Synthesis and fractionated crystallization of organic-inorganic hybrid composite materials from an amphiphilic polyethylene-block-poly (ethylene oxide) diblock copolymer

Mesostructurally ordered inorganic–organic hybrid composite materials were successfully synthesized by utilizing a low-molecular-weight amphiphilic polyethylene-block-poly(ethylene oxide) (PE–PEO) diblock copolymer as the directing agent. The hybrid composites were formed via the sol–gel reaction of inorganic precursor tetraethoxysilane (TEOS) in an acidic ethanol/water solution with various amounts of PE–PEO. In these composite materials, the hydrophobic PE block of the PE–PEO copolymer forms separate microphase on the nanoscales within the rigid matrix of silica network. The crystallization of the PE block is strictly restricted within the microphase by the rigid silica matrix and takes place through homogeneous nucleation under the nanoscale confinement environment.

Novel Na+ Ion diffusion mechanism in mixed organic-inorganic ionic liquid electrolyte leading to high Na+ transference number and stable, high rate electrochemical cycling of sodium cells

Ambient temperature sodium batteries hold the promise of a new generation of high energy density, low-cost energy storage technologies. Particularly challenging in sodium electrochemistry is achieving high stability at high charge/discharge rates. We report here mixtures of inorganic/organic cation fluorosulfonamide (FSI) ionic liquids that exhibit unexpectedly high Na+ transference numbers due to a structural diffusion mechanism not previously observed in this type of electrolyte. The electrolyte can therefore support high current density cycling of sodium. We investigate the effect of NaFSI salt concentration in methylpropylpyrrolidinium (C3mpyr) FSI ionic liquid (IL) on the reversible plating and dissolution of sodium metal, both on a copper electrode and in a symmetric Na/Na metal cell. NaFSI is highly soluble in the IL allowing the preparation of mixtures that contain very high Na contents, greater than 3.2 mol/kg (50 mol %) at room temperature. Despite the fact that overall ion diffusivity decreases substantially with increasing alkali salt concentration, we have found that these high Na+ content electrolytes can support higher current densities (1 mA/cm2) and greater stability upon continued cycling. EIS measurements indicate that the interfacial impedance is decreased in the high concentration systems, which provides for a particularly low-resistance solid-electrolyte interphase (SEI), resulting in faster charge transfer at the interface. Na+ transference numbers determined by the Bruce-Vincent method increased substantially with increasing NaFSI content, approaching >0.3 at the saturation concentration limit which may explain the improved performance. NMR spectroscopy, PFG diffusion measurements, and molecular dynamics simulations reveal a changeover to a facile structural diffusion mechanism for sodium ion transport at high concentrations in these electrolytes.

Visible transparent, UV-blocking polymer nanocomposite films containing nano-sized organic-LDH (Layered Double Hydroxide) hybrid

A nano-sized Mg2Al layered double hydroxide (LDH) was used for encapsulating an organic UV absorber, 2-hydroxy-4- methoxybenzeophenone-5-sulfonic acid (HMBS), to produce HMBS@LDH hybrid nano-platelets. Upon dispersing this organic-inorganic hybrid LDH into ethylene-vinyl alcohol copolymer (EVOH) for film casting, a thin polymer
nanocomposite film that is UV opaque but highly transparent to visible light (higher than 90%) was formed. Thermogravimetry (TG) analysis confirmed that the intercalation of HMBS into LDH considerably increased the thermal stability of HMBS. Such an improvement was attributed to the strong guest-host interaction between the HMBS anions and the LDH layers. Also, the nanocomposite films were flexible and had good mechanical properties.

Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

In situ synthesis of natural rubber latex-supported gold nanoparticles for flexible SERS substrates

Natural rubber latex (NRL) from Hevea brasiliensis was used as a matrix to synthesize gold nanoparticles (AuNPs), leading to an organic-inorganic hybrid latex of NRL-supported AuNPs (AuNPs@NRL). The in situ and environmentally friendly preparation of AuNPs in an NRL matrix was developed by thermal treatment without using any other reducing agents or stabilizers because natural rubber particles and non-rubber components present in serum can serve as supporters for the synthesized AuNPs. As a result, the nanosized and well-dispersed AuNPs not only are decorated on the surface of natural rubber particles, but also can be found in the serum of NRL. The size of the AuNPs presented in NRL matrix can be controlled by adjusting the concentration of NRL. Furthermore, the flexible surface-enhanced Raman scattering (SERS) substrates made from the AuNPs@NRL through vacuum filtration presented good enhancement of the Raman probe molecule of 4-mercaptopyridine and outstanding SERS reproducibility. The capability of synthesizing the bio-supported nanohybrid latex provides a novel green and simple approach for the fabrication of flexible and effective SERS substrates.

