Ludovic F. Dumée

Recent Developments in Carbon Nanotube Membranes for Water Purification and Gas Separation

Carbon nanotubes (CNTs) are nanoscale cylinders of graphene with exceptional properties such as high mechanical strength, high aspect ratio and large specific surface area. To exploit these properties for membranes, macroscopic structures need to be designed with controlled porosity and pore size. This manuscript reviews recent progress on two such structures: (i) CNT Bucky-papers, a non-woven, paper like structure of randomly entangled CNTs, and (ii) isoporous CNT membranes, where the hollow CNT interior acts as a membrane pore. The construction of these two types of membranes will be discussed, characterization and permeance results compared, and some promising applications presented.

Metal organic framework based catalysts for CO2 conversion

Metal organic frameworks (MOFs) are hybrid crystalline materials, exhibiting high specific surface areas, controllable pore sizes and surface chemistry. These properties have made MOFs attractive for a wide range of applications including gas separation, gas storage, sensing, drug delivery and catalysis. This review focuses on recent progress in the application of MOF materials as catalysts for CO2 conversion through chemical fixation, photocatalysis and electrocatalysis. In particular, this review discusses the co-relationship between the physicochemical properties of MOF materials including their catalytic performance as well as their stability and recyclability under different reaction conditions, relevant to CO2 conversion. Current modification techniques for improving MOF performance are highlighted along with the recent understanding of their electronic properties. The limitations of MOF based catalysts are also discussed and potential routes for improvement are suggested.

Seeded growth of ZIF-8 on the surface of carbon nanotubes towards self-supporting gas separation membranes

We report the synthesis of the first continuous, inter-grown ZIF-8 membrane via the secondary growth method. ZIF-8 crystals were seeded and strongly anchored onto porous carbon nanotube bucky-paper supports and hydrothermally grown into a dense and continuous ZIF-8 network. The self-supporting hybrid metal organic framework membranes were characterized by scanning electron microscopy and shown to exhibit both a very homogeneous structure and a very smooth nanotube-metal organic framework interface. Gas adsorption (H2, CH4, CO2, N2) and permeation (He, CO2, N2 and Xe) tests were performed to evaluate the permeance of each gas and to predict the selectivity. The membranes were highly robust and sustained pressures as high as 500 kPa. Furthermore, the high selectivity of N2 over CO2 and Xe (33 and 163 respectively), shown by gas adsorption single gas permeation and mixed gas permeation clearly demonstrates the near defect-free nature of the membranes while the high hydrothermal stability of ZIF-8 makes these novel composites highly promising for water vapour saturated gas treatment.

Control of porosity and pore size of metal reinforced carbon nanotube membranes.

Membranes are crucial in modern industry and both new technologies and materials need to be designed to achieve higher selectivity and performance. Exotic materials such as nanoparticles offer promising perspectives, and combining both their very high specific surface area and the possibility to incorporate them into macrostructures have already shown to substantially increase the membrane performance. In this paper we report on the fabrication and engineering of metal-reinforced carbon nanotube (CNT) Bucky-Paper (BP) composites with tuneable porosity and surface pore size. A BP is an entangled mesh non-woven like structure of nanotubes. Pure CNT BPs present both very high porosity (>90%) and specific surface area (>400 m2/g). Furthermore, their pore size is generally between 20–50 nm making them promising candidates for various membrane and separation applications. Both electro-plating and electroless plating techniques were used to plate different series of BPs and offered various degrees of success. Here we will report mainly on electroless plated gold/CNT composites. The benefit of this method resides in the versatility of the plating and the opportunity to tune both average pore size and porosity of the structure with a high degree of reproducibility. The CNT BPs were first oxidized by short UV/O3 treatment, followed by successive immersion in different plating solutions. The morphology and properties of these samples has been investigated and their performance in air permeation and gas adsorption will be reported.

