Robert Menzel

Solvent Exfoliation of Transition Metal Dichalcogenides: Dispersibility of Exfoliated Nanosheets Varies Only Weakly between Compounds

We have studied the dispersion and exfoliation of four inorganic layered compounds, WS(2), MoS(2), MoSe(2), and MoTe(2), in a range of organic solvents. The aim was to explore the relationship between the chemical structure of the exfoliated nanosheets and their dispersibility. Sonication of the layered compounds in solvents generally gave few-layer nanosheets with lateral dimensions of a few hundred nanometers. However, the dispersed concentration varied greatly from solvent to solvent. For all four materials, the concentration peaked for solvents with surface energy close to 70 mJ/m(2), implying that all four have surface energy close to this value. Inverse gas chromatography measurements showed MoS(2) and MoSe(2) to have surface energies of ∼75 mJ/m(2), in good agreement with dispersibility measurements. However, this method suggested MoTe(2) to have a considerably larger surface energy (∼120 mJ/m(2)). While surface-energy-based solubility parameters are perhaps more intuitive for two-dimensional materials, Hansen solubility parameters are probably more useful. Our analysis shows the dispersed concentration of all four layered materials to show well-defined peaks when plotted as a function of Hansens dispersive, polar, and H-bonding solubility parameters. This suggests that we can associate Hansen solubility parameters of δ(D) ∼ 18 MPa(1/2), δ(P) ∼ 8.5 MPa(1/2), and δ(H) ∼ 7 MPa(1/2) with all four types of layered material. Knowledge of these properties allows the estimation of the Flory-Huggins parameter, χ, for each combination of nanosheet and solvent. We found that the dispersed concentration of each material falls exponentially with χ as predicted by solution thermodynamics. This work shows that solution thermodynamics and specifically solubility parameter analysis can be used as a framework to understand the dispersion of two-dimensional materials. Finally, we note that in good solvents, such as cyclohexylpyrrolidone, the dispersions are temporally stable with >90% of material remaining dispersed after 100 h.

Inverse Gas Chromatography of As-Received and Modified Carbon Nanotubes

The surface properties of chemical vapor deposition (CVD)-grown, multiwalled carbon nanotubes (CNTs) have been studied using inverse gas chromatography (IGC). By adapting known IGC methodologies to these challenging materials, the surface character of a broad range of CNT materials can be reliably compared and quantified in terms of dispersive and specific surface energies, electron acceptor and donor numbers, and adsorption capacities. The effect of CNT surface modification by high temperature annealing, thermal oxidation, and grafting of methyl methacrylate was explored. The IGC surface characterization of these materials was consistent with results from other surface-sensitive analytical techniques, including X-ray photoelectron spectroscopy (XPS), titration, and electron microscopy, confirming the validity and sensitivity of our approaches. The same IGC methodologies were successfully applied to characterize three as-received CNT materials which differed significantly in their specific surface areas and functional surface group concentrations.

A versatile, solvent-free methodology for the functionalisation of carbon nanotubes

High temperature activation of carbon nanotubes (CNTs) provides a new and highly versatile functionalisation strategy. The reaction allows the attachment of a wide variety of functional species onto the nanotube surface at grafting ratios between 1–8 wt%, whilst maintaining the intrinsic properties of the untreated materials. The underlying, radical-based, reaction mechanism has been established by quenching experiments and EPR studies. The distribution of the functionalised sites has been investigated at the microscopic scale using tagging reactions. The grafted products have been characterized by electron microscopy, thermal analysis (TGA), Raman spectroscopy, and inverse gas chromatography (IGC). The change in the CNT surface properties after grafting has been quantified in terms of dispersive and specific surface energies, and altered dispersibilities in a broad range of solvents. It is possible to carry out the reaction using gas phase reagents, providing a clean, efficient, and scalable methodology, relevant to a diverse range of applications.

Nacre-nanomimetics: Strong, Stiff, and Plastic

The bricks and mortar in the classic structure of nacre have characteristic geometry, aspect ratios and relative proportions; these key parameters can be retained while scaling down the absolute length scale by more than 1 order of magnitude. The results shed light on fundamental scaling behavior and provide new opportunities for high performance, yet ductile, lightweight nanocomposites. Reproducing the toughening mechanisms of nacre at smaller length scales allows a greater volume of interface per unit volume while simultaneously increasing the intrinsic properties of the inorganic constituents. Layer-by-layer (LbL) assembly of poly(sodium 4-styrenesulfonate) (PSS) polyelectrolyte and well-defined [Mg2Al(OH)6]CO3.nH2O layered double hydroxide (LDH) platelets produces a dense, oriented, high inorganic content (∼90 wt %) nanostructure resembling natural nacre, but at a shorter length scale. The smaller building blocks enable the (self-) assembly of a higher quality nanostructure than conventional mimics, leading to improved mechanical properties, matching those of natural nacre, while allowing for substantial plastic deformation. Both strain hardening and crack deflection mechanisms were observed in situ by scanning electron microscopy (SEM) during nanoindentation. The best properties emerge from an ordered nanostructure, generated using regular platelets, with narrow size dispersion.

