¹³H₂ and S¹⁰O₂ groups were far from the silver surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and spectroscopic investigation of iron(III) complexes of N′-(thioaroyl)pyridine-2-carbohydrazides

A new series of iron(III) complexes [Fe(L¹)(HL¹)], [Fe(L¹)Cl]; [H₂L¹ = N′-(2-methoxythiobenzoyl)pyridine-2-carbohydrazide], [Fe(L²)(acac)], [Fe(HL²)₂Cl]; [H₂L² = N′-(4-methoxythiobenzoyl)pyridine-2-carbohydrazide] and [Fe(L³) (acac)]; [H₂L³ = N′-(2-hydroxythiobenzoyl)pyridine-2-carbohydrazide] were prepared by stirring/refluxing/mixing the respective ligand with FeCl₃/Fe(acac)₃ in chloroform/methanol. All the compounds were characterized by elemental analyses, magnetic susceptibility, IR, UV and Mössbauer spectral data. The complexes posses high/ low spin state and have tetrahedral/octahedral geometry.     

The sonochemical decolourisation of textile azo dye Orange II: Effects of Fenton type reagents and UV light

The removal of Orange II (O-II) from aqueous solution under irradiation at 850 kHz has been studied. The effects of both homogeneous (with FeSO₄/H₂O₂)_, and heterogeneous (Fe containing ZSM-5 zeolite/H₂O₂) Fenton type reagents are reported together with the effect of UV irradiation in combination with ultrasound both alone and with homogeneous Fenton-type reagent.Degrees of decolourisation of 6.5% and 28.9% were observed using UV radiation and ultrasound, respectively, whereas under the simultaneous irradiation of ultrasound and UV light, the decolourisation degree reached 47.8%, indicating a synergetic effect of ultrasound and UV light. The decolourisation was increased with the addition of Fenton’s reagent with an optimal Fenton molar reagent ratio, Fe²⁺:H₂O₂ of 1:50. In the combined process of ultrasound and UV light with the homogeneous Fenton system 80.8% decolourisation could be achieved after 2 h indicating that UV improves this type of Orange II degradation. The degree of decolourisation obtained using the heterogeneous sono-Fenton system (Fe containing ZSM-5 zeolite catalysts + H₂O₂ + ultrasound) were consistently lower than the traditional homogeneous ultrasound Fenton system. This can be attributed to the greater difficulty of the reaction between Fe ions and hydrogen peroxide.In all cases the Orange II ultrasonic decolourisation was found to follow first order kinetics.     

On the direct formation of HO2 radicals after 248 nm irradiation of benzene C6H6 in the presence of O2

We present in this work the direct observation of HO₂ radicals after irradiation of benzene C₆H₆ at 248 nm in the presence of O₂. HO₂ radicals have been unambiguously identified using the very selective and sensitive detection of continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled to a laser photolysis reactor. HO₂ radicals were detected in the first vibrational overtone of the OH stretch at 6638.20 cm^-1, using a DFB diode laser. This reaction might be important because 248 nm photolysis of H₂O₂ has often been used in the past for studying the OH^•-initiated degradation of C₆H₆, often using a large excess of C₆H₆ over H₂O₂. The possible importance of the title reaction with respect to these former laboratory studies has been quantified through comparison with HO₂ ^• signals obtained from 248 nm photolysis of H₂O₂: one obtains under our conditions (excess O₂ and total pressure of 6.6 kPa helium) from the 248 nm irradiation of identical initial concentrations [C₆H₆]=[H₂O₂] the following relative initial radical concentrations: [HO₂ ^•]=(0.28±0.05)×[OH^•]. Experiments with various O₂ concentrations have revealed that the origin of the HO₂ radicals is not the reaction of H-atoms with O₂, but must originate from the reaction of O₂ with excited C₆H₆ ^*. The quantum yield of C₆H₆ ^* formation has been deduced to ϕ=0.2±0.1. PACS  42.62.Fi; 82.20.Pm; 82.33.Tb     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Sono-photo-degradation of carbamazepine in a thin falling film reactor: Operation costs in pilot plant

The photo-Fenton degradation of carbamazepine (CBZ) assisted with ultrasound radiation (US/UV/H₂O₂/Fe) was tested in a lab thin film reactor allowing high TOC removals (89% in 35 min). The synergism between the UV process and the sonolytic one was quantified as 55.2%.To test the applicability of this reactor for industrial purposes, the sono-photo-degradation of CBZ was also tested in a thin film pilot plant reactor and compared with a 28 L UV-C conventional pilot plant and with a solar Collector Parabolic Compound (CPC). At a pilot plant scale, a US/UV/H₂O₂/Fe process reaching 60% of mineralization would cost 2.1 and 3.8 €/m³ for the conventional and thin film plant respectively. The use of ultrasound (US) produces an extra generation of hydroxyl radicals, thus increasing the mineralization rate.In the solar process, electric consumption accounts for a maximum of 33% of total costs. Thus, for a TOC removal of 80%, the cost of this treatment is about 1.36 €/m³. However, the efficiency of the solar installation decreases in cloudy days and cannot be used during night, so that a limited flow rate can be treated.     

Mössbauer studies of selected synthetic silicates

Mössbauer spectra of fayalite-, 7#x03B1;-Fe₂SiO₄, powder and single crystals were taken in the antiferromagnetic temperature region below T _N?65 K. The orientation of the efg and H(0) with respect to the crystallographic axes was determined as function of the temperature and compared to neutron diffraction and magnetic susceptibility data. A similar study was performed with Li‐acmite LiFeSi₂O₆, whose magnetic structure can be regarded as a model compound for quasi one‐dimensional systems. Synthetic annite KFe₃[AlSi₃O₁₀(OH)₂] has to contain at least about 10% Fe³⁺ in order to be stable. A comparison of the evaluation of the spectra assuming either Lorentzian line shape of the doublets or quadrupole splitting distributions QSDs shows that Fe³⁺/Fe²⁺‐ratios can be determined precisely by both methods. However, M2/M1-site distributions cannot be evaluated with great accuracy. In ilvaite CaFe₃[Si₂O₇/O/(OH)], there is a thermally activated intersite electron hopping between Fe²⁺ and Fe³⁺ at temperatures around 300 K in a double octahedron chain. At temperatures above 395 K there is extended electron delocalization in a narrow d‐ or polaron‐band. The substitution of Fe by Mn favours both effects and lowers the temperature of the crystallographic phase transition monoclinic to orthorhombic distinctly. In the solid solution series member acmite(50%)‐hedenbergite(50%) Na_0.5Ca_0.5Fe₂[Si₂O₆] just intersite electron hopping between Fe²⁺ and Fe³⁺ in the M1 octahedron chain and no formation of polaron bands is observed. This is explained by the larger Fe–Fe‐intrachain distances compared to those in ilvaite or magnetite.