Evaluation of triphenylene-based MOF ultrathin films for lithium batteries.

Metal-organic frameworks (MOFs) are attractive candidates to meet the requirement of next-generation batteries, as functional materials with a high surface area, well-defined metal centers, and organic linkers through coordination bonds. Due to their great tunability, MOFs have been investigated as electrodes or electrolytes in lithium batteries and more recently as protective layers in anode-less batteries. Here, we synthesize a Ni3(HHTP)2 MOF directly at the air-liquid interface of a Langmuir trough and grow the electrode on a conductive substrate by the transference process. The characterization during Langmuir film formation shows that the addition of crystallization time during the compression process enhances the formation of 2D crystalline domains, as observed by in situ grazing-incidence X-ray diffraction. Next, the transferred Ni3(HHTP)2 ultrathin films were studied as working electrodes in Li batteries in a half-cell configuration and compared with bare copper. The results show that the Ni3(HHTP)2 film protects the Cu collector from oxidation, and the negative charge accumulates in the organic ligand during the lithiation process while NiII oxidizes to NiIII, unlike other triphenylene-based MOFs with CuII or CoII metal nodes. The galvanostatic plating-stripping cycles of the batteries show that the inclusion of the crystallization time improves the coulombic efficiency, especially significantly in the first cycles when the SEI is formed. This work shows the Langmuir technique as a useful tool to test MOF based materials for batteries with the advantages of using a low amount of raw materials and without the need to introduce additives (binder and electron conductor) in the electrodes. The electrochemical study of this type of electrode allows a first screening to synthesize electrodes based on MOFs and can be a tool for the preparation of protective coatings under optimized conditions.

Solar Energy Storage Using a Cu2 O-TiO2 Photocathode in a Lithium Battery.

A Cu2 O-TiO2 photoelectrode is pr+oposed for simultaneous solar light energy harvesting and storing of electrochemical energy in an adapted lithium coin cell. The p-type Cu2 O semiconductor layer is the light harvester component of the photoelectrode and the TiO2 film performs as the capacitive layer. The rationale of the energy scheme shows that the photocharges generated in the Cu2 O semiconductor induce lithiation/delithiation processes in the TiO2 film as a function of the applied bias voltage and light power. A photorechargeable lithium button cell drilled on one side recharges with visible white light in ≈9 h in open circuit. It provides an energy density of ≈150 mAh g-1 at 0.1 C discharge current in dark, and the overall efficiency is 0.29%. This work draws a new approach for the photoelectrode role to advance in monolithic rechargeable batteries.

New approaches to the lithiation kinetics in reaction-limited battery electrodes through electrochemical impedance spectroscopy.

Electrochemical impedance spectroscopy is a widely employed technique probing kinetic limitations in the charging of battery electrodes. Hindrance mechanisms locate at the interfaces between the active material and the electrolyte, and in the bulk of the reacting compound. Rate-limiting mechanisms are viewed as resistive circuit elements and can be extracted using standard impedance analyzers. Classical impedance models consider charge transport, mainly ion diffusion as slower carrier, as the principal kinetic limitation impeding full electrode charging. This is indeed the case for many technologically relevant battery compounds. In other instances, instead of being diffusion-limited, electrodes may undergo charging limitation caused by the kinetics of the reduction reaction itself. Specific impedance models for reaction-limited mechanisms are summarized here and proved for relevant electrode compounds, in particular for conversion or alloying electrodes in which Li+ intake produces a full rearrangement of the lattice structure with significant atomic displacement.

Nanoscale Heterogeneity of Multilayered Si Anodes with Embedded Nanoparticle Scaffolds for Li-Ion Batteries.

A new approach on the synthesis of Si anodes for Li-ion batteries is reported, combining advantages of both nanoparticulated and continuous Si films. A multilayered configuration prototype is proposed, comprising amorphous Si arranged in nanostructured, mechanically heterogeneous films, interspersed with Ta nanoparticle scaffolds. Particular structural features such as increased surface roughness, nanogranularity, and porosity are dictated by the nanoparticle scaffolds, boosting the lithiation process due to fast Li diffusion and low electrode polarization. Consequently, a remarkable charge/discharge speed is reached with the proposed anode, in the order of minutes (1200 mAh g-1 at 10 C). Moreover, nanomechanical heterogeneity self-limits the capacity at intermediate charge/discharge rates; as a consequence, exceptional cycleability is observed at 0.5 C, with 100% retention over 200 cycles with 700 mAh g-1. Higher capacity can be obtained when the first cycles are performed at 0.2 C, due to the formation of microislands, which facilitate the swelling of the active Si. This study indicates a method to tune the mechanical, morphological, and electrochemical properties of Si electrodes via engineering nanoparticle scaffolds, paving the way for a novel design of nanostructured Si electrodes for high-performance energy storage devices.

