Free-Standing Graphene Oxide and Carbon Nanotube Hybrid Papers with Enhanced Electrical and Mechanical Performance and Their Synergy in Polymer Laminates.

Hybrid nanomaterials fabricated by the heterogeneous integration of 1D (carbon nanotubes) and 2D (graphene oxide) nanomaterials showed synergy in electrical and mechanical properties. Here, we reported the infiltration of carboxylic functionalized single-walled carbon nanotubes (C-SWNT) into free-standing graphene oxide (GO) paper for better electrical and mechanical properties than native GO. The stacking arrangement of GO sheets and its alteration in the presence of C-SWNT were comprehensively explored through scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The C-SWNTs bridges between different GO sheets produce a pathway for the flow of electrical charges and provide a tougher hybrid system. The nanoscopic surface potential map reveals a higher work function of the individual functionalised SWNTs than surrounded GO sheets showing efficient charge exchange. We observed the enhanced conductivity up to 50 times and capacitance up to 3.5 times of the hybrid structure than the GO-paper. The laminate of polystyrene composites provided higher elastic modulus and mechanical strength when hybrid paper is used, thus paving the way for the exploitation of hybrid filler formulation in designing polymer composites.

Sonochemical edge functionalisation of molybdenum disulfide.

Liquid-phase exfoliation (LPE) has been shown to be capable of producing large quantities of high-quality dispersions suitable for processing into subsequent applications. LPE typically requires surfactants for aqueous dispersions or organic solvents with high boiling point. However, they have major drawbacks such as toxicity, aggregation during solvent evaporation or the presence of residues. Here, dispersions of molybdenum disulfide in acetone are prepared and show much higher concentration and stability than predicted by Hansen parameter analysis. Aiming to understand these enhanced properties, the nanosheets were characterised using UV-visible spectroscopy, zeta potential measurements, atomic force microscopy, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and scanning transmission microscopy combined with spatially-resolved electron energy loss spectroscopy. Also, the performance of the MoS2 nanosheets exfoliated in acetone was compared to that of those exfoliated in isopropanol as a catalyst for the hydrogen evolution reaction. The conclusion from the chemical characterisation was that MoS2 nanosheets exfoliated in acetone have an oxygen edge functionalisation, in the form of molybdenum oxides, changing its interaction with solvents and explaining the observed high-quality and stability of the resulting dispersion in a low boiling point solvent. Exfoliation in acetone could potentially be applied as a pretreatment to modify the solubility of MoS2 by edge functionalisation.

Charge Transfer Hybrids of Graphene Oxide and the Intrinsically Microporous Polymer PIM-1.

Nanohybrid materials based on nanoparticles of the intrinsically microporous polymer PIM-1 and graphene oxide (GO) are prepared from aqueous dispersions with a reprecipitation method, resulting in the surface of the GO sheets being decorated with nanoparticles of PIM-1. The significant blueshift in fluorescence signals for the GO/PIM-1 nanohybrids indicates modification of the optoelectronic properties of the PIM-1 in the presence of the GO due to their strong interactions. The stiffening in the Raman G peak of GO (by nearly 6 cm-1) further indicates p-doping of the GO in the presence of PIM. Kelvin probe force microscopy (KPFM) and electrochemical reduction measurements of the nanohybrids provide direct evidence for charge transfer between the PIM-1 nanoparticles and the GO nanosheets. These observations will be of importance for future applications of GO-PIM-1 nanohybrids as substrates and promoters in catalysis and sensing.

Platinum Nanoparticle Inclusion into a Carbonized Polymer of Intrinsic Microporosity: Electrochemical Characteristics of a Catalyst for Electroless Hydrogen Peroxide Production.

The one-step vacuum carbonization synthesis of a platinum nano-catalyst embedded in a microporous heterocarbon (Pt@cPIM) is demonstrated. A nitrogen-rich polymer of an intrinsic microporosity (PIM) precursor is impregnated with PtCl62- to give (after vacuum carbonization at 700 °C) a nitrogen-containing heterocarbon with embedded Pt nanoparticles of typically 1⁻4 nm diameter (with some particles up to 20 nm diameter). The Brunauer-Emmett-Teller (BET) surface area of this hybrid material is 518 m² g-1 (with a cumulative pore volume of 1.1 cm³ g-1) consistent with the surface area of the corresponding platinum-free heterocarbon. In electrochemical experiments, the heterocarbon-embedded nano-platinum is observed as reactive towards hydrogen oxidation, but essentially non-reactive towards bigger molecules during methanol oxidation or during oxygen reduction. Therefore, oxygen reduction under electrochemical conditions is suggested to occur mainly via a 2-electron pathway on the outer carbon shell to give H2O2. Kinetic selectivity is confirmed in exploratory catalysis experiments in the presence of H2 gas (which is oxidized on Pt) and O2 gas (which is reduced on the heterocarbon surface) to result in the direct formation of H2O2.

Intrinsically Microporous Polymer Retains Porosity in Vacuum Thermolysis to Electroactive Heterocarbon.

Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer-Emmet-Teller (BET) surface area of 1027 m(2)g(-1)), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m(2)g(-1), but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg(-1) (when oxidized) to ca. 147 Fg(-1) (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1-2 µm thick film.

Metastable ionic diodes derived from an amine-based polymer of intrinsic microporosity.

A highly rigid amine-based polymer of intrinsic microporosity (PIM), prepared by a polymerization reaction involving the formation of Tröger's base, is demonstrated to act as an ionic diode with electrolyte-dependent bistable switchable states.