Andrea Merenda

Silver metal nano-matrixes as high efficiency and versatile catalytic reactors for environmental remediation

Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications.

Assessing the temporal stability of surface functional groups introduced by plasma treatments on the outer shells of carbon nanotubes.

Plasma treatments are emerging as superior efficiency treatment for high surface to volume ratio materials to tune functional group densities and alter crystallinity due to their ability to interact with matter at the nanoscale. The purpose of this study is to assess for the first time the long term stability of surface functional groups introduced across the surface of carbon nanotube materials for a series of oxidative, reductive and neutral plasma treatment conditions. Both plasma duration dose matrix based exposures and time decay experiments, whereby the surface energy of the materials was evaluated periodically over a one-month period, were carried out. Although only few morphological changes across the graphitic planes of the carbon nanotubes were found under the uniform plasma treatment conditions, the time dependence of pertinent work functions, supported by Raman analysis, suggested that the density of polar groups decreased non-linearly over time prior to reaching saturation from 7 days post treatment. This work provides critical considerations on the understanding of the stability of functional groups introduced across high specific surface area nano-materials used for the design of nano-composites, adsorptive or separation systems, or sensing materials and where interfacial interactions are key to the final materials performance.

Functional Nanoporous Titanium Dioxide for Separation Applications: Synthesis Routes and Properties to Performance Analysis

Titanium dioxide represents an attractive industrial material for a wide range of applications, however in the last decades, research has been focused on its implementation in remediation systems for water treatment. The need to design nanoporous and nanotextured titania materials has arisen from the unique, beneficial properties of nanoscale titania for catalysis, separation and membrane sieving. This chapter reviews the synthesis procedures to generate tuneable titania materials either as self-supporting structures or as active layers on top of other porous materials. Finally, the catalytic properties of nanoporous and nanostructured TiO2 are reviewed for the degradation of organic compounds in wastewater. Significant parameters, such as specific surface area and crystallite size, are shown to be critical and must be optimised towards the fabrication of catalytic reactors for Advanced Oxidation Processes (AOP).

Single step synthesis of Schottky-like hybrid graphene - titania interfaces for efficient photocatalysis

The development of 2D nanomaterial coatings across metal surfaces is a challenge due to the mismatch between the metal microstructure and the nanoscale materials. The naturally occurring thin oxidative layer present across all metal surfaces, may lead to low adherence and connectivity. In this paper, graphene/titania/Titanium hybrid films were for the first time fabricated by a single step chemical vapour deposition process across Titanium foils. The presence of graphene as a dopant was found to enhance the photocatalytic performance of the final products, applied to the degradation of organic molecules and to lead to Schottky-like junction formation at the metal/oxide interface. These Schottky junctions, where vacancies are present across the titania material due to the graphene doping and where Ti3+ ions are predominantly located, yield enhanced catalytic performance. The highest degradation rate was found to be 9.66 × 10−6 min−1, achieved by the sample grown at 700 °C for 5 min, which was 62% higher than the sample just treated at that temperature without graphene growth. This work provides evidence that graphene may be grown across pure Titanium metal and opens new avenues in biomedical devices design, tribological or separation applications.

Single step synthesis of Janus nano-composite membranes by atmospheric aerosol plasma polymerization for solvents separation

Solvent permeation across membranes is limited due to physical resistance to diffusion from the selective layer within the membrane and to plasticizing effects generated by the solvent molecules onto the polymeric macromolecular matrix. Nano-composite thin film membranes provide promising routes to generate controlled microstructural separation materials with higher selectivities and permeabilities. Here, the fabrication of nano-composite based on octamethyl-polyhedral oligomeric silsesquioxane - hexamethyldisiloxane thin film membranes is demonstrated by aerosol assisted atmospheric plasma deposition onto pre-formed nano-porous membrane supports for the first time. Stable, atomically smooth and continuous solid films with controllable thickness down to 50 nm were achieved. The deposition process allowed for the control of the wettability of the surfaces to water and organic solvents, leading to the generation of hydrophobic but alcohol-philic surfaces. The liquid entry pressure of the films to water was found to be 8 bar from plasma polymerization as oppose to 3 bar for the bare nano-porous support only. In addition, the ideal separation selectivity for ethanol to water, up to 6.5, highlight the impact of both the surface energy and level of cross-linking of the hexamethyldisiloxane nanostructures on the diffusion mechanisms. This new atmospheric plasma deposition strategy opens-up cost-effective and environmentally friendly routes for the design of the smart Janus membrane with customizable properties and performance.

Short Review on Porous Metal Membranes—Fabrication, Commercial Products, and Applications

Porous metal membranes have recently received increasing attention, and significant progress has been made in their preparation and characterisation. This progress has stimulated research in their applications in a number of key industries including wastewater treatment, dairy processing, wineries, and biofuel purification. This review examines recent significant progress in porous metal membranes including novel fabrication concepts and applications that have been reported in open literature or obtained in our laboratories. The advantages and disadvantages of the different membrane fabrication methods were presented in light of improving the properties of current membrane materials for targeted applications. Sintering of particles is one of the main approaches that has been used for the fabrication of commercial porous metal membranes, and it has great advantages for the fabrication of hollow fibre metal membranes. However, sintering processes usually result in large pores (e.g., >1 µm). So far, porous metal membranes have been mainly used for the filtration of liquids to remove the solid particles. For porous metal membranes to be more widely used across a number of separation applications, particularly for water applications, further work needs to focus on the development of smaller pore (e.g., sub-micron) metal membranes and the significant reduction of capital and maintenance costs.