Efficient management of drinking water distribution systems through the application of water quality modeling

The quality of drinking water generally degrades when it is delivered through a distribution system due to the decay of disinfectant, which subsequently allows the re-growth of microorganisms in the distribution system. A model that describes the changes that occur in the water quality in distribution system is needed to determine whether to enhance the treatment processes or to improve the distribution system so that microbiological criteria are met. This paper describes how chlorine decay kinetics are modeled and the model output is used in finding the elements that are contributing to the consumption of chlorine at the treatment plant other than the water itself; this allows better control of chlorine dosing at the treatment plant, which in tum will reduce the formation of disinfectant by-products. In addition, the model will accurately predict the decay due to the organic/inorganic and nitrogenous compounds that are remaining in the water at any point in the distribution system, which will indicate the status of the distribution system with respect to its chlorine consumption. Further, if re-chlorination is introduced in the distribution system downstream of the treatment plant, the model will predict the chlorine decay due to the slow reacting organic and nitrogenous compounds accurately.

Rapid water quality characterization for chlorine demand and THM formation in drinking waters

The quality of drinking water generally deteriorates when it is delivered through a distribution system due to the decay of disinfectant, which subsequently allows the re-growth of microorganisms in the distribution system in addition to the formation of trihalomethane (THM). Therefore, a model which describes the changes that occur in the water quality in the distribution system is needed to determine whether to enhance the treatment processes or to improve the distribution system so that microbiological criteria are met. In this paper the chlorine decay kinetics and THM formation in treated water is modeled considering the reaction of chlorine with fast and slow reacting organic and nitrogenous compounds which are present in that water. The treated water was also passed through three types of resins to fractionate very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), hydrophilic charged (CHA) and hydrophilic neutral (NEU) compounds which are present in the water. Chlorine decay tests were conducted on the effluents emerging from the resins to evaluate the chlorine demand and THM formation potential of those organic fractions. The model shows that the CHA presented in the waters has a very high THM formation potential (around 62% of the THM produced). VHA, NEU and CHA contributed to chlorine demand in the water.

[Al4(OH)2(OCH3)4(H2N-bdc)3]⋅x H2O: A 12-connected porous metal–organic framework with an unprecedented aluminum-containing brick

A new stable aluminum aminoterephthalate system contains octameric building blocks that are connected by organic linkers to form a 12-connected net (see picture). The structure adopts a cubic centered packing motive in which octameric units replace individual atoms, thus forming distorted octahedral (red sphere) and tetrahedral cages (green spheres) with effective accessible diameters of 1 and 0.45 nm, respectively

Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology, interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.

Qualitative spectroscopic characterization of the matrix-silane coupling agent interface across metal fibre reinforced ion exchange resin composite membranes

The characterization of novel metal reinforced electro-dialysis ion exchange membranes, for water desalination, by attenuated total reflectance Fourier transform infrared spectroscopy mapping is presented in this paper. The surface of the porous stainless steel fibre meshes was treated in order to enhance the amount of surface oxide groups and increase the material hydrophilicity. Then, the metal membranes were functionalized through a sol-gel reaction with silane coupling agents to enhance the affinity with the ion exchange resins and avoid premature metal oxidation due to redox reactions at the metal-polymer interface. Polished cross sections of the composite membranes embedded into an epoxy resin revealed interfaces between metallic frameworks and the silane layer at the interface with the ion exchange material. The morphology of the metal-polymer interface was investigated with scanning electron microscopy and Fourier transform infrared micro-spectroscopy. Fourier transform infrared mapping of the interfaces was performed using the attenuated total reflectance mode on the polished cross-sections at the Australian Synchrotron. The nature of the interface between the metal framework and the ion exchange resin was shown to be homogeneous and the coating thickness was found to be around 1 μm determined by Fourier transform infrared micro-spectroscopy mapping. The impact of the coating on the properties of the membranes and their potential for water desalination by electro-dialysis are also discussed.

Capsular polypyrrole hollow nanofibers: an efficient recyclable adsorbent for hexavalent chromium removal

Capsular polypyrrole hollow nanofibers (PPy-HNFs) were fabricated via in situ polymerization of pyrrole on an organic-inorganic template, followed by acid etching. Their application in removing hexavalent chromium (Cr(vi)) from aqueous solution was then investigated. The morphologies of the capsular PPy-HNFs were studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which showed that the PPy-HNFs had a capsular structure in the walls of hollow nanofibers. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) data confirmed the adsorption of Cr on capsular PPy-HNFs. The adsorption capacity increased with reduced pH of the initial solution and the adsorption process can be described using the pseudo-second-order model. These capsular PPy-HNFs showed a high Cr(vi) adsorption capacity up to 839.3 mg g-1. This adsorption capacity was largely retained even after five adsorption/desorption cycles. Electrostatic attraction between Cr and PPy-HNFs was studied using a proposed adsorption mechanism. The capsular PPy-HNFs formed a flexible membrane, which allowed easy handling during application. This study has demonstrated the possibilities of using this capsular PPy-HNF membrane for heavy metal removal from aqueous solution.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate ligand with bivalent metals: a new 2D-layered phenylphosphinate zinc(II) complex

By reaction of Zn(CH₃COO)₂ with p,p′-diphenylmethylenediphosphinic acid in water a new inorganic–organic polymeric hybrid of formula [Zn(CH₂(P(Ph)O₂)₂)] has been synthesized and completely characterized. The X-ray analysis established that the structure consists of 2D-layered polymeric array, the 2D-sheets being built up through strong covalent linkages between the zinc metal and the oxygen donors of the phenylphosphinate ligand. The 2D-layers, which are featuring a mesh-net fashion, present voids of various dimensionality, up to 24-membered rings. The organic parts of the hybrid ligand, namely the phenyl rings, are shielding the inorganic skeleton of the layers, preventing the propagation of the polymer in the third dimension. No water molecules are present in the lattice, both of coordination and crystallization. Crystal data are: monoclinic, P2₁Ic, a=11.840(2), b=9.646(9), c=12.516(5) Å, β=95.03(2), V=1423.9(15) ų, Z=4. The solid material has been characterized by ³¹P MAS NMR spectroscopy and thermogravimetric analysis.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. synthesis, characterization and XRPD structures of [Sn(pcp)] and [Cu(pcp)]

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp = CH₂(PhPO₂)₂^2-, have been synthesized and structurally chracterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H₂pcp) in water with SnCl₂·2H₂O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H₂pcp acid and Cu(O₂CMe)₂·H₂O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2₁Ic, a = 11.2851(1), b = 15.4495(6), c = 8.6830(1) Å, ^β= 107.546(1)°, V = 1443.44(9) Å, Z = 4. Crystal data for [Cu(pcp)]: triclinic, space group P, a = 10.7126(4), b = 13.0719(4), c = 4.9272(3) Å, α= 92.067(5), β= 95.902(7), γ= 87.847(4)°, V = 685.47(7), Z = 2. The tin compound has been characterized by ¹¹⁹Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

Abnormal transmittance of refractive-index-modified ZnO/organic hybrid films

The refractive index of ZnO/organic nanocomposite films was modified in the range from 1.44 to 1.55, while maintaining high visible transparency. The transparency of the nanocomposite films showed an abnormal behaviour as a function of the loading level of inorganic particles, because it did not decrease according to the Beer-Lambert law, but rather saturated to a near-constant value at high particle loading levels above 8 vol.-%. On the other hand, the refractive index of the film showed good agreement with the Bruggemann model, linearly increased as particle concentration increased. This result indicates the possibility of fabricating highly transparent nanocomposite films with controlled refractive indices.

Abnormally high optical transmittance of refractive-index modified ZnO / organic hybrid films

Hybrid films consisting of ZnO nanoparticles and organic matrices were fabricated at particle concentration levels of up to 60 wt%. The correlation between the refractive index and optical transmittance in the visible light region was investigated. The refractive index of the hybrid films was modified in a continuous manner in the range from 1.44 to 1.55. The refractive index increased linearly as a function of particle concentration. On the other hand, optical transmittance showed little change above the particle volume fraction of 0.08.