Basicities of alumina-supported alkaline earth metal oxides

A series of alumina-supported alkaline earth metal oxide catalysts were prepared by incipient-wetness impregnation. These catalysts were characterized by nitrogen-sorption to determine their surface areas and pore size distributions. The basicities of these catalysts were characterized by temperature-programmed desorption of carbon dioxide. The TPD results demonstrate that all of the catalysts have one-peak profiles. The basicity increases with increasing atomic number of the alkaline earth metal. The alumina-supported alkaline earth oxides exhibit the same basic properties as bulk metal oxides. However, the presence of alumina can increase the mechanical strength of the catalyst, since the alkaline earth oxides have a weak mechanical strength. The basic properties of the catalysts are strongly influenced by the calcination temperature.     

Sample preparation in alkaline media

The use of tetramethylammonium hydroxide, tertiary amines and strongly alkaline reagents for sample treatment involving extraction and digestion procedures is discussed in this review. The preparation of slurries is also discussed. Based on literature data, alkaline media offer a good alternative for sample preparation involving an appreciable group of analytes in different types of samples. These reagents are also successfully employed in tailored speciation procedures wherein there is a critical dependence on maintenance of chemical forms. The effects of these reagents on measurements performed using spectroanalytical techniques are discussed. Several undesirable effects on transport and atomization processes necessitate use of the method of standard additions to obtain accurate results. It is also evident that alkaline media can improve the performance of techniques such as inductively coupled plasma mass spectrometry and accessories, such as autosamplers coupled to graphite furnace atomic absorption spectrometers.     

Chemiluminescence of luminol induced by dissolution of oxide-covered aluminum in alkaline aqueous solution

One-electron reduction of oxygen, hydrogen peroxide, potassium peroxodisulphate and potassium peroxodiphosphate was studied during the dissolution of oxide-covered aluminum in alkaline aqueous solution. The production of free oxidizing radicals was monitored by luminol chemiluminescence (CL). It was observed superoxide, hydroxyl, sulphate and phosphate radicals can be generated by the present method. In addition, luminol can be detected below nanomolar level, the linear logarithmic calibration range covering several orders of magnitude of concentration. The metallic aluminum and low-valent aluminum ions are the primary reductants of the system. The electron transfer to the solution is proposed to occur by tunneling through a thin insulating aluminum oxide film at the solid/electrolyte interface in moderately alkaline solutions with simultaneous dissolution of the forming oxide film. In a highly alkaline solution, it is more probable that the oxidation of aluminum species occurs in direct contact of the metallic aluminum with the aqueous solution. In the latter case, short-lived solvated low-valent aluminum ions, hydrogen atom and its deprotonated form, the hydrated electron, can exist as reducing mediators in the chemical reactions in the close vicinity of the dissolving solid/electrolyte interface. Luminol was also observed to exhibit CL under purely reducing conditions produced by a presently unknown excitation pathway.     