Direct Hydrogen Evolution from Saline Water Reduction at Neutral pH using Organic Photocathodes.

Here, we have developed an organic photocathode for water reduction to H2 , delivering more than 1 mA cm-2 at 0 V versus RHE and above 3 mA cm-2 at -0.5 V versus RHE with moderate stability under neutral pH conditions. The initial competitive reduction of water to H2 and ZnO to metallic Zn is responsible for the dynamic behaviour of both photocurrent and Faradaic efficiency of the device, which reaches 100 % Faradaic efficiency after 90 min operation. In any case, outstanding stable H2 flow of approximately 2 µmol h-1 is measured over 1 h at 0 V versus RHE and at neutral pH, after equilibrium between the Zn2+ /Zn0 concentration in the AZO film is reached. This achievement opens new avenues for the development of allsolution-processed organic photoelectrochemical cells for the solar generation of H2 from sea water.

Modulating the interaction between gold and TiO2 nanowires for enhanced solar driven photoelectrocatalytic hydrogen generation.

The interaction strength of Au nanoparticles with pristine and nitrogen doped TiO2 nanowire surfaces was analysed using density functional theory and their significance in enhancing the solar driven photoelectrocatalytic properties was elucidated. In this article, we prepared 4-dimethylaminopyridine capped Au nanoparticle decorated TiO2 nanowire systems. The density functional theory calculations show {101} facets of TiO2 as the preferred phase for dimethylaminopyridine-Au nanoparticles anchoring with a binding energy of -8.282 kcal mol(-1). Besides, the interaction strength of Au nanoparticles was enhanced nearly four-fold (-35.559 kcal mol(-1)) at {101} facets via nitrogen doping, which indeed amplified the Au nanoparticle density on nitrided TiO2. The Au coated nitrogen doped TiO2 (N-TiO2-Au) hybrid electrodes show higher absorbance owing to the light scattering effect of Au nanoparticles. In addition, N-TiO2-Au hybrid electrodes block the charge leakage from the electrode to the electrolyte and thus reduce the charge recombination at the electrode/electrolyte interface. Despite the beneficial band narrowing effect of nitrogen in TiO2 on the electrochemical and visible light activity in N-TiO2-Au hybrid electrodes, it results in low photocurrent generation at higher Au NP loading (3.4 × 10(-7) M) due to light blocking the N-TiO2 surface. Strikingly, even with a ten-fold lower Au NP loading (0.34 × 10(-7) M), the synergistic effects of nitrogen doping and Au NPs on the N-TiO2-Au hybrid system yield high photocurrent compared to TiO2 and TiO2-Au electrodes. As a result, the N-TiO2-Au electrode produces nearly 270 µmol h(-1) cm(-2) hydrogen, which is nearly two-fold higher than the pristine TiO2 counterpart. The implications of these findings for the design of efficient hybrid photoelectrocatalytic electrodes are discussed.

Germanium coating boosts lithium uptake in Si nanotube battery anodes.

Si nanotubes for reversible alloying reaction with lithium are able to accommodate large volume changes and offer improved cycle retention and reliable response when incorporated into battery anodes. However, Si nanotube electrodes exhibit poor rate capability because of their inherently low electron conductivity and Li ion diffusivity. Si/Ge double-layered nanotube electrodes show promise to improve structural stability and electrochemical kinetics, as compared to homogeneous Si nanotube arrays. The mechanism explaining the enhancement in the rate capabilities is revealed here by means of electrochemical impedance methods. The Ge shell efficiently provides electrons to the active materials, which increase the semiconductor conductivity thereby assisting Li(+) ion incorporation. The charge transfer resistance which accounts for the interfacial Li(+) ion intake from the electrolyte is reduced by two orders of magnitude, indicating the key role of the Ge layer as an electron supplier. Other resistive processes hindering the electrode charge-discharge process are observed to show comparable values for Si and Si/Ge array electrodes.

Air-water interfacial behavior of linear-dendritic block copolymers containing PEG and azobenzene chromophores.

