Electrochemically reduced single-layer MoS₂ nanosheets: characterization, properties, and sensing applications

The electrochemical study of single‐layer, 2D MoS₂ nanosheets reveals a reduction peak in the cyclic voltammetry in NaCl aqueous solution. The electrochemically reduced MoS₂ (rMoS₂) shows good conductivity and fast electron transfer rate in the [Fe(CN)₆]^3‐/4? and [Ru(NH₃)₆]^2+/3+ redox systems. The obtained rMoS₂ can be used for glucose detection. In addition, it can selectively detect dopamine in the presence of ascorbic acid and uric acid. This novel material, rMoS₂, is believed to be a good electrode material for electrochemical sensing applications.     

Deposition of α-SiΜο12Ο40-[Ru(bipyridine)(terpyridine)Cl] multilayer film on single wall carbon nanotube modified glassy carbon electrode: Improvement of the electrochemical properties and chemical stability

A simple procedure was developed for the preparation of glassy carbon electrodes modified with single wall carbon nanotubes (SWCNTs) and multilayers of SiΜο₁₂Ο₄₀⁴⁻-[Ru(bpy)(tpy)Cl]⁺(byp; bipyridine, tpy; terpyridine). Layer-by-layer deposition technique was used for the multilayer formation of SiΜο₁₂Ο₄₀⁴⁻-[Ru(bpy)(tpy)Cl]⁺ onto SWCNTs films. Based on the strong electrostatic attraction of oppositely charged species a Ru-complex/poly oxometalate hybrid film strongly and irreversibly adsorbed on the glassy carbon electrode modified with single walled carbon nanotubes. The multilayer assembly exhibited good stability and excellent electrochemical reversibility for both redox systems in the pH range1-7. It was found that up to fifteen monolayers could be deposited onto a carbon nanotube film with well defined redox behavior. The modified electrode shows excellent electrocatalytic activity towards sulfite oxidation. Due to synergistic effect between SWCNTs and oppositely charged species the repeated alternate adsorption of anions and cations by this simple dipping method leads to molecular sandwiches with interesting redox activity and remarkable stability.     

Electrochemical and morphological studies of an electroactive material derived from 3-hydroxyphenylacetic acid: a new matrix for oligonucleotide hybridization

This paper describes the formation of polymeric films derived from 3-hydroxyphenylacetic acid electropolymerized onto graphite electrodes through cyclic voltammetry. We observed the formation of an electroactive material over the electrode surface. The modified electrode showed significant blocking behavior to electron transfer reaction of the pair redox ferricyanide/ferrocyanide, indicating repulsion electrostatic with the negatively charged carboxylate groups of the polymer. The quasi-reversible behavior to Ru(NH₃)₆Cl₂ suggests electrostatic attraction, facilitating the charge transfer. The modified electrode was studied through electrochemical quartz crystal microbalance, electrochemical impedance spectroscopy, and atomic force microscopy. These analyses indicate modification of the graphite electrode. Surface analysis by AFM showed that the morphology of the modified electrode surface presents globular form, randomly distributed, and formed by lower globules with diameter near 100 nm. Immobilization and hybridization of oligonucleotide onto the modified electrode were successfully carried out by using both direct electrochemical oxidation of nitrogenated bases and the redox electroactive indicator methylene blue.     

Direct imaging by atomic force microscopy of surface-localized self-assembled monolayers on a cuprate superconductor and surface X-ray scattering analysis of analogous monolayers on the surface of water

A self-assembled monolayer of CF₃(CF₂)₃(CH₂)₁₁NH₂ atop the (001) surface of the high-temperature superconductor YBa₂Cu₃O_7-x was imaged by atomic force microscopy (AFM). The AFM images provide direct 2D-structural evidence for the epitaxial 5.5 Å square √2 × √2R45° unit cell previously predicted for alkyl amines by molecular modeling [J.E. Ritchie, C.A. Wells, J.-P. Zhou, J. Zhao, J.T. McDevitt, C.R. Ankrum, L. Jean, D.R. Kanis, J. Am. Chem. Soc. 120 (1998) 2733]. Additionally, the 3D structure of an analogous Langmuir monolayer of CF₃(CF₂)₉(CH₂)₁₁NH₂ on water was studied by grazing-incidence X-ray diffraction and specular X-ray reflectivity. Structural differences and similarities between the water-supported and superconductor-localized monolayers are discussed.     