Superhydrophobic and Superoleophilic Micro-Wrinkled Reduced Graphene Oxide as a Highly Portable and Recyclable Oil Sorbent

The potential of superhydrophobic and superoleophilic microwrinkled reduced graphene oxide (MWrGO) structures is here demonstrated for oil spill cleanup. The impact of the thickness of MWrGO films on the sorption performance of three different oils was investigated. Water contact angles across the MWrGO surfaces were found to exceed 150°, while oil could be easily absorbed by the microwrinkled structures of MWrGO within seconds after contact. Although the oil surface diffusion rate was not found to be dependent on the thickness of the graphene oxide films, the oil sorption capacity was the largest with the thinner MWrGO films due to the high surface area resulting from their fine surface texture. Furthermore, the composite films can be repeatedly used for at least 20 oil sorption-removal cycles without any notable loss in selectivity and uptake capacity. These MWrGO/elastomer composite films could be applied as a potential candidate material for future oil spill cleanup.

Activation of gold decorated carbon nanotube hybrids for targeted gas adsorption and enhanced catalytic oxidation

Free standing assemblies of carbon nanotubes (CNTs), known as bucky-paper (BP), have been functionalised through the in situ plating of gold nanoparticles within the interstitial spaces in the BP. The nanoparticles are extremely small and well distributed at short plating times, so much so that the specific surface area of the BP is actually increased by the gold incorporation. These well distributed nanoparticles exhibit high enthalpy hydrogen storage and selective carbon dioxide adsorption over other gases, in particular methane. In concert with the conductive BP substrate, it has been demonstrated that these materials can also act as high turnover heterogeneous catalysts.

Silver nanoparticles prepared by gamma irradiation across metal–organic framework templates

In this study, we demonstrate for the first time the successful fabrication of well-dispersed ultrafine silver nanoparticles inside metal–organic frameworks through a single step gamma irradiation at room temperature. HKUST-1 crystals are soaked in silver nitrate aqueous solution and irradiated with a Cobalt 60 source across a range of irradiation doses to synthesize highly uniformly distributed silver nano-particles. The average size of the silver nanoparticles across the Ag@HKUST-1 materials is found to vary between 1.4 and 3 nm for dose exposures between 1 and 200 kGy, respectively. The Ag@HKUST-1 hybrid crystals exhibit strong surface plasmon resonance and are highly durable and efficient catalytic materials for the reduction of 4-nitrophenol to 4-aminophenol (up to 14.46 × 10−3 s−1 for 1 kGy Ag@HKUST-1). The crystals can be easily recycled for at least five successive cycles of reaction with a conversion efficiency higher than 99.9%. The gamma irradiation is demonstrated to be an effective and environmental friendly process for the synthesis of nano-particles across confined metal–organic frameworks at room temperature with potential applications in environmental science.

The fabrication and surface functionalization of porous metal frameworks : a review

Porous metal frameworks offer potentially useful applications for the aerospace, automotive and bio-medical industries. They can be used as electrodes, actuators, or as selective membrane films. The versatility of the physical features (pore size, pore depth, overall porosity and pore surface coverage) as well as the large range of surface chemistries for both metal oxides and pure noble metals offers scope to functionalise metal nano-particles and networks of nano-porous metal structures. As well as traditional routes to producing metal structures, such as metal sintering or foaming, novel high-throughput techniques have recently been investigated. Nanoparticle self-assembly, metal ion reduction and deposition as well as metal alloy de-alloying were identified as sustainable routes to produce large surface areas of such nano-porous metal frameworks. The main limitations of the current fabrication techniques include the difficulty to process stable and homogeneous arrays of nano-scale pores and the control of their morphology due to the high reactivity of nano-structured metal structures. This paper aims at critically reviewing the various fabrication techniques and surface functionalization routes used to produce advanced functional porous metal frameworks. The limitations and advantages of the different fabrication techniques will be discussed in light of the final material properties and targeted applications.

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.

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.