Adsorption mode of cinchonidine on Cu(111) surface

The adsorption mode of cinchonidine on Cu(111) was directly obtained by in situ STM. The molecules were found to adsorb on the substrate surface and form a long-range ordered adlayer with (4 x 4) symmetry. While the quinoline rings lie parallel to Cu(111), the chiral quinuclidine moiety extends out of the surface. The enantioselectivity of catalysts may relate to this special adsorption conformation of cinchonidine on the surface.     

Adsorption of Cu(II) in aqueous solution by sodium dodecyl benzene sulfonate-modified montmorillonite

The pristine montmorillonite (P-Mt) was modified with sodium dodecyl benzene sulfonate (SDBS) to form SDBS montmorillonite (SDBS-Mt) for the purpose of enhancing the removal performance of Cu(II) from aqueous solution. The materials were characterized by means of XRD, SEM-EDS, BET, and FTIR to analyze the surface morphology and structure. SDBS-Mt displayed a higher adsorption capacity than P-Mt. The adsorption kinetic model and the adsorption isotherm model are depicted by the pseudo-second-order kinetic equation and the Langmuir equation, respectively. The adsorption of Cu(II) on SDBS-Mt is a spontaneous and endothermic process. The order of influence of coexisting cations on the adsorption of Cu(II) is Ni(II) > Co(II) > Zn(II). In addition, the adsorbent has great regeneration performance after five cycles of regeneration. The main mechanisms of Cu(II) adsorption by SDBS-Mt may include electrostatic attraction, ion exchange, and complexation of sulfonate groups. In brief, SDBS-Mt may be a promising, simple, and low-cost adsorbent for the treatment of Cu(II) in aqueoussolutions.     

一氧化氮在Cu_3Pt(111)表面的吸附行为

运用密度泛函理论中广义梯度近似(GGA)的PW91方法,结合周期性平板模型,探讨了NO分子在Cu3Pt(111)表面上不同吸附位的吸附行为.结果表明:NO分子以N端朝下方式吸附在top-Pt以及hcp1和fcc2位(分别为表面Cu2Pt和Cu3簇)的吸附模式最稳定,吸附能分别为101.8、124.5和118.1kJ·mol-1.对于hcp1和fcc2位的吸附,NO中的N原子分别与底物的Cu2Pt和Cu3簇成键.吸附前后的电荷布居、态密度和振动频率的分析结果表明,净电子从底物合金表面转移到NO,N—O键伸长,频率发生红移.合金Cu3Pt和纯贵金属Pt对NO的吸附性质相似.     

Adsorption of Pb(II) and Cu(II) from aqueous solution on magnetic porous ferrospinel MnFe2O4

The adsorption of Pb(II) and Cu(II) from aqueous solution on magnetic porous ferrospinel MnFe(2)O(4) prepared by a sol-gel process was investigated. Single batch experiment was employed to test pH effect, sorption kinetics, and isotherm. The interaction mechanism and the regeneration were also explored. The results showed that Pb(II) and Cu(II) removal was strongly pH-dependent with an optimum pH value of 6.0, and the equilibrium time was 3.0 h. The adsorption process could be described by a pseudo-second-order model, and the initial sorption rates were 526.3 and 2631.5 μmol g(-1)min(-1) for Pb(II) and Cu(II) ions, respectively. The equilibrium data were corresponded well with Langmuir isotherm, and the maximum adsorption capacities were 333.3 and 952.4 μmol g(-1) for Pb(II) and Cu(II) ions, respectively. The adsorbed Pb(II) and Cu(II) ions were in the form of the complex with oxygen in carboxyl and hydroxyl groups binding on the surface of magnetic porous MnFe(2)O(4). The sorbent could be reused for five times with high removal efficiency.     

Thermodynamics of copper(II) dicarboxylate coordination in aqueous solution

Summary The association of H⁺ and Cu²⁺ with malonate, maleate, succinate and phthalate ions has been investigated both potentiometrically and calorimetrically at 25° and I = 0.1 mol dm^–3 (NaClO₄).The structures of the complexes existing in aqueous solution are proposed on the basis of thermodynamic data.     

Homochiral conglomerates and racemic crystals in two dimensions: tartaric acid on Cu(110)

Two-dimensional lattice structures formed by racemic tartaric acid on a single crystalline Cu(110) surface have been studied and compared with the enantiopure lattices. At low coverage, the doubly deprotonated bitartrate species is separated into two-dimensional conglomerates showing opposite enantiomorphism. At higher coverage, however, a singly deprotonated monotartrate species forms a heterochiral, racemic crystal lattice. While the enantioseparated bitartrate system undergoes decomposition at the same temperature as the enantiopure system, the racemic monotartrate lattice has a lower thermal stability than the enantiopure lattice of identical periodicity and surface density. At monolayer saturation coverage, the pure enantiomers form a denser lattice than the racemate. This is in contrast to the three-dimensional tartaric acid crystals, where the racemate crystallizes in a lattice of higher density, which is also more thermally stable than the enantiopure tartaric acid crystals.     

N.m.r. studies of complexes of molybdenum(VI) with tartaric acid in aqueous solution

Summary Complex formation between molybdate ions and R,R-(+)-tartaric acid has been studied in aqueous solution, and to a limited extent in DMSO, over a range of concentrations and pH at 298K, using¹H and¹³C n.m.r. techniques. Only four main species are evident; two, which have Mo: L ratios of 11 and 12, are bondedvia a carboxylic oxygen atom and an adjacent hydroxyl oxygen atom. The 12 species forms stereospecifically. The other two main species contain bridging tartaric acid molecules, and a 22 species, also formed stereo-specifically in solution, have been isolated and characterised in the solid state. A limited number of experiments with racemic acid and meso-tartaric acid indicate that only a few species are formed in these systems and with a good deal of stereospecificity also.     

An effective Cu(II) quenching fluorescence sensor in aqueous solution and 1D chain coordination polymer framework

In the article, a novel fluorescent probe for the copper cation based on fluorescence quenching mechanism was designed. It exhibited high selectivity for Cu(II) over other common metal ions in aqueous media. Furthermore the coordination between Cu(II) and the organic molecule sensor fabricated an interesting 1D chain coordination polymer framework.     

Adsorption and charge transfer dynamics of bi-isonicotinic acid on Au(111)

The interaction of bi-isonicotinic acid (4,4(')-dicarboxy-2,2(')-bipyridine) with the Au(111) surface has been investigated using electron spectroscopic techniques. Near edge x-ray absorption fine structure (NEXAFS) spectra show that monolayers of the molecule lie flat to the surface and also reveal that the monolayer is sensitive to the preparation conditions employed. Core level x-ray photoelectron spectroscopy (XPS) shows that the adsorbed molecule does not undergo deprotonation upon adsorption. The "core-hole clock" implementation of resonant photoemission has been used to probe the coupling between molecule and substrate. This technique has revealed the possibility of ultrafast backtransfer from the substrate into the molecule upon resonant excitation of a N 1s core level electron. This is supported by a NEXAFS and XPS investigation of energy level alignments in the system.     

Adsorption geometry and core excitation spectra of three phenylpropene isomers on Cu(111)

Theoretical C 1s near edge x-ray absorption fine structure (NEXAFS) spectra for the C(9)H(10) isomers trans-methylstyrene, alpha-methylstyrene, and allylbenzene in gas phase and adsorbed at Cu(111) surfaces have been obtained from density functional theory calculations where adsorbate geometries were determined by corresponding total energy optimizations. The three species show characteristic differences in widths and peak shapes of the lowest C 1s-->pi(*) transitions which are explained by different coupling of the pi-electron system of the C(6) ring with that of the side chain in the molecules as well as by the existence of nonequivalent carbon centers. The adsorbed molecules bind only weakly with the substrate which makes the use of theoretical NEXAFS spectra of the oriented free molecules meaningful for an interpretation of experimental angle-resolved NEXAFS spectra of the adsorbate systems obtained in this work. However, a detailed quantitative account of relative peak intensities requires theoretical angle-resolved NEXAFS spectra of the complete adsorbate systems which have been evaluated within the surface cluster approach. The comparison with experiment yields almost perfect agreement and confirms the reliability of the calculated equilibrium geometries of the adsorbates. This can help to explain observed differences in the catalytic epoxidation of the three molecules on Cu(111) based on purely geometric considerations.     

Investigation of a Cu(II)-poly(gamma-glutamic acid) complex in aqueous solution and its insulin-mimetic activity

The complexation between cupric ions (Cu(II)) and poly(gamma-glutamic acid) (gamma-PGA) in aqueous solutions (pH 3-11) has been studied by UV-visible absorption and electron spin resonance (ESR) techniques. Formation of the Cu(II)-gamma-PGA complex is confirmed by the observation of the blue shift of the absorption band in the visible region, anisotropic line shapes in the ESR spectrum at room temperature, and a computer simulation of the visible absorption spectrum of the complex. The structure of the Cu(II)-gamma-PGA complex, depending on the pH, has been determined. The in vitro insulin-mimetic activity of the Cu(II)-gamma-PGA complex is examined by determining both inhibition of free fatty acid release and glucose uptake in isolated rat adipocytes treated with epinephrine, in which the concentration of the Cu(II)-gamma-PGA complex for 50% inhibition of free fatty acid release is very similar to that of CuSO4. However, it is significantly lower than that of a previously reported insulin-mimetic bis(3-hydroxypicolinato)copper(II), [Cu(3hpic)2], complex.     

CO和H2分子在Cu(111)面的吸附和溶剂化效应

采用广义梯度近似(GGA)密度泛函理论(DFT)的PW91方法结合周期性模型, 在DNP基组下, 利用Dmol3模块研究了CO和H2在真空和液体石蜡环境下在Cu(111)表面上不同位置的吸附. 计算结果表明, 溶剂化效应对H2和CO的吸附结构参数和吸附能的影响非常显著. 在液体石蜡环境下, H2平行吸附在Cu(111)表面是解离吸附, 而CO 和H2在两种环境下的垂直吸附都是非解离吸附. 相比真空环境吸附, 在液体石蜡环境中, Cu(111)吸附CO时, 溶剂化效应能够提高CO吸附的稳定性, 同时有利于CO的活化. 在真空中, H2只能以垂直方式或接近垂直方式吸附在Cu(111)表面. 当Cu(111)顶位垂直吸附H2, 相比真空环境吸附, 溶剂化效应能够提高H2吸附的稳定性, 但对H2的活化没有明显影响. Cu(111)表面的桥位或三重穴位(hcp和fcc)垂直吸附H2时, 溶剂化效应能明显提高H2的活化程度, 但降低H2的吸附稳定性; 在液体石蜡中, 当H2平行Cu(111)表面吸附时, 溶剂化效应使H—H键断裂, 一个H原子吸附在fcc位, 另一个吸附在hcp位.     

On Cu(Hg)/Cu(II) equilibria and reactions in aqueous sulphate solution

Combined thermodynamic and kinetic studies have revealed amalgam properties, solution activities, and diffusion data besides charge-transfer parameters and exchange rates for either step of the Cu(Hg)/Cu(II) electrode in aqueous solutions of xM CuSO₄+(0.5?x) M MgSO₄+H₂SO₄ (to pH about 2.5) at 25°C. The studies allow separation of mean ionic activities into convenient single-ion ones. The kinetic results demonstrate the consecutive two-step mechanism involved. Comparison is made to the solid Cu/Cu(II) electrode, and double-layer effects are discussed.     

Metal-organic coordination interactions in Fe-terephthalic acid networks on Cu(100)

Metal-organic coordination interactions are prime candidates for the formation of self-assembled, nanometer-scale periodic networks with room-temperature structural stability. We present X-ray photoelectron spectroscopy measurements of such networks at the Cu(100) surface which provide clear evidence for genuine metal-organic coordination. This is evident as binding energy shifts in the O 1s and Fe 3p photoelectron peaks, corresponding to O and Fe atoms involved in the coordination. Our results provide the first clear evidence for charge-transfer coordination in metal-organic networks at surfaces and demonstrate a well-defined oxidation state for the coordinated Fe ions.     

Swelling and dissolution mechanism of lyocell fiber in aqueous alkaline solution containing ferric tartaric acid complex

Swelling properties of lyocell fibers in FeTNa (ferric tartaric acid complex) solutions were studied. Concentrations of Fe and free NaOH in FeTNa were varied, while the ratio between FeCl₃.6H₂O: tartaric acid was kept constant as 1:3.28. The concentration of Fe ion varied from 0.15 to 0.55 M. The free NaOH concentration in FeTNa solutions was chosen as 0.4; 0.8; 1.25; 2.5 and 5 M. Fiber diameter measurements following 2 min of swelling and swelling rate of lyocell fiber up to 60 min were studied. Depending on concentration of Fe and free NaOH in FeTNa solutions and fiber swelling time; swelling, dissolution, disintegration or dramatic swelling were observed. 0.4 and 5 M free NaOH containing FeTNa solutions could only swell the fiber but could not dissolve it. 2.5 M free NaOH containing FeTNa solutions dissolved the fiber in a few minutes. FeTNa solutions containing free NaOH concentration from 0.8 to 1.25 M resulted in either dissolution or limited swelling depending on Fe concentration.     

Adsorption of Cu(II) from aqueous solution by anatase mesoporous TiO2 nanofibers prepared via electrospinning

Anatase mesoporous titanium nanofibers (m-TiO(2) NFs) have been synthesized from calcination of the as-spun TiO(2)/polyvinyl pyrrolidone (PVP)/pluronic123 (P123) composite nanofibers at 450 °C in air for 3h. The structures and the physicochemical properties of m-TiO(2) NFs are characterized by scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption isotherm analysis, and determination point of zero charge, respectively. An investigation of Cu(II) adsorption onto m-TiO(2) NFs has been studied in this research. The pH effect, adsorption kinetics, and adsorption isotherms are examined in batch experiments. Experimental data were analyzed using pseudo-first order and pseudo-second order kinetic models. It was found that adsorption kinetics were the best fitting by a pseudo-second order kinetic model. The optimum pH for Cu(II) adsorption was found to be 6.0. The equilibrium data were analyzed by the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, which revealed that the Freundlich isotherm is the best-fit isotherm for the adsorption of Cu(II). Compared to the TiO(2) NFs (regular anatase titanium nanofibers) in the same experimental conditions to elucidate the role of the mesoporous structure of m-TiO(2) NFs, experimental results showed that the m-TiO(2) NFs had a better adsorption capacity for Cu(II) due to its higher surface area.     

Structure and Conformation of Individual Molecules upon Adsorption of a Mixture of Benzoporphyrins on Ag(111), Cu(111), and Cu(110) Surfaces

The front cover artwork is provided by the groups of Prof. Dr. Hans-Peter Steinrück and Prof. Dr. Norbert Jux at the Friedrich-Alexander-Universität (FAU) Erlangen-Nürnberg. The image shows a mixture of six 2H-tetrakis-(3, 5-di-tert-butyl-phenyl)(x)benzoporphyrins (2H-diTTBP(x)BPs, x = 0, 1, 2-cis, 2-trans, 3, or 4) molecules forming a porous square structure on Ag(111) as observed in scanning tunneling microscopy (STM) at room temperature. Read the full text of the Research Article at 10.1002/cphc.202300355 .     

Electron-induced isomerisation of dichlorobenzene on Cu(111) and Ag(111)

The constitutional isomerisation of single dichlorobenzene molecules adsorbed on the surfaces of Ag(111) and Cu(111) between their meta- and para-isomers is induced and investigated by means of a low temperature scanning tunneling microscope. On both substrates similar isomerisation thresholds are found indicating that the excitation mechanism of this reaction does not depend significantly on the underlying substrate. The isomerisation threshold voltage of (170 +/- 7) meV most likely corresponds to excitation of a C-C stretch mode whose gas-phase energies we calculated ab initio to lie at 174 and 172 meV for meta- and para-isomers respectively. Though the reaction is found to be localized on the submolecular scale, it depends heavily on the second substituent both in terms of excitation energy and reaction outcome.     

Adsorption of a single molecule of a diarylethene photochromic dye on Cu(111)

On the route to single (large) molecule unimolecular chemistry, the adsorption of a photochromic dithienylethene dye on Cu(111) at a submonolayer level has been studied by Ultra High Vacuum-Scanning Tunneling Microscopy at Low Temperature. This technique has shown that the observed adsorbed molecule's shape is compatible with an helical conformation but has also revealed a surrounding electronic corrugation due to the perturbed surface states. Careful examination of the standing wave pattern indicated that only a part of the molecule is indeed interacting with the metallic substrate. Geometric considerations were used to infer that the bridging ethene moiety could be responsible for the electronic scattering. Scanning Tunneling Spectroscopy has shown a substantial amount of charge transfer from the surface to the adsorbate. The hypothesis that this precise double bond is a reactive locus toward charge transfer processes is confirmed by the electrochemical results: this double bond is indeed reduced upon coulometric reduction on glassy carbon. Furthermore, the use of a copper cathode strongly facilitates the reduction since a +0.6 V shift was recorded.