氧化铁对铂在碱性介质中催化氧化甲醇的促进作用

Pt催化剂是电催化领域用途最为广泛的贵金属催化剂.Pt资源稀缺,价格昂贵,同时它的物理化学特性又决定了其在多种催化反应中难以被替代.在质子交换膜燃料电池的小分子醇类电氧化过程中,难免存在Pt的毒化现象,其催化性能有待进一步提升.因此,围绕着Pt催化剂纳米结构的设计、抗毒性及反应机理的探索一直是电催化研究面临的重要课题.目前,已被广泛认可的提高Pt催化性能的方法之一是引入第二种金属,通过金属间协同效应(双功能机理)、张力效应或电子效应等对Pt的催化行为进行改性.对于由双/多金属组成的纳米结构催化剂,无论是协同效应还是电子效应,催化活性的提高都需要金属间有丰富的接触界面和恰当的邻近状态.通过调变两组元的种类、原子比和接触状态等可以实现对金属-金属界面的调控,进而调变催化剂性能.除金属助剂外,金属氧化物对Pt催化剂的助催化作用也引起广泛关注.由于金属氧化物与Pt之间的密切接触作用,氧化物的形貌特点对Pt的催化性能可产生重要影响.到目前为止,有关催化剂形貌效应的研究主要集中于贵金属纳米颗粒上(Pt,Au,Pd等),但关于金属氧化物载体/助剂的形貌对贵金属催化性能影响的研究尚不多.具有明确形貌的金属氧化物载体/助剂,暴露的晶面不同,表面原子的配位状态也不同,从而造成与之密切接触的Pt的性质发生改变.因此,金属氧化物的表面性质以及Pt-金属氧化物的界面性质将对电催化性能产生重要影响,深入阐释贵金属-金属氧化物的表/界面性质以及建立有效的构效关系,对设计和制备高效电催化剂具有一定的指导意义.为了提高Pt基催化剂活性、抗CO中毒能力以及稳定性,本文采用共沉淀法和水热法分别制备了纳米棒和六边形纳米片状的Fe2O3作为Pt催化剂的助剂,考察了助剂形貌对Pt催化剂在碱性介质中催化氧化甲醇的促进作用.通过X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱以及电化学技术对催化剂进行了表征.结果显示,Fe2O3的存在能显著提高Pt催化剂在碱性介质中对甲醇氧化的电催化性能,而且以Fe2O3纳米棒为助剂制备的Pt-Fe2O3/C-R催化剂催化活性以及稳定性比Fe2O3纳米片为助剂制备的Pt-Fe2O3/C-P催化剂更高.这种促进效应可能与助剂Fe2O3的形态有关.Pt-Fe2O3/C-R催化剂中Pt的质量比活性为5.32 A/mgPt,本征活性为162.7 A/m2Pt,分别是Pt-Fe2O3/C-P催化剂的1.67和2.04倍,是商业PtRu/C样品的4.19和6.16倍.协同效应和电子效应是Pt催化性能提升的主要原因.此外,Pt-Fe2O3/C-R样品中高价态Pt的含量较高,可能也是加速甲醇氧化反应动力学的原因之一.高价态的Pt可能会增强甲醇分子在Pt表面的吸附强度,促进Pt上甲醇氧化反应初始步.这些发现不仅可对甲醇电催化氧化机理有了更深的理解,而且对设计和制备高性能甲醇氧化电催化剂也具有一定的指导意义.     

Effect of alkaline materials on interfacial rheological properties of oil-water systems

Interfacial rheological properties of a model crude oil-water system were studied in the presence of sodium hydroxide. The interfacial viscosity, the non-Newtonian flow behavior and the activation energy of viscous flow were determined as a function of shear rate, alkali concentration and aging time. The fundamental conclusion of the experimental results is that the interfacial viscosity drastically decreases in the presence of alkaline materials and the change under favorable conditions may exceed 3 or 4 orders of magnitude. Simultaneously, the sodium hydroxide effectively suppresses the non-Newtonian flow behavior of the interfacial layer. The experimental observations are explained by simultaneous chemical processes taking place in the boundary layer. The present data may help to elucidate the formation, stability and breaking of alkali-containing oil-water emulsions and they provide additional information for better understanding of the displacement mechanism and for the formulation of alkaline flooding as a potential chemically enhanced oil-recovery method. Received: 6 April 1998 Accepted: 18 August 1998     

Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties

The basis set polarization method is used to generate the first-order polarized basis sets for Sn, Sb, Te, and I. The standard (spd) and extended (spdf) versions of those basis sets are derived for the purpose of calculations of dipole moments and dipole polarizabilities for molecules involving the fourth-row atoms. The verification of the performance of the generated polarized basis sets is achieved mainly by a cross-examination of different atomic and molecular results calculated in this paper. The role of the core-polarization and relativistic effects is investigated. It is shown that the relativistic contribution to dipole moments of the fourth-row hydrides is commensurate with the contribution due to electron correlation and must be explicitly considered in accurate calculations. The detailed basis set data for Sn through I are presented in the Appendix.     

Mixed complexes of alkaline earth uranyl carbonates: a laser-induced time-resolved fluorescence spectroscopic study

The interaction of the alkaline earth ions Mg(2+), Sr(2+) and Ba(2+) with the uranyl tricarbonato complex has been studied by time-resolved laser-induced fluorescence spectroscopy. In contrast to the non-luminescent uranyl tricarbonato complex at ambient temperature the formed products show luminescence properties. These have been used to determine the stoichiometry and complex stabilities of the formed compounds. As the alkaline earth elements are located in an outer shell of the complex the influence of the type of the alkaline earth element on the stability constant is not very drastic. The stability constants range from logbeta(113) degrees =26.07+/-0.13 to logbeta(113) degrees =26.93+/-0.25 for the first reaction step and from logbeta(213) degrees =29.73+/-0.47 to logbeta(213) degrees =30.79+/-0.29 for the overall complex formation with two alkaline earth ions.     

Graphene oxide decorated bimetal (MnNi) oxide nanoflakes used as an electrocatalyst for enhanced oxygen evolution reaction in alkaline media

Precious non-noble metals have been constantly attracting research attention in order to realize an inexpensive, extra active and more stable electrocatalysts in terms of various oxidation states and structures for their applications in oxidation (splitting) of water. In the present work graphene oxide incorporated, MnO₂-NiO composite metal oxide nanoflakes were synthesized on the stainless steel substrate using efficient electrodeposition route in alkaline media and drop casting method with further annealing treatment at 400 °C for 4 h. Initially MnO₂-NiO nanoflakes were deposited using different cyclic sweep rates, later graphene oxide suspension was drop casted on the MnO₂-NiO nanoflakes and subsequently subjected to annealing at 200 °C for 2 h. The prepared electrode material is denoted as GO/MnO₂-NiO/SS and used as an electrocatalyst for oxygen evolution. Field emission scanning electron microscopy, transmission electron microscopy, Energy dispersive electron spectroscopy and X-ray diffraction spectroscopy were used to study the crystalline nature and morphologies of the deposited films. The electrochemical properties of the electrode material were investigated using cyclic voltammetry and linear sweep voltammetry. The electrode exhibits low overpotential and small Tafel slope of 379 mV and 47.84 mVdec⁻¹ at the current density of 10 mA cm⁻² in alkaline (KOH) medium. In addition, the electrode shows a long time stability of 28800 s. Hence, the present study suggests that the GO incorporated Mn-Ni bimetal oxide modified electrode is suitable electrode material for oxygen evolution reaction (OER), owing to its facile preparation, inexpensive, easy handling and high active nature.     

Pseudopotential study of the ground and excited states of Yb2

The ground state of the van der Waals-type lanthanide dimer Yb₂ has been studied by means of relativistic energy-consistent ab initio pseudopotentials using three different core definitions. Electron correlation was treated by coupled-cluster theory, whereby core-valence correlation effects have been accounted for either explicitly by correlating the energetically highest coreorbitals or implicitly by means of an effective core-polarization potential. Results for the first and second atomic ionization potentials, the atomic dipole polarizability, and the spectroscopic constants of the molecular ground state are reported. Low-lying excited states have been investigated with spin-orbit configuration interaction calculations. It is also demonstrated for the whole lanthanide series that correlation effects due to the atomic-like, possibly open 4f-shell in lanthanides can be modeled effectively by adding a core-polarization potential to pseudopotentials attributing the 4f-shell to the core. Received: 3 April 1998 / Accepted: 27 July 1998 / Published online: 9 October 1998     

Fluorescent pH probes for alkaline pH range based on perylene tetra-(alkoxycarbonyl) derivatives

The pH detection in the alkaline range is particularly important in many fields such as leather processing, waste water treatment, paper industry, and metal mining and finishing. Compared with traditional analysis methods such as colorimetric sensors and electrochemical sensors, the fluorescence and colorimetric probes for pH measurements have attracted much more attention due to their advantages of high sensitivity, excellent selectivity, noninvasiveness, low cost, fast response time, the possibility of continuously measurement, etc. However, there are few fluorescent probes fiting for alkaline pH monitoring. Acturally, the design and synthesis of them were more significant for new probes producing. In this study, the design, synthesis, and practical application of two novel fluorescent pH probes for alkaline pH assay were discussed. Both of the two probes were derived from perylene tetra-(alkoxycarbonyl). The red or blue shift of the absorption/fluorescence spectrum was caused by the introduction of electron donor amino or oxygen ring in the bay region. Due to electronic separation of the OH group from the electron-withdrawing core, the probes have high pKa values and cover the pH range from 8 to 12. They exist in either fluorescent acid form or non-fluorescent basic form. It was investigated that the amino substituent at bay region had a higher pKa value than O-heterocyclic annulated perylene, which showed that the adjustable pKa value could be achieved by the modification of electron withdrawing groups. The probes would have a wide use for testing strips measurements and monitoring pH changes in concrete.     

Properties of Zinc alloy electrodeposits produced from acid and alkaline electrolytes

Zinc–cobalt (Zn–Co) and zinc–nickel (Zn–Ni) alloy electrodeposits each prepared from acid and alkaline formulations were compared for their properties. Compared to alkaline baths, acid baths offer higher metal percent of the alloying element and higher current efficiency. In alkaline baths, the variation of metal percent in deposit with current density is less significant, but that of current efficiency with current density is more. Electrolyte pH does not change significantly in alkaline solutions compared to acid solutions. X-ray diffraction evaluation of Zn–Co deposits from both electrolytes indicated their presence in the η-phase, while Zn–Ni shows pure γ-phase for deposits obtained from alkaline solutions and the existence of γ-phase with traces of η-phase of zinc for deposits obtained from the acid electrolytes. Scanning electron microscope examination shows finer grain structure for deposits obtained from alkaline solutions, and atomic force microscope studies confirm their nanostructure with reduced surface roughness. Deposits obtained from the alkaline baths exhibited higher corrosion resistance probably due to their nanostructure.     

Negative-type photosensitive polyimide precursors developable with aqueous alkaline solutions

New photosensitive polyimide precursors developable with aqueous alkaline solutions were synthesized. Among diamine monomers having a photofunctional group, 2′-(methacryloyloxy)ethyl 3,5-diaminobenzoate yields high molecular weight polyamic acid. A photosensitive polymer composition consisting of Michler's ketone and a thermally stable peroxide, 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone, results in a high photosensitivity of 200 J/m². The photosensitive coating of the composition is soluble in aqueous alkaline solutions as well as in organic aprotic polar solvents, and both solvents can be used as developers. However, the resolution of patterns is quite different, especially in thick films. Solvent developers results in poor resolution, whereas aqueous alkaline developers give patterns of high aspect ratio even in thick films. This is probably due to the difference in the diffusion efficiency and swelling properties of the polymer compared to the developers.     

4-Amino-1-naphthylphosphate as a substrate for the amperometric detection of alkaline phosphatase activity and its application for immunoassay

Immunosensors and biochemical array detection systems based on electrochemical transducers have many advantages such as low detection limit, fast response, simple design and ease of miniaturization. However, further development of such sensors will depend on the availability of suitable substrates that can be converted by a labeling enzyme to an electrochemically active product. Here, we report the synthesis of 4-amino-1-naphthylphosphate and it’s application as a new substrate for alkaline phosphatase. The electrochemical and enzymatic properties of this compound were investigated and compared with the properties of other aromatic 1,4-dihydroxy and 1,4-hydroxy-amine derivatives. The product of the enzyme reaction was 4-aminonaphthol, which was rapidly converted in the presences of air to 1,4-iminonaphthoquinone. This compound could then be detected in an amperometric flow injection assay (AFIA) with −200 mV versus Ag/AgCl potential application. The analytical range for mouse IgG, in an alkaline phosphatase amplified sandwich immuoassay with amperometric detection, was 0.01-100 μg ml⁻¹.     

Purification and characterization of an alkaline protease prot 1 frombotrytis cinerea

Alkaline thiol protease named Prot 1 was isolated from a culture filtrate ofBotrytis cinerea. The enzyme was purified by ammonium sulfate fractionation, gel filtration, and ion-exchange chromatography. Thus, the enzyme was purified to homogeneity with specific activity of 30-fold higher than that of the crude broth. The purified alkaline protease has an apparent molecular mass of 43 kDa under denaturing conditions as estimated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The native molecular mass (45 kDa), determined by gel filtration, indicated that the alkaline protease has a monomeric form. The purified protease was biochemically characterized. The enzyme is active at alkaline pH and has a suitable and high thermostability. The optimal pH and temperature for activity were 9.0–10.0 and 60°C, respectively. This protease was stable between pH 5.0 and 12.0. The enzyme retained 85% of its activity by treatment at 50°C over 120 min; it maintained 50% of activity after 60 min of heating at 60°C. Furthermore, the protease retained almost complete activity after 4 wk storage at 25°C. The activity was significantly affected by thiol protease inhibitors, suggesting that the enzyme belongs to the alkaline thiol protease family. With the aim on industrial applications, we focused on studying the stability of the protease in several conditions. Prot 1 activity was not affected by ionic strength and different detergent additives, and, thus, the protease shows remarkable properties as a biodetergent catalyst.     