Exploring Carbon Nanomaterial Diversity for Nucleation of Protein Crystals.

Controlling crystal nucleation is a crucial step in obtaining high quality protein crystals for structure determination by X-ray crystallography. Carbon nanomaterials (CNMs) including carbon nanotubes, graphene oxide, and carbon black provide a range of surface topographies, porosities and length scales; functionalisation with two different approaches, gas phase radical grafting and liquid phase reductive grafting, provide routes to a range of oligomer functionalised products. These grafted materials, combined with a range of controls, were used in a large-scale assessment of the effectiveness for protein crystal nucleation of 20 different carbon nanomaterials on five proteins. This study has allowed a direct comparison of the key characteristics of carbon-based nucleants: appropriate surface chemistry, porosity and/or roughness are required. The most effective solid system tested in this study, carbon black nanoparticles functionalised with poly(ethylene glycol) methyl ether of mean molecular weight 5000, provides a novel highly effective nucleant, that was able to induce crystal nucleation of four out of the five proteins tested at metastable conditions.

Two-stage, non-hydrolytic synthesis for improved control of TiO2 nanorod formation

TiO2 anatase nanorods were grown via the non-hydrolytic elimination reaction between TiCl4 and Ti(OiPr)4 in the presence of oleic acid. The reaction was carried out in two stages in order to separate TiOx seed nucleation at lower temperatures from nanorod growth at higher temperatures. This separation made it possible to study the crystal growth mechanism in more detail, indicating that nanorod formation occurred through a combination of atom-by-atom addition and oriented attachment of the initial seeds. The two-stage reaction approach also enabled considerably improved control of titania nanorod formation in terms of product morphology, crystallinity and uniformity. The effects of a range of reaction parameters, including reaction duration, temperature, dilution and stoichiometry, were investigated.

Cross-linked single-walled carbon nanotube aerogel electrodes via reductive coupling chemistry

Single-walled carbon nanotube (SWCNT) anions can be cross-linked by a dielectrophile to form covalent, carbon-bonded organogels. Freeze-drying produces cryogels with low density (2.3 mg cm−3), high surface area (766 m2 g−1), and high conductivity (9.4 S m−1), showing promise as supercapacitor electrodes. Counterion concentration controls debundling, grafting ratio, as well as all the resulting properties.

Aqueous dispersions of oligomer-grafted carbon nanomaterials with controlled surface charge and minimal framework damage

Functionalised carbon nanomaterials (CNMs), with an undamaged carbon framework and controlled physiochemical properties, are desirable for a wide range of scientific studies and commercial applications. The use of a thermochemical grafting approach provides a versatile means to functionalise both multi-walled carbon nanotubes (MWCNTs) and carbon black (CB) nanoparticles without altering their inherent structures. The functionalisation process was investigated by employing various types of grafting monomers; to improve water solubility, reagents were chosen that introduced an ionic character either intrinsically or after further chemical reactions. The degree of grafting for both MWCNTs and CB ranged from 3-27 wt%, as established by thermal gravimetric analysis (TGA). Raman spectroscopy confirmed that the structural framework of the MWCNTs was unaffected by the thermochemical treatment. The effectiveness of the surface modification was demonstrated by significantly improved dispersibility and stability in water, and further quantified by zeta-potential analysis. The concentration of stable, individualised and grafted MWCNTs in water ranged from ∼30 to 80 μg mL(-1) after centrifugation at 10 000 g for 15 min, whereas functionalised CB in water showed improved dispersibility up to ∼460 μg mL(-1). The successful preparation of structurally identical but differently functionalised nanoparticle panels, with high water compatibility and minimal framework damage, is useful for controlled experiments. For example, they can be used to explore the relationship between toxicological effects and specific physiochemical properties, such as surface charge and geometry.

Size effects in nanoscale dielectric materials

The electronic properties of materials change substantially when size and shape are reduced to the nanometre scale. In this study we focus on the size dependence of the dielectric function in novel TiO2 anatase nanoplatelets. Measurements of the dielectric function are obtained by electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM). We present data collected from platelets along the [002] and [200] zone axes and observe that interpretation of the size effects requires a full understanding of the anisotropic effects on the energy-loss function. First principles DFT calculations of the bulk energy-loss function are used as an aid to the interpretation of crystal orientation effects on the EEL spectrum.