Apostolos Enotiadis

Graphene-Based Nafion Nanocomposite Membranes: Enhanced Proton Transport and Water Retention by Novel Organo-functionalized Graphene Oxide Nanosheets

Novel nanostructured organo-modified layered materials based on graphene oxide carrying various hydrophilic functional groups (-NH(2), -OH, -SO(3)H) are prepared and tested as nanofillers for the creation of innovative graphene-based Nafion nanocomposites. The hybrid membranes are characterized by a combination of analytical techniques, which show that highly homogeneous exfoliated nanocomposites are created. The pulsed field gradient NMR technique is used to measure the water self-diffusion coefficients. Remarkable behavior at temperatures up to 140 °C is observed for some composite membranes, thereby verifying the exceptional water retention property of these materials. Dynamic mechanical analysis shows that hybrid membranes are much stiffer and can withstand higher temperatures than pure Nafion.

Large‐Yield Preparation of High‐Electronic‐Quality Graphene by a Langmuir–Schaefer Approach

Graphene was discovered less than five years ago and proved the existence of pure two-dimensional systems, thought physically impossible in the past. It appeared very quickly that this exceptionalmaterial showedmany outstanding properties. Since electrons and holes in graphene have potential for high carrier mobilities, this novel material has become an exciting new playground for physicists; properties such as the halfinteger quantum Hall effect at room temperature, spin transport, high elasticity, electromechanicalmodulation, and ferromagnetism all contribute to the fame of graphene. Since the first experiments conducted five years ago on micromechanically cleaved graphite (the renowned but lowyield adhesive tape method), the growing appeal of graphene’s properties has focused much of the research attention towards the conception of a reliable method for large-scale production. Recent advances using chemical vapor deposition and successful transfer of the prepared films to arbitrary substrates brought impressive results in terms of crystalline quality of the layers and consequent electrical and mechanical properties. Notwithstanding these results, truly controllable singleor multilayer large-scale deposition is still a pressing issue and a method for depositing high-quality graphene at variable coverage on an arbitrary surface is not yet available. Moreover, for practical application or simply for fundamental research purposes, good adhesion of graphene to the substrate is of great importance.

Effective improvement of water-retention in nanocomposite membranes using novel organo-modified clays as fillers for high temperature PEMFCs.

Toward an enhanced water-retention of polymer electrolyte membranes at high temperatures, novel organo-modified clays were prepared and tested as fillers for the creation of hybrid Nafion nanocomposites. Two smectite clays (Laponite and montmorillonite), with different structural and physical parameters, were loaded with various cationic organic molecules bearing several hydrophilic functional groups (-NH(2), -OH, -SO(3)H) and incorporated in Nafion by solution intercalation. The resulted hybrid membranes were characterized by a combination of powder X-ray diffraction, FTIR spectroscopy, and thermal analysis (DTA/TGA) showing that highly homogeneous exfoliated nanocomposites were created where the individual organoclay layers are uniformly dispersed in the continuous polymeric matrix. In this paper, water-transport properties were investigated by NMR spectroscopy, including pulsed-field-gradient spin-echo diffusion and spectral measurements conducted under variable temperature. Organo-montmorillonite nanofillers demonstrate a considerable effect on the Nafion polymer in terms both of water absorption/retention and water mobility with a remarkable behavior in the region of high temperatures (100-130 °C), denoting that the surface modifications of this clay with acid organic molecules significantly improve the performance of the final composite membrane. (1)H NMR spectral analysis allowed a general description of the water distribution in the system and an estimation of the number of water molecules involved in the hydration shell of the sulfonic groups as well as that absorbed on the organoclay particles.

Effects of acetate on cation exchange capacity of a Zn-containing montmorillonite: physicochemical significance and metal uptake.

Fundamental properties such as cation exchange capacity (CEC), permanent charge, pH(PZC), and metal uptake of a Zn-containing montmorillonite are modified, in a predictable manner, by a mild chemical treatment using acetate. Acetate treatment allows a controllable increase of the CEC of montmorillonite up to 180 mequiv/100 g. The CEC of the clay is increasing for decreasing Zn content, with a slope of Delta[Zn]/Delta[CEC] approximately -2. X-ray powder diffraction analysis shows that the lamellar structure of the clay remains unaltered by the acetate treatment, while XPS substantiates the removal of Zn. H(+) uptake data show that the intrinsic protonation pK values and concentration of the variable charge sites ( identical with SOH) are not modified by the acetate treatment. In contrast, the concentration of the permanent charge sites ( identical with X(-)) increased linearly with Zn removal by acetate, leading to a significant H(+) and Cd(2+) uptake enhancement. A physical model is suggested where acetate removes Zn ions strongly bound in the clay, and this in turn modulates the permanent charge and the CEC of the clay.

Physicochemical study of amino-functionalized organosilicon cubes intercalated in montmorillonite clay: H-binding and metal uptake

Two organic-modified montmorillonite clays were prepared by embedding organosilanes bearing different chelating amino-functional groups [Apteos] (3-amino-propyltriethoxysilane), and [Edaptmos] (3-(2-aminoethylamino)propyltrimethoxysilane), in the interlayer space of a Zenith montmorillonite. XRD and FTIR spectroscopic data show that the amino organosilanes are intercalated into the interlamelar space forming cube-like structures bearing one polymanino tail at each cube apex. The intercalated cubes cause an increase of the interlayer spacing of the clay sheets by 6.6 A in [Zenith-Apteos] and by 7.1 A in [Zenith-Edaptmos]. The H-binding properties of the intercalated polyamino organosilanes were studied by potentiometric titration. The Cu-, Cd-, and Pb-binding capacity of [Zenith-Apteos] and [Zenith-Edaptmos] were evaluated in aqueous solution as a function of the pH. Both [Zenith-Apteos] and [Zenith-Edaptmos] showed improvement vs Zenith for metal binding in the order Cu > Pb > Cd. [Zenith-Edaptmos] showed the most important results vs Zenith. Theoretical analysis of the pH edge, achieved by a surface complexation model, shows that (a) the amino-functionalized cube-like structures constitute high affinity metal-binding sites; and (b) the metal ions are bound in a monodendate mode with the amino group of the cube, thus resulting in a maximization of metal-binding efficiency.

