Guennadi Evmenenko

Preparation and characterization of graphene oxide paper.

Free-standing paper-like or foil-like materials are an integral part of our technological society. Their uses include protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, electronic or optoelectronic components, and molecular storage. Inorganic ‘paper-like’ materials based on nanoscale components such as exfoliated vermiculite or mica platelets have been intensively studied and commercialized as protective coatings, high-temperature binders, dielectric barriers and gas-impermeable membranes4,5. Carbon-based flexible graphite foils composed of stacked platelets of expanded graphite have long been used in packing and gasketing applications because of their chemical resistivity against most media, superior sealability over a wide temperature range, and impermeability to fluids. The discovery of carbon nanotubes brought about bucky paper, which displays excellent mechanical and electrical properties that make it potentially suitable for fuel cell and structural composite applications. Here we report the preparation and characterization of graphene oxide paper, a free-standing carbon-based membrane material made by flow-directed assembly of individual graphene oxide sheets. This new material outperforms many other paper-like materials in stiffness and strength. Its combination of macroscopic flexibility and stiffness is a result of a unique interlocking-tile arrangement of the nanoscale graphene oxide sheets.

Self-Propagating Assembly of a Molecular-Based Multilayer

Accelerated growth of a molecular-based material that is an active participant in its continuing self-propagated assembly has been demonstrated. This nonlinear growth process involves diffusion of palladium into a network consisting of metal-based chromophores linked via palladium.

Selective monitoring of parts per million levels of CO by covalently immobilized metal complexes on glass

Optical detection of parts-per-million (ppm) levels of CO by a structurally well-defined monolayer consisting of bimetallic rhodium complexes on glass substrates has been demonstrated.

Stepwise Assembly of Coordination-Based Metal−Organic Networks

Metal-organic networks (MONs) were created by a stepwise solution deposition approach from vinylpyridine-based building blocks and PdCl(2). The combined experimental and computational study demonstrates the formation of saturated, structurally organized systems on solid supports. The rigid nature and geometry of the components are well-suited to form honeycomb and parallelogram structures, as predicted by a computational study. Detailed structural information of the new MONs was obtained by optical (UV/vis) spectroscopy, ellipsometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and synchrotron X-ray reflectivity (XRR). Notably, the XPS elemental composition indicates the formation of a palladium coordination-based network.

Molecular Assembly of a 3D-Ordered Multilayer

Combining strong metal-ligand coordination and pi-pi interactions affords a 3D-ordered molecular-based multilayer. The organization of the assembly is apparent from the optical properties and X-ray reflectivity.

Triarylamine siloxane anode functionalization/hole injection layers in high efficiency/high luminance small-molecule green- and blue-emitting organic light-emitting diodes

High efficiency/high luminance small-molecule organic light-emitting diodes (OLEDs) are fabricated by combining thin, covalently bound triarylamine hole injection/adhesion interlayers with hole- and exciton-blocking/electron transport interlayers in tris(8-hydroxyquinolato)aluminum(III) (Alq) and tetrakis(2-methyl-8-hydroxyquinolinato)borate (BQ4−)-based OLEDs. Green-emitting OLEDs with maximum luminance ∼85000cd∕m2, power and forward external quantum efficiencies as high as 15.2lm∕W and 4.4±0.5%, respectively, and turn-on voltages ∼4.5V are achieved in devices of the structure, ITO∕N,N′-diphenyl-N,N′-bis(p-trichlorosilylpropylphenyl)(1,1′-biphenyl)-4,4′-diamine (TPD-Si2)/1,4-bis(1-naphthylphenylamino)biphenyl (NPB)/Alq doped with N,N′-di(3-heptyl)quinacridone (DIQA)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)∕Li∕AgMg. Also, bright and efficient blue-emitting OLEDs with turn-on voltages ∼5.0V, maximum luminance ∼30000cd∕m2, and ∼5.0lm∕W and 1.6±0.2% power and external forward quantum efficiencies,...

Observation of surface layering in a nonmetallic liquid.

Oscillatory density profiles (layers) have previously been observed at the free surfaces of liquid metals but not in other isotropic liquids. We have used x-ray reflectivity to study a molecular liquid, tetrakis(2-ethylhexoxy)silane. When cooled to T/Tc approximately 0.25 (well above the freezing point for this liquid), density oscillations appear at the surface. Lateral order within the layers is liquidlike. Our results confirm theoretical predictions that a surface-layered state will appear even in dielectric liquids at sufficiently low temperatures, if not preempted by freezing.

Assembly of Surface-Confined Homochiral Helicates: Chiral Discrimination of DOPA and Unidirectional Charge Transfer

Surface-confined double-helical polymers are generated by dynamic covalent assembly with preservation of chirality, metal coordination environment, and oxidation state of the precursor complexes. This one-step procedure involves both in solution and solution-to-surface assembly and resulted in chiral interfaces where pairs of ligands are wrapped around arrays of metal ions. In-plane XRD experiments revealed the formation of a highly ordered structure along the substrate surface. The chirality of the surfaces is expressed by the selective recognition of 3,4-dihydroxyphenylalanine (DOPA). The CD measurements show a response of the Δ-polymer-modified quartz substrates toward D-DOPA, whereas no change was observed after treatment with L-DOPA. These coordination-based interfaces assembled on metal-oxide substrates in combination with a redox-probe, [Os(bpy)3](PF6)2, in solution can resemble the behavior of a rectifier.

Characterization of Transparent Conducting Oxide Surfaces Using Self-Assembled Electroactive Monolayers

The electronic properties of various transparent conducting oxide (TCO) surfaces are probed electrochemically via self-assembled monolayers (SAMs). A novel graftable probe molecule having a tethered trichlorosilyl group and a redox-active ferrocenyl functionality (Fc(CH2) 4SiCl3) is synthesized for this purpose. This molecule can be self-assembled via covalent bonds to form monolayers on various TCO surfaces. On as-received ITO, saturation coverage of 6.6 x 10(-10) mol/cm2 by a close-packed monolayer and an electron-transfer rate of 6.65 s(-1) is achieved after 9 h of chemisorption, as determined by cyclic voltammetry (CV) and synchrotron X-ray reflectivity. With this molecular probe, it is found that O2 plasma-treated ITO has a significantly greater electroactive coverage of 7.9 x 10 (-10) mol/cm2 than as-received ITO. CV studies of this redox SAM on five different TCO surfaces reveal that MOCVD-derived CdO exhibits the greatest electroactive coverage (8.1 x 10(-10) mol/cm2) and MOCVD-derived ZITO (ZnIn2.0Sn1.5O) exhibits the highest electron transfer rate (7.12 s(-1)).

Specular x-ray reflectivity study of ordering in self-assembled organic and hybrid organic–inorganic electro-optic multilayer films

Specular x-ray reflectivity has been used to probe the microstructures of siloxane-based self-assembled electro-optic superlattices composed of high-hyperpolarizable organic chromophore arrays intercalated with Ga and In oxide sheets. The film thickness increases linearly as a function of the number of layers, underscoring the high structural regularity and efficiency of the synthetic approach. Relatively dense metal oxide structures are detected in these systems. The x-ray reflectivity data also indicate that the dependence of the relative surface roughness on the number of layers is nearly identical for self-assembled organic and organic–inorganic hybrid film structures.