Specific heat of para-hydrogen monolayers on graphite

The specific heat of para-hydrogen films has been measured from 1 to 20 K for areal densities between 0.01 and 0.055 atoms/Å ² of the partial monolayer adsorbed on grafoil. The results are compared with the specific heat of ⁴ He films at equivalent densities. It is argued that a nonideal gas regime and liquefaction are present in both systems and that solidification of thep-H ₂ films has been suppressed to below the temperature range of the experiment. Implications regarding 2D superfluidity in hydrogen monolayers are discussed briefly.     

Catalytic and antibacterial activities of green-synthesized silver nanoparticles on electrospun polystyrene nanofiber membranes using tea polyphenols

An efficient and environmentally friendly method has been developed to prepare Ag nanoparticles (AgNPs) coated tea polyphenols/polystyrene (Ag-TP/PS) nanofiber membrane, which combines electrospinning and in situ reduction of [Ag(NH₃)₂]⁺ using TP as the reductant and stabilizer. In this method, TP/Pluronic/PS nanofiber membranes are fabricated by electrospinning and then immersed in the aqueous solution of [Ag(NH₃)₂]⁺. While TP is being released from TP/Pluronic/PS nanofibers, the surface of TP/Pluronic/PS nanofibers could function as reactive sites for reduction of [Ag(NH₃)₂]⁺ without any extra reagents. XRD results indicate that AgNPs thus formed are in metallic form of Ag⁰. SEM images show that AgNPs can be densely and uniformly coated on the surface of TP/Pluronic/PS nanofibers. The as-prepared Ag-TP/PS nanofiber membranes exhibit excellent catalytic properties for the degradation of methylene blue. Furthermore, the effect of [Ag(NH₃)₂]⁺ concentration on the morphology and catalytic activity of the membrane is investigated. In addition, the antibacterial assays reveal that Ag-TP/PS nanofiber membrane possesses extraordinary antibacterial activity against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli microorganisms. The free-standing membrane is flexible and easy to handle, which is promising for potential applications in catalysis, antibacterial agents and water remediation fields.     

Self-quenching of a photo-excited ruthenium complex in component-controllable mixed Langmuir-Blodgett films

The miscibility and phase behavior of the mixed monolayer of Ru(dpphen)₃²⁺ (dpphen=4,7-diphenyl-1,10-phenanthroline) (abbreviated as Ru(II)), octadecyltrichlorosilane (OTS) and stearic acid (SA) at air/water interface had been investigated in detail. Two-dimensional density of Ru(II) could be easily adjusted by changing the mixing ratio of Ru(II)/SA/OTS. The mixed monolayer of Ru(II)/SA/OTS with different molar proportions had been deposited and characterized by low angle X-ray diffraction, UV-visible absorption spectra and photo-induced emission spectra. The possible structure of its resulting LB film was proposed based on the results of the π-A isotherms and low angle X-ray diffraction. Photo-induced electron transfer and self quenching of Ru(II) in mixed LB films had been investigated in detail.     

Direct synthesis of Zn-ZSM-5 with novel morphology

Zinc-containing ZSM-5 zeolite with novel morphology was firstly synthesized in a one-step route using [Zn(NH₃)₄]²⁺ aqueous solution as zinc resource and n-butylamine as template. The materials were characterized by XRD, SEM, diffuse reflectance UV–vis spectra, FTIR for pyridine adsorption. The results showed that the formation of this novel structure might be related to the introduction of [Zn(NH₃)₄]²⁺ aqueous solution and the zinc existent state in zeolite.     