Nanocomposites of Polystyrene-b-Poly(isoprene)-b-Polystyrene Triblock Copolymer with Clay–Carbon Nanotube Hybrid Nanoadditives

Polystyrene-b-polyisoprene-b-polystyrene (PS-b-PI-b-PS), a widely used linear triblock copolymer of the glassy-rubbery-glassy type, was prepared in this study by anionic polymerization and was further used for the development of novel polymer nanocomposite materials. Hybrid nanoadditives were prepared by the catalytic chemical vapor deposition (CCVD) method through which carbon nanotubes were grown on the surface of smectite clay nanolayers. Side-wall chemical organo-functionalization of the nanotubes was performed in order to enhance the chemical compatibilization of the clay-CNT hybrid nanoadditives with the hydrophobic triblock copolymer. The hybrid clay-CNT nanoadditives were incorporated in the copolymer matrix by a simple solution-precipitation method at two nanoadditive to polymer loadings (one low, i.e., 1 wt %, and one high, i.e., 5 wt %). The resulting nanocomposites were characterized by a combination of techniques and compared with more classical nanocomposites prepared using organo-modified clays as nanoadditives. FT-IR and Raman spectroscopies verified the presence of the hybrid nanoadditives in the final nanocomposites, while X-ray diffraction and transmission electron microscopy proved the formation of fully exfoliated structures. Viscometry measurements were further used to show the successful incorporation and homogeneous dispersion of the hybrid nanoadditives in the polymer mass. The so prepared nanocomposites exhibited enhanced mechanical properties compared to the pristine polymer and the nanocomposites prepared by conventional organo-clays. Both tensile stress and strain at break were improved probably due to better interfacial adhesion of the clay-CNT hybrid of the flexible rubbery PI middle blocks of the triblock copolymer matrix.

Enhanced hydrogen and methane storage of hybrid mesoporous organosilicas

In this study, hybrid mesoporous organosilicas (HMOs) were synthesized by using tetraethyl orthosilicate (TEOS) as the silica source and 1,4-bis(triethoxysilyl)benzene (BTB) in various ratios of BTB to TEOS. The two extreme cases of 0 and 100 mol% BTB were compared with the partial addition of BTB (25 mol%) and the partial absence of TEOS (75 mol% BTB). The synthesized mesoporous materials were characterized by means of powder X-ray diffraction (PXD), scanning electron microscopy (SEM) and helium pycnometry for the determination of skeletal density. The Brunauer–Emmett–Teller (BET) method was used for the determination of the specific surface area (SSA) and non-local density functional theory (NLDFT) calculations were employed for the determination of the pore size distribution (PSD). The hydrogen and methane sorption properties were investigated using a Sieverts apparatus under isothermal sorption equilibrium conditions at cryogenic and close to ambient temperatures, respectively. For hydrogen, the combination of phenyl rings with pores at the micro/mesopore border resulted in an increase in sorption capacity. The simultaneous presence of two different precursors increased the surface inhomogeneity, which led to a wider distribution of adsorption sites close to the micro/mesopore border, which favored the hydrogen sorption properties. The presence of the phenyl rings doubled the number of methane molecules that the material surface could accommodate. The partial substitution of TEOS by BTB (25 mol%) gave the same density of adsorbed methane as the non-hybrid material, which consisted of 100% BTB. The materials exhibited excellent reversibility and sorption stability upon aging. Their sorption performance was evaluated using the Toth model and was correlated with their structural characteristics. The fraction of micropores among the total number of pores was quantitatively correlated with the maximum storage capacity and the adsorbate–adsorbent interaction strength. Finally, for a low coverage of methane the enthalpy of adsorption was calculated by the Clausius–Clapeyron equation.

A facile approach to fabricating organosilica layered material with sulfonic groups as an efficient filler for polymer electrolyte nanocomposites

We report the one-pot synthesis of a siliceous layered material bearing sulfonic group functionalities through the simple sol–gel process of 3-(trihydroxy silyl) propyl-1-propane-sulfonic acid. This easy-fabricated layered nanomaterial can possess a high number of organo-sulfonic groups, rendering it an attractive, multifunctional filler for polymer electrolyte nanocomposites for energy applications such as lithium batteries and fuel cells. X-ray diffraction and photoelectron spectroscopy confirm the layered structure and the presence of sulfonic groups, respectively. In the present work, the silica nanomaterial was tested as a nanofiller for the development of innovative Nafion nanocomposite membranes for proton exchange membrane fuel cells (PEMFCs). Pristine functional material and nanocomposites were characterized by a combination of analytical techniques. The dynamic mechanical analysis showed that composite membranes are much stiffer and can withstand higher temperatures than recast Nafion membrane. Proton transport properties and water management were investigated by 1H pulsed field gradient (PFG) NMR spectroscopy, by measuring the water self-diffusion coefficients in a wide temperature range (20–130 °C). The data showed a remarkable high water retention capacity of composite membranes and high proton diffusion in the temperature region above 100 °C, representing a significant advance in the current state-of-the-art technology of PEMFCs.