Leonora Velleman

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.

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.

Grafting of poly(ethylene glycol) on click chemistry modified Si(100) surfaces.

Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent.

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.

The control of epidermal growth factor grafted on mesoporous silica nanoparticles for targeted delivery

The performance of biomaterials in a biological environment is largely influenced by the surface properties of the biomaterials. In particular, grafted targeting ligands significantly impact the subsequent cellular interactions. The utilisation of a grafted epidermal growth factor (EGF) is effective for targeted delivery of drugs to tumours, but the amount of these biological attachments cannot be easily quantified as most characterization methods could not detect the extremely low amount of EGF ligands grafted on the surface of nanoparticles. In this study, hollow mesoporous silica nanoparticles (HMSNs) were functionalized with amine groups to conjugate with EGFs via carbodiimide chemistry. Time of flight secondary ion mass spectrometry (ToF-SIMS), a very surface specific technique (penetration depth <1.5 nm), was employed to study the binding efficiency of the EGF to the nanoparticles. Principal component analysis (PCA) was implemented to track the relative surface concentrations of EGFs on HMSNs. It was found that ToF-SIMS combined with the PCA technique is an effective method to evaluate the immobilization efficiency of EGFs. Based on this useful technique, the quantity and density of the EGF attachments that grafted on nanoparticles can be effectively controlled by varying the EGF concentration at grafting stages. Cell experiments demonstrated that the targeting performance of EGFR positive cells was affected by the number of EGFs attached on HMSNs.

Atomic layer deposition of SIO2 on porous alumina membranes: controlling the pore size and transport properties

Atomic layer deposition (ALD) of SiO2 onto nanoporous alumina (PA) membranes was investigated with the aim of adjusting the pore size and transport properties. PA membranes from commercial sources with a range of pore diameters (20 nm, 100 nm and 200 nm) were used and modified by atomic layer deposition using tris(tert-butoxy)silanol and water as the precursor couple. By adjusting the number of deposition cycles, the thickness of the conformal silica coating was controlled, reducing the effective pore diameter, and subsequently changing the transport properties of the PA membrane. Silica coated PA membranes with desired pore diameters from <5 nm to 100 nm were fabricated. In addition to the pore size, the transport properties and selectivity of fabricated silica coated PA membranes were controlled by chemical functionalisation using a silane with hydrophobic properties. Structural and chemical properties of modified membranes were studied by dynamic secondary ion mass spectrometry (DSIMS) and scanning electron microscopy (SEM). Spectrophotometric methods were used to evaