Anodic stripping determination of Pt(IV) based on the anodic oxidation of Hg and Cd from electrochemically deposited Hg–Pt and Hg–Cd alloy phases

An anodic stripping voltammetric determination of Pt(IV) is described which is based on depositing intermetallic mercury–platinum and cadmium–platinum alloy phase on the surface graphite electrode, and recording the oxidation peak of mercury and cadmium from these phases with the help of linear scan voltammetry. Three alloy phases are formed in the case of mercury–platinum, whereas only one phase appears in the case of cadmium–platinum.     

Electrodeposition of Thin Cu–Cd–Se Film Layers

The formation of ternary Cu–Cd–Se thin film layers on a polycrystalline Pt electrode during the voltammetric scanning is examined. A sulfuric acid matrix containing selenious acid and uncomplexed Cu²⁺ and Cd²⁺ ions is used in all the cases. The growth kinetics is monitored by cyclic voltammetric measurements. The composition and structure are analyzed by XRD and ex situ Auger electron spectroscopy techniques. An underlying electrodeposition mechanism is proposed for the ternary system formation. It is shown that the growth process has a multistage character. Cu–Cd–Se film layers up to 2.5 m are obtained on a polycrystalline Pt cathode by potentiostatic electrolysis at E = 0.05 V (SHE). The chemical composition of the obtained layer is 39.1, 10.6, and 50.3 at. % Cu, Cd, and Se, respectively.     

Construction of Cd(II)–ferrocenesuccinate coordination complexes via changing adjuvant ligands and anions

Seven Cd(II)–ferrocenesuccinate coordination complexes with the formulas [Cd(η²-FcCOC₂H₄COO)₂(pbbbm)]₂ (1), [Cd(η²-FcCOC₂H₄COO)(pbbbm)Cl]₂ (2), [Cd(η²-FcCOC₂H₄COO)(pbbbm)I]₂ (3), {[Cd(η²-FcCOC₂H₄COO)₂(btx)₂]₂(CH₃OH)_0.5} (4), [Cd(η²-FcCOC₂H₄COO)₂(bix)]₂(H₂O) (5), {[Cd(η²-FcCOC₂H₄COO)(bbbm)_1.5Cl] · (CH₃OH)_0.5}_n (6), and {[Cd(η²-FcCOC₂H₄COO)(mbbbm)Cl] · (H₂O)_2.75}_n (7) [pbbbm = 1,4-Bis(benzimidazole-1-ylmethyl)benzene), btx = 1,4-bis(triazol-1-ylmethyl)benzene), mbbbm = 1,3-bis(benzimidazole-1-ylmethyl)benzene), bix = 1,4-bis(imidazol-1-ylmethyl)benzene, bbbm = 1,1-(1,4-Butanediyl)bis-1H-benzimidazole)] have been synthesized and characterized. Single-crystal X-ray analysis reveals that complexes 1–5 are all dimers and bridged by pbbbm, btx and bix, respectively. But the five complexes present some differences in their dimeric conformations, which can be ascribed to the impacts of adjuvant ligands and counter anions. In contrast to complexes 1–5, both 6 and 7 are of 1-D structures (with the same counter anions), and the former is double ladder-like structure only bridged by bbbm, while the latter is chain-like structure bridged by chlorine anions and adjuvant ligand mbbbm. Notably, various π–π interactions are found in complexes 1–7, and they have significant contributions to molecular self-assembly processes. The electrochemical studies of complexes 1–7 in DMF solution display irreversible redox waves and indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of ferrocenesuccinate.     

Crystal engineering of Cd(II) metal–organic frameworks bridged by dicarboxylates and N-donor coligands

Two new metal–organic coordination polymers, {[Cd₄(bpea)₄(IP)₈]?·?6H₂O} _n (1) and {[Cd_1.5(suc)_1.5(IP)_1.5]?·?4H₂O} _n (2) (bpea?=?biphenylethene-4,4′-dicarboxylate, H₂suc?=?succinic acid and IP?=?1H-imidazo[4,5-f][1,10]-phenanthroline), have been obtained through two types of dicarboxylate linkers. Complex 1 contains a neutral 2-D puckered sheet that is interdigitated by neutral 1-D zigzag chains. Compound 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak aromatic interactions. The different structures demonstrate the effect of the dicarboxylate ligands on the formation of such coordination architectures. The fluorescence property of the two complexes was also investigated.     

A sinapic acid–calix[4]arene hybrid selectively binds Pb over Hg and Cd

The binding affinity for Pb²⁺, Cd²⁺ and Hg²⁺ of the sinapic acid–calix[4]arene hybrid 2, having four sinapyl pendants at the upper rim, has been investigated via an UV–Vis study. Compound 2 has better complexing ability than the monomeric p-phenetidine derivative 1. This highlights that the clustering of sinapyl units in a basket-like structure, dictated by the calixarene scaffold, greatly enhances the complexing properties. Ligand 2 forms complexes even with Hg²⁺, which is not complexed by 1 at all; the complexes formed by 2 with Pb²⁺ and Cd²⁺ are much stronger than the analogous complexes formed by 1. The UV–Vis investigation shows that the hybrid 2 markedly favors Pb²⁺ over Cd²⁺ and Hg²⁺. Information on the structural properties of the complex species was obtained by ¹H NMR spectroscopy. NMR data show that all three metal ions are placed into the cavity consisting of the calixarene scaffold and the sinapyl pendants, though their binding affects the coordinating regions to a different extent.     

Study on a single flow acid Cd–chloranil battery

This paper describes a novel redox flow battery–single flow acid Cd–chloranil battery. The electrolyte of this battery for both negative electrode and positive electrode is the aqueous intermixture of H₂SO₄–(NH₄)₂SO₄–CdSO₄, the negative electrode is inert metal such as copper foil, and the positive electrode is an insoluble organic material, tetrachloro-p-benzoquinone (chloranil). Typically, the electrolyte is continuously circulated to pass though the cells by means of a single pump as the battery is on duty. There is no requirement for a membrane. Tetrachloro-p-benzo-hydroquinone is oxidized to chloranil at positive electrode and the cadmium ions is reduced to cadmium and electroplated onto the negative electrode during charge. The reverse occurs during discharge. Results obtained with a small laboratory cell show that high efficiencies can be achieved with an average coulombic efficiency of 99% and energy efficiency of 82% over 100 cycles at the current density of 10 mA cm^?2.     

An improved method for ratiometric fluorescence detection of pH and Cd using fluorescein isothiocyanate–quantum dots conjugates

In this study, thioglycolic acid capped-CdTe quantum dots (QDs) were modified by polyethylenimine (PEI), and then combined with fluorescein isothiocyanate (FITC) to fabricate FITC–CdTe conjugates. The self-assembly of FITC, CdTe and PEI was ascribed to electrostatic interactions in aqueous solution. The resulting conjugates were developed toward two routes. In route one, ratiometric photoluminescence (PL) intensity of conjugates (I_FITC/I_QDs) was almost linear toward pH from 5.3 to 8.7, and a ratiometric PL sensor of pH was favorable obtained. In route two, firstly added S²⁻ induced remarkable quenching of QDs PL peak (at the “OFF” state), which was restored due to following addition of Cd²⁺ (at the “ON” state). In the conjugates, successive introduction of S²⁻ and Cd²⁺ hardly influenced on FITC PL peaks. According to this PL “OFF-ON” mode, a ratiometric PL method for the detection of Cd²⁺ was achieved. Experimental results confirmed that the I_FITC/I_QDs exhibited near linear proportion toward Cd²⁺ concentration in the range from 0.1 to 15 μM, and the limit of detection was 12 nM. Interferential experiments adequately testified that the proposed sensors of pH and Cd²⁺ were practicable in real samples and complex systems. In comparison with conventional analytical techniques, the ratiometric PL method was simple, rapid, economic and highly selective.     

Predicting the formation enthalpies of Cd–Ga–In–Sn–Zn liquid alloys by the limiting partial enthalpies

The formation enthalpies of Cd–Ga–Sn, In–Sn–Zn, Cd–Ga–In–Sn, Ga–In–Sn–Zn and Cd–Ga–In–Sn–Zn liquid alloys are calculated by molecular interaction volume model (MIVM), which only using the limiting partial enthalpies of binary systems and the coordination numbers of the constituent elements in liquid alloys. The predicted values are compared with the experimental data and the values calculated using Hoch–Arpshofen model, which indicate that the model is reliable and convenient.     

Bubble points of hydrogen chloride–water–isopropanol and hydrogen chloride–water–isopropanol–benzene systems and liquid–liquid equilibria of hydrogen chloride–water–benzene and hydrogen chloride–water–isopropanol–benzene systems

Bubble points of the HCl–water–isopropanol and the HCl–water–isopropanol–benzene systems and liquid–liquid equilibria (LLE) of the HCl–water–benzene and the HCl–water– isopropanol–benzene systems were measured at 25–85°C and 30–70°C, respectively. The electrolyte nonrandom two-liquid model proposed by Chen et al. [C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, AIChE J. 28 (1982) 588–596] can satisfactorily correlate bubble points and liquid–liquid equilibria of the present mixed-solvent electrolyte systems over the entire range of temperature and concentrations using only binary adjustable parameters.     

智能石墨消解–ICP–MS法测定空气PM2.5中的Pb和Cd

建立电感耦合等离子体质谱(ICP–MS)测定空气PM2.5中的Pb和Cd元素的分析方法。采用连续β射线–DHS PM2.5大气颗粒物浓度监测仪采集空气中的PM2.5,以智能石墨消解PM2.5滤膜样品,ICP–MS测定其中的Pb和Cd元素含量。在优化的仪器条件下,元素Pb和Cd标准曲线的线性相关系数均为0.999 9,检出限分别为0.018,0.52ng/m3,满足HJ 657–2013的要求。Pb和Cd的加标回收率分别为95.8%~101.4%,99.3%~104.9%,测定结果的相对标准偏差分别为4.20%和2.38%(n=6)。对滤膜标准样品进行了测定,测定结果与标准值一致。该方法测定结果准确、可靠,可用于测定空气PM2.5中的Pb和Cd。     

Distribution of Cd and Pb in a wetland ecosystem

Cadmium and lead contents in sediments, dominant species of plants (Phargmites aus-tralis and Scripus mariquter), benthos (Helice tridens tientsinensis, llyoplax deschampsi, and Bul-lacta exarata), and waders (Calidris ruficollis) on the Eastern End of Chongming Island were measured. The results showed that, for cadmium, there are clear stratification in the sediment of reclaimed area and bio-amplification in food chain. However, for lead, a phenomenon was different. The amplification factors (AFs) for cadmium of primary producers, primary consumers, and secondary consumers were 2.59-12.38, 0.09-8.44, and 51.1, respectively. For lead, AFs of primary producers, primary consumers and the top trophic layer were 0.29-2.62, 0.06-5.62, and 7.31, respectively. Each species of macrobenthos showed different strategies to cadmium and lead. Large-sized crabs accumulated more lead, while small-sized crabs and snails accumulated more cadmium. Waders had significantly highest AFs for cadmium and lead in the study. Tha     

Electrochemical and structural characterization of sputter-deposited Mg–Nb and Mg–Nb–Al–Zn alloy films

Nanocrystalline Mg–Nb and Mg–Nb–Al–Zn alloy films were deposited by dc magnetron sputtering on glass and quartz substrates in a wide range of niobium concentrations from 6 to 80 at.%. Structural, electrochemical and corrosion properties of the films were studied by X-ray diffraction, dc voltammetry, electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance. Development of body-centred cubic Nb structure in the Mg–Nb alloy matrix yielded the effects of lattice contraction, grain refining and electrochemical passivity. The measurements showed high corrosion resistance of the films in alkaline solutions when niobium content was one third or more. An increased corrosion resistance was achieved by introducing minor amounts of Al (ca. 2 at.%). In particular, such Al effect was pronounced at lower Nb concentrations (20 to 30 at.%). Semiconductor properties of spontaneously formed oxide on Mg–Nb alloy were studied by Mott–Schottky plots, which indicated highly doped n-type oxide structures on Mg–Nb surface. The paper fills some gap in understanding of niobium–magnesium systems, which show potential for applications in hydrogen storage, switchable mirrors and corrosion protection.     

Electrochemical and microgravimetric characterization of magnetron-sputtered Fe–Cr–Ni–Ta and Fe–Cr–Ni alloy films in neutral and strongly acidic media

The Fe–Cr–Ni and Fe–Cr–Ni–Ta alloy films were deposited on quartz substrates by magnetron-sputtering using targets of AISI 316 stainless steel and in combination with pure tantalum. The conventional melting of the Fe–Cr–Ni–Ta alloy formed is virtually impossible because the melting point of tantalum is higher than the boiling points of the other components. Elemental content of the films was determined by XPS analysis. Corrosion behaviour of both alloy films was studied in 5% NaCl and 10 M HCl by electrochemical quartz crystal microgravimetry (EQCM), electrochemical impedance spectroscopy (EIS) and dc-voltammetry. The corrosion resistance of Fe–Cr–Ni–Ta appeared to be significantly higher than that of Fe–Cr–Ni in both neutral (5% NaCl) and strongly acidic (10 M HCl) media. The Fe–Cr–Ni–Ta specimen exhibited an extremely high corrosion resistance in 10 M HCl, where the corrosion rates were about one order of magnitude lower than those of Fe–Cr–Ni in neutral solution. EQCM measurements in NaCl solution indicated accumulation of corrosion products on the Fe–Cr–Ni–Ta surface, which was evident from a distinctive increase in electrode mass. By contrast, the mass of the tantalum-free alloy film decreased with a constant rate, which indicated alloy dissolution to prevail. The corrosion current calculated from the mass decrease was in good agreement with that derived from voltammetric measurements. The EQCM data showed that the corrosion resistance of the Fe–Cr–Ni–Ta alloy film in 10 M HCl was about two orders of magnitude higher than that of the Fe–Cr–Ni.     

The density and surface tension of In–Sn and Cu–In–Sn alloys

Abstract  

The density and surface tension of binary In–Sn and ternary Cu–In–Sn alloys have been measured by a sessile-drop method. Decrease of the density and of the surface tension was observed with rising temperature. With increased Sn content in the alloys, the density increased while the surface tension reduced slightly. Addition of Cu could significantly increase the density and surface tension in the Cu–In–Sn system. The surface tension of the Cu–In–Sn alloys was also calculated by means of Butler’s equation, and compared with experimental values, showing good agreement.     

Electrical Double Layer Structure in Surface-Inactive Electrolytes on a Liquid Cd–Ga Electrode in Methanol and Propylene Carbonate

Differential capacitance curves and potentials of zero charge are obtained for liquid Cd–Ga electrodes in methanol and propylene carbonate solutions of a surface-inactive electrolyte. It is found that double-layer characteristics of the Cd–Ga electrode differ from those of a Ga electrode both in nonaqueous solutions and in water. The lyophilic nature of the Cd–Ga electrode, relative to methanol and propylene carbonate, is shown to approach that of the In–Ga electrode. In the absence of a metal–solvent chemisorption interaction, the difference between reciprocal metallic capacitances for Cd–Ga and Hg electrodes is independent of the solvent nature. The chemisorption interaction between the solvents and Cd–Ga, Ga, and In–Ga electrodes increases with the solvents' donor number.     

Three metal-organic polymers assembled from Cd(II)–fluconazole: Syntheses,crystal structures,and characterization

Three new complexes [Cd(Hflu)₂(NO₃)](NO₃) 1, [Cd(H₂O)(Hflu)₂(Hmalo)](NO₃)?2(H₂O) 2, and [Cd(H₂O)(Hflu)₂(Hfum)](NO₃)?2(H₂O) 3 (Hflu = [2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol], H2fum = fumaric acid, H₂malo = malonate acid) are synthesized by a solution diffusion method and characterized by single crystal X-ray diffraction methods, elemental analyses, IR spectroscopy as well as thermal analyses. In compound 1, Cd(II) cations are bridged by fluconazole ligands to form 2D Cd?Hflu layers, and these layers are further connected by C–H???F hydrogen bonds to form a complicated 3D structure with the topology of (4?6?8)(4?64?84?10)(6?3). Compounds 2 and 3 are isostructural, and in them the Cd(II) cations are bridged by fluconazole ligands to form a 2D network, which is connected by C–H???O hydrogen bonds to form a complicated 3D (3,4)-connected framework with the topology of (4?8²)(4?8⁵).