Self-chemisorption of azurin on functionalized oxide surfaces for the implementation of biomolecular devices

In this work, we investigate the formation of redox protein Azurin (Az) monolayers on functionalized oxygen exposing surfaces. These metallo-proteins mediate electron transfer in the denitrifying chain of Pseudomonas bacteria and exhibit self-assembly properties, therefore they are good candidates for bio-electronic applications. Azurin monolayers are self-assembled onto silane functionalized surfaces and characterized by atomic force microscopy (AFM). We show also that a biomolecular field effect transistor (FET) in the solid state can be implemented by interconnecting an Azurin monolayer immobilized on SiO₂ with two gold nanoelectrodes. Transport experiments, carried out at room temperature and ambient pressure, show FET behavior with conduction modulated by the gate potential.     

E.s.r. and i.r. studies of ruthenium (III) hexaamine-exchanged zeolites

The chemistry of Ru(III) hexaamine complex imbedded in zeolite has been investigated by e.s.r., i.r., and other techniques. Zeolite-supported Ru(III)(NH₃)₆ exhibited e.s.r. signal characteristic for four d⁵ low-spin configuration species in an octahedral tetragonally distorted crystal field symmetry. Upon thermal activation, change from axial to orthorhombic symmetry occurred. I.r. analysis in the δNH₃ region also indicated that the symmetry of the NH₃ ligand coordination sphere was lowered upon thermal activation. Activation at temperature higher than 523 K resulted in the formation of RuO_x species. The results will be discussed in terms of rapid hydrolysis of the cationic Ru(III), with the subsequent formation of ruthenium red complexes that were decomposed into ruthenium oxide at higher temperature. The stability of Ru(III)(NH₃)₆ toward hydrolysis depended on the zeolite type used. Finally, we report that the dispersion of the Ru metal, formed upon H₂ reduction, was controlled by the state of the dispersion of the oxidized Ru.     

Synthesis and crystal structure of double Ln(III) malonates with Co(NH3) 6 3+ in the outer sphere

Double Ln(III) malonates of two different compositions crystallize from malonate solutions containing [Co(NH₃)₆]³⁺ ions. Lanthanides of the beginning of the series form compounds of the composition [Co(NH₃)₆][Ln(mal)₂]₃·6H₂O (I) (Ln = La, Ce, Pr, Nd; mal = C₃H₂O^2?), and those of the end of the series form compounds of the composition [Co(NH₃)₆]₂[Ln₃(mal)₇(Hmal)(H₂O)₄]·nH₂O (II) (Ln = Tb, Ho, Er, Tm). Structure I is based on trimeric anionic complexes [Ln₃(mal)₆]^3? linked with each other to form a branched 3D network with [Co(NH₃)₆]³⁺ cations and water molecules accommodated in large voids. The coordination mode of malonate ions in I with the coordination capacity equal to 5 was unknown previously for lanthanide malonate compounds. The Ln(1) atom has the maximum possible for malonate compounds coordination number (CN) 12, and the Ln(2) atom has CN 9. The structure of II consists of anionic chains [Ln₃(mal)₇(Hmal)(H₂O)₄] _n ^3? between which the [Co(NH₃)6]₃₊ cations and water molecules are arranged. One independent malonate ion in the structure is coordinated in the bidentate chelate fashion to the Ln(1) atom, and the other independent chelate-bridging ligand is coordinated in the bidentate fashion to the Ln(2) atom and in the monodentate fashion to the Ln(1) atom. As a result, tetrameric fragments linked in anionic chains are formed in the structure of II. The Ln(1) and Ln(2) atoms have CN 8.     

Kinetics of ion-exchange binding of redox metal cations to thiolate-DNA monolayers on gold

The ion-exchange kinetics of metal cation binding to and dissociation from thiolate-DNA monolayers on gold can be monitored by a simple electrochemical protocol. The apparent first-order rate constants were obtained by analyzing the time-dependent voltammetric behavior of the redox cation [Ru(NH3)6]3+. It was found that the binding kinetics is dominated by the structural nature of the film; i.e., the apparent first-order rate constant (kapp) decreases significantly upon increasing the surface density of DNA strands. Dissociation rate constants were obtained by transferring the incubated electrode into redox-free buffer solution. The kinetic data augment our fundamental understanding of metal ion-DNA interactions and are critical to ensure the accuracy and reliability of experimental DNA detection protocols.     

Growth kinetics and thermodynamic stability of octadecyltrichlorosilane self-assembled monolayer on Si (100) substrate

We have studied the growth kinetics and thermodynamic stability of octadecyltrichlorosilane (OTS) self-assembled monolayers on Si (100) substrate in order to understand its role in controlling the adhesion and surface hydrophobicity. Time-dependent contact angle measurements, using water as a function of OTS concentration, show rapid monolayer formation in the initial stage followed by a slow attainment of full coverage and the overall kinetics approximately follows the Langmuir adsorption isotherm. The adsorption rate constant (k_a = 150 M^− 1 s^− 1) is found to be significantly greater than the desorption rate constant (k_d = 0.156 s^− 1) while the Gibbs free energy (ΔG_ads) change amounts to − 4.2 kcal/mol suggesting thermodynamic stability of OTS monolayer on a silicon surface. Partial monolayer formation by a ‘uniform’ growth mechanism, even at low coverage, is revealed by atomic force microscopy (AFM) in conjunction with grazing angle FTIR spectroscopy. Analysis of the interfacial adhesion properties using Zisman plot suggests a critical surface tension (γ_c) of 20.7 dyn/cm for OTS monolayer on Si (100) surface.     

Elucidating the role of charge density on the growth of CaCO3 crystals underneath Calix[4]arene monolayers

The amphiphilic 5,11,17,23-tetrakis-(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(2-hydroxyethoxy)calix[4]arene (1) forms stable monolayers at the air–water interface. The growth of CaCO₃ crystals underneath monolayers of 1 is strongly inhibited, in contrast to the corresponding carboxylic acid derivative 5,11,17,23-tetrakis-(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(carboxymethoxy)calix[4]arene (2), the monolayers of which lead to growth of preferentially oriented calcite single crystals. The growth morphology of CaCO₃ crystals is correlated with the phase behaviour and surface potential of the monolayers. The investigations demonstrate that the average charge density is the dominant factor for heterogeneous nucleation of CaCO₃ crystals at the calixarene monolayer/solution interface.     

Topotactic redox reactions and ion exchange of layered MoO3 bronzes

Chemical or electrochemical reduction of MoO₃ in neutral aqueous electrolyte solutions results in the reversible topotactic formation of a new type of molybdenum oxide bronzes A⁺_x(H₂O)_y[MoO₃]^x?. The latter are built up by negatively charged [MoO₃]^x? layers with exchangeable hydrated cations in the interlayer space. Non-solvated cations are taken up between the MoO₃ sheets on cathodic reduction of the oxide in organic electrolyte solutions. Galvanostatic studies on the reduction of MoO₃ in aqueous acids reveal the strong influence of kinetics on hydrogen ion uptake. Earlier results of Glemser (2) on “genotypic” hydrogen bronzes of MoO₃ are confirmed. H_0.5MoO₃ was found to exhibit Brönsted acid character and to form a novel type of layer intercalation compounds L_xH_0.5MoO₃ with Lewis bases.     

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air–water interface

Phospholipid monomolecular films at the air–water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)–area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)–dipalmitoylphosphatidylcholine (DPPC) and DoTAP–dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π–A isotherm. Associative interactions were identified in DPPC–DoTAP mixtures compared to the pure components, while DPPG–DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC–DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X_DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC–DoTAP mixtures with increasing X_DoTAP. However, DPPG–DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.     

Magnetism of epitaxial Ru and Rh monolayers on graphite

Recently, Pfandzelter et al. (1995) reported the first observation of monolayer ferromagnetism of a 4d metal, namely in a Ru monolayer grown on graphite. Using the tight-binding linear-muffin-tin-orbital (TB-LMTO) method we have calculated the electronic and magnetic structure of epitaxial Ru and Rh monolayers on graphite with the experimentally determined atomic density. Monolayers of the other 4d elements were found to be non-magnetic already in the free-standing limit. The magnetic structure of the Ru and Rh monolayers is studied as a function of metal-graphite interlayer distance h. They become magnetic at h = 4.5 a.u. (Ru) and h = 4.8 a.u. (Rh) in a first-order transition. In the assumed p(2 × 2) super-structure, the moments on the “hollow” site atoms are up to four times bigger than those on the “on-top” site atoms. For h > 5.4 a.u. (Ru) and h > 5.1 a.u. (Rh) the site dependence vanishes and the moments of the free monolayers are approximately reached (1.9 μ_B and 1.2 μ_B, respectively).     

Silicon nitride layers of various n-content: Technology, properties and structure

Two series of amorphous silicon nitride layers (a-SiN_x:H) were formed with Radio Frequency Chemical Vapor Deposition method (13.56 MHz) from a NH₃/SiH₄ gas mixture: the first one on Si (001) and the second on glass. The deposition process was repeated at various [NH₃]/[SiH₄] ratios, while the other parameters (pressure, plasma generator power, substrate temperature, total gas flow, and time) were kept constant. It has been confirmed in optical measurements that the refractive indexes decrease for the layers obtained at increasing [NH₃]/[SiH₄] ratios. Simultaneously, the position of the band assigned to Si-H stretching vibrations (at about 2100 cm^− 1) shifts towards higher frequencies. The observed dependencies were applied in evaluation of nitrogen and hydrogen contents in the respective layers. It has been shown that when [NH₃]/[SiH₄] increases from 0 (no silane flow) to 0.2 then the a-SiN_x:H layers of x = [N]/[Si] increasing between 0 and nearly 1.4 may be obtained. The obtained layers have the refractive indexes higher than 2.1 and lower than 2.7 which make them good materials for antireflective coatings on crystalline and multicrystalline silicon solar cells.     

Cathodic reduction of layered transition metal chalcogenides

Layered binary transition metal chalcogenides MX₂ (M = transition metal, X=S, Se) may be reduced electrochemically in aqueous electrolyte solutions to give hydrated polyelectrolyte compounds (A_x)^x+ (H₂O)_y [MX₂]^x? (I). The latter consist of negatively charged layers [MX₂]^x? with hydrated cations A⁺ positioned between the metal chalcogenide sheets. The interlayer cations may be exchanged against other mono- or polyvalent inorganic or organic cations. Reductions may also be carried out in nonaqueous electrolyte solutions. Galvanostatic and potentiostatic measurements show clearly the reversibility of the electrode process and provide evidence for the occurrence of intermediate reaction steps.     

Faster Electron Injection and More Active Sites for Efficient Photocatalytic H2 Evolution in g‐C3N4/MoS2 Hybrid

Herein, the structural effect of MoS₂ as a cocatalyst of photocatalytic H₂ generation activity of g‐C₃N₄ under visible light irradiation is studied. By using single‐particle photoluminescence (PL) and femtosecond time‐resolved transient absorption spectroscopies, charge transfer kinetics between g‐C₃N₄ and two kinds of nanostructured MoS₂ (nanodot and monolayer) are systematically investigated. Single‐particle PL results show the emission of g‐C₃N₄ is quenched by MoS₂ nanodots more effectively than MoS₂ monolayers. Electron injection rate and efficiency of g‐C₃N₄/MoS₂‐nanodot hybrid are calculated to be 5.96 × 10⁹ s^?1 and 73.3%, respectively, from transient absorption spectral measurement, which are 4.8 times faster and 2.0 times higher than those of g‐C₃N₄/MoS₂‐monolayer hybrid. Stronger intimate junction between MoS₂ nanodots and g‐C₃N₄ is suggested to be responsible for faster and more efficient electron injection. In addition, more unsaturated terminal sulfur atoms can serve as the active site in MoS₂ nanodot compared with MoS₂ monolayer. Therefore, g‐C₃N₄/MoS₂ nanodot exhibits a 7.9 times higher photocatalytic activity for H₂ evolution (660 µmol g?¹ h^?1) than g‐C₃N₄/MoS₂ monolayer (83.8 µmol g^?1 h^?1). This work provides deep insight into charge transfer between g‐C₃N₄ and nanostructured MoS₂ cocatalysts, which can open a new avenue for more rationally designing MoS₂‐based catalysts for H₂ evolution.