Electrochemical behaviour of alkaline copper complexes

A search for non-cyanide plating baths for copper resulted in the development of alkaline copper complex baths containing trisodium citrate [TSC] and triethanolamine [TEA]. Voltammetric studies were carried out on platinum to understand the electrochemical behaviour of these complexes. In TSC solutions, the deposition of copper involves the slow formation of a monovalent species. Adsorption of this species obeys Langmuir isotherm. In TEA solutions the deposition involves the formation of monovalent ions obeying the non-activated Temkin isotherm. Conversion of divalent to monovalent copper is also slow. In TEA and TSC alkaline copper solutions, the predominant species that undergo stepwise reduction contain only TEA ligands.     

Electrooxidation of 2-propanol on Pt, Pd and Au in alkaline medium

Pd and Au are investigated as electrocatalysts for 2-propanol oxidation and compared with the conventional catalyst of Pt in alkaline medium. The current density for 2-propanol oxidation on Pd electrode is much higher than that on Pt electrode. The onset potential for 2-propanol oxidation on Pd electrode is more negative compared with that on Pt electrode. The results show that Pd is a good electrocatalyst for 2-propanol oxidation and the activity for the electrooxidation of 2-propanol is higher than Pt and Au in alkaline medium. Pd has higher electrocatalytic activity and better stability for the electrooxidation of 2-propanol. The present study shows a promising choice of Pd as effective electrocatalyst for 2-propanol electrooxidation in alkaline medium.     

A fast assay of water hardness ions based on alkaline earth metal induced coacervation (HALC)

In this work, a rapid assay of water hardness is presented based on the formation of a coacervate phase made up of multilamellar vesicles and close bilayers produced upon the reaction of alkaline earth metals with a carboxylate anionic surfactant in the presence of a co-surfactant (methanol). The procedure exploits the light scattering abilities of the coacervate phase which can be logarithmically linked to total hardness as CaCO₃ equivalents via spectrophotometric detection at 350 nm. The method, abbreviated as HALC, stemming from hardness by alkaline earth metal coacervation, is straightforwardly applicable overcoming the requirement for regulation of the experimental parameters involved in the determination procedure. In total, 28 water samples with various matrix compositions and hardness contents were analyzed with satisfactory accuracy as evidenced by comparison of the results with EDTA complexometric titration. The method is free from interferences from environmentally significant metal cations and inorganic anions affording detection limits as low as 13.5 mg L⁻¹ CaCO₃ with the aid of a correction factor, which is determined by the non-linear absorbance properties of the solution mixture, and satisfactory reproducibility (RSD = 4.21-8.08%).     

小功率空气冷却电感耦合等离子体发射光谱的研究 Ⅱ.碱金属和碱土金属分析特性

本文测定了碱金属、碱土金属九个元素48条谱线在空气冷却ICP中的信背比和检出限,并同全氩ICP的检出限进行了比较。本工作还测绘了各元素灵敏线与9个常见共存元素的光谱重叠扫描图,以了解可能存在的光谱干扰。     

Non-precious metal-based integrated electrodes for overall alkaline water splitting

A bifunctional electrocatalyst interface requires a superior charge transfer and good electric conductivity to produce an efficient and stable water splitting reaction. In the context of controlling the electrochemical activity of bifunctional catalytic materials, we demonstrate a novel approach to bridge conductive C-Qd-Mn interfaces with precise control. The excellent performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be dominantly attributed to the unique structure of C-Qds-Mn, which provides abundant active sites and facilitates electron transfer between electrode and electrolyte. Eco-friendly C-Qds were synthesized using a large-scale thermal assisted technique and utilized as electrocatalysts with Mn₃O₄ in alkaline splitting ToF (Turn over Frequency) calculation to make an effective combination. Due to their increased ECSA, conductivity, and electron-hole transfer, the prepared C-Qds-Mn delivered excellent HER/OER (0.494 V/1.6671V) activity, lower Standard deviation 0.006 V and 0.009V, surpassing the 10 mA limit comparable to commercially.     

电沉积磷酸钙生物活性陶瓷

在医用合金Ti6A14V基底上研究了电流密度、阴极电位和电解液温度等实验条件对磷酸钙生物陶瓷电沉积层的组成、结构和表面形貌等特性的影响，用扫描电子显微镜（SEM）、X射线衍射（XRD）、傅立叶变换红外光谱（FTIR）和感耦等离子体原子发射光谱（ICP／AES）等技术对磷酸钙陶瓷沉积层进行了表征．依据各种用酸钙盐的热力学性质，采用低温城液后处理的方法将前驱体转化为均匀单一的多孔状纯羟基历灰石沉积层．