Fabrication of Langmuir films at the air-water interface of four linear-dendritic block copolymers (LDBCs) is described. The LDBCs are composed of a linear hydrophilic chain of poly(ethylene glycol) (PEG) and the first four generations of hydrophobic aliphatic polyester dendrons functionalized at the periphery with cyanoazobenzene chromophores. Langmuir films of the LDBCs, coded as PEG-AZOn (n indicates the number of cyanoazobenzene units at the periphery of the dendritic block), have been characterized by a combination of surface pressure versus area per molecule isotherms, UV-vis reflection spectroscopy and Brewster angle microscopy. The observed PEG-AZOn Langmuir film behavior depends strongly on the hydrophilic/hydrophobic ratio. A typical transition, related to PEG chains desorption from the air-water interface into the water subphase is observed for all the LDBCs, except for PEG-AZO16. In addition, PEG-AZO2 and PEG-AZO4 show a second transition whose nature has been studied in detail. Azobenzene chromophore interactions have been shown to be relevant in the organization of PEG-AZOn (n=4, 8 and 16) Langmuir films. Moreover, for PEG-AZO16 the orientation of the azobenzene units has been determined, revealing the formation of a well organized structure of azobenzene moieties at the air-water interface.

Supramolecular architecture in Langmuir and Langmuir-Blodgett films incorporating a chiral azobenzene.

This article describes the synthesis and fabrication of Langmuir and Langmuir-Blodgett (LB) films incorporating a chiral azobenzene derivative, namely, ( S)-4- sec-butyloxy-4'-[5''-(methyloxycarbonyl)pentyl-1''-oxy]azobenzene, abbreviated as AZO-C4(S). Appropriate conditions for the fabrication of monolayers of AZO-C4(S) at the air-water interface have been established, and the resulting Langmuir films have been characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and UV-vis reflection spectroscopy. The results indicate the formation of an ordered trilayer at the air-water interface with UV-vis reflection spectroscopy showing a new supramolecular architecture for multilayered films as well as the formation of J aggregates. Films were transferred onto solid substrates, with AFM revealing well-ordered multilayered films without 3D defects. Infrared and UV-vis absorption spectroscopy indicate that the supramolecular architecture may be favored by the formation of H bonds between acid groups in neighboring layers and pi-pi intermolecular interactions. Circular dichroism spectra reveal chiro-optical activity in multilayered LB films.

Structural characterization and properties of an azopolymer arranged in Langmuir and Langmuir-Blodgett films.

The fabrication of Langmuir and Langmuir-Blodgett (LB) films of an acid-azopolymer (PAzCOOH) is reported. Several techniques were used in their characterization: surface pressure (pi) and surface potential (DeltaV) isotherms, UV-vis reflection spectroscopy, and Brewster angle microscopy (BAM) for the Langmuir films and contact angle measurements, UV-vis, fluorescence, IR and Raman spectroscopy and scanning electronic microscopy (SEM) for the LB films. Our study reveals that lateral chains of the polymer situate preferentially onto the water surface with the acid group in contact with the water, where aggregates are scarcely formed. Therefore, the lateral chains of PAzCOOH can be treated as individual monomers to determine structural properties of the fabricated Langmuir and LB films. Monomeric treatment has been used to interpret UV-vis reflection spectroscopy, and a monomer model has been performed to represent lateral chains using density functional theory at B3LYP 6-31G(d,p) level of theory to assign the observed vibrational spectra.

Spectroscopic characterization and Langmuir-Blodgett films of a novel azopolymer material.

Spectroscopic characterization and fabrication of Langmuir and Langmuir-Blodgett (LB) films of an azopolymer-pyridine (PAzPy) are reported. UV-visible absorption and fluorescence spectra, Fourier transform infrared (FTIR) spectra, and Raman spectra were recorded. The vibrational assignment of the observed spectra is supported by a complete geometry optimization, followed by vibrational frequency and intensity computations of both the trans and cis forms of the monomer (AzPy) using density functional theory at the B3LYP 6-31G(d,p) level of theory. Langmuir monolayers of the polymer (PAzPy) were formed at the water-air interface, and LB films of high quality were formed onto solid substrates. The polymer LB films were investigated by surface-enhanced Raman scattering.

Mixed Langmuir and Langmuir-Blodgett films of a proton sponge and a fatty acid: influence of the subphase nature on the interactions between the two components.

The H+ acceptor activity of a proton sponge, namely, diphenyl bis(octadecylamino)phosphonium bromide, has been studied at the air-liquid interface using several subphases. Mixed Langmuir and Langmuir-Blodgett (LB) films containing the proton sponge and a fatty acid (behenic acid) in the whole composition range have been prepared. Surface pressure versus area per molecule isotherms were recorded and excess Gibbs energies of mixing calculated. The existence of strong interactions between the proton sponge and the fatty acid is observed when the subphase is either pure water or a NaOH aqueous solution. A stoichiometric 1:1 reaction between both molecules takes place at the air-water interface. This reaction has an efficiency close to 100% at high surface pressures, provided the majority anion present in the subphase is OH-. However, when the majority anion is another one, this complex is hardly formed. From the experimental results, we conclude that the acid-base reaction is highly dependent on the protonation state of the proton sponge at the air-liquid interface that is a function of the present counterion in the subphase. The floating films were also transferred onto solid substrates and characterized by means of IR spectroscopy, atomic force microscopy (AFM), and X-ray diffraction to investigate in more detail the complex formation. The interactions between the complex (when formed) and the excess component have been studied in terms of the subphase nature. It was found that the complex is immiscible with the proton sponge, yielding films made of different domains. Nevertheless, the complex is miscible with the fatty acid when the subphase used is an alkaline solution, presumably due to electrostatic interactions between the carboxylate group of the acid and the complex.

Pure and mixed films of a nitrostilbene derivative at the air-water interface, Langmuir-Blodgett multilayer fabrication, and optical characterization.

This paper reports the preparation and characterization of pure Langmuir and Langmuir-Blodgett (LB) films of a stilbene derivative containing two alkyl chains, namely 4-dioctadecylamino-4'-nitrostilbene. Mixed films incorporating docosanoic acid and the stilbene derivative are also studied. Brewster angle microscopy (BAM) analysis has revealed the existence of randomly oriented three-dimensional (3D) aggregates, spontaneously formed immediately after the spreading process of the stilbene derivative onto the water surface. These 3D aggregates coexist with a Langmuir film that shows the typical gas, liquid, and solid-like phases in the surface pressure and surface potential vs area per molecule isotherms, indicative of an average preferential orientation of the stilbene compound at the air-water interface, and a gradual molecular arrangement into a defined structure upon compression. A blue shift of 55 nm of the reflection spectrum of the Langmuir film with respect to the spectrum of a chloroform solution of the nitrostilbene indicates that two-dimensional (2D) H-aggregates are formed at the air-water interface. The monolayers are transferred undisturbed onto solid substrates with atomic force microscopy (AFM) revealing that the one layer LB films are constituted by a monolayer of the stilbene derivative together with some 3D aggregates. When the nitrostilbene compound is blended with docosanoic acid, the 3D aggregation is avoided in the Langmuir and Langmuir-Blodgett films, but does not limit the formation of 2D H-aggregates, desirable for second-order nonlinear optical response in the blue domain. The AFM images of the mixed LB films show that they are formed by a docosanoic acid monolayer and, on the top of it, a bilayer of the stilbene derivative.

Interfacial properties of a synthetic peptide derived from hepatitis G virus E2 protein: interaction with lipid monolayers.

A useful approach to get information about the potential fusogenic ability of virus synthetic peptides is the study of its interfacial properties and subsequent study in mono- and bilayers. In this work, we have characterized by means of physicochemical tools (i.e. compression isotherms and surface activity) the sequence 267-284, LLGTEVSEVLGGAGLTGG, derived from the E2 structural protein of HGV/GBV-C. The adsorption of the peptide at the air/water interface was monitored by following the increase in surface pressure as a function of time at two different pH values: 5 and 7. Parameters such as surface excess or molecular area were calculated from the equation of Gibbs. The peptide showed a tendency to migrate to the surface of a saline-buffered solution. It formed stable monolayers at the air/water interface giving a compression isotherm with a shape consistent with that of some alpha-helical peptide conformations. Brewster angle microscopy (BAM) showed that through compression the peptide formed multilayers. The studies with lipid monolayers (DPMC, DMPC/DMPG, and DMPC/DMTAP) showed that the peptide interacts with all the lipids assayed producing a marked disrupting effect upon them. In these effects electrostatic interactions seem to have some participation.

Proton sponge and fatty acid interactions at the air-water interface. Thermodynamic, spectroscopic, and microscopic study.

Mixed Langmuir and Langmuir-Blodgett (LB) films of a proton sponge, namely, diphenyl bis(octadecylamino)phosphonium bromide, and a fatty acid, docosanoic acid, with different molar ratios have been fabricated. Surface pressure versus area per molecule isotherms were registered, and the excess areas and excess Gibbs energy of mixing were calculated. Strong interactions between the proton sponge and the fatty acid take place at the air-water interface. The existence of a stoichiometric 1:1 acid-base reaction between the two components forming a complex on the water surface at high surface pressures has been demonstrated. Furthermore, the reaction had an efficiency close to 100% at the air-water interface; meanwhile, it hardly takes place in organic solvents such as chloroform or even a mixture of chloroform and dimethyl sulfoxide. The floating films were transferred to solid supports and characterized by means of several techniques including IR spectroscopy, X-ray diffraction, and atomic force microscopy, revealing the presence of highly ordered alkyl chains and a constant architecture along the different layers as well as the presence of different domains in the LB films, except those having a 1:1 proton sponge-fatty acid ratio that are homogeneous. Such domains have been interpreted as the presence of two different phases, the 1:1 complex plus the excess component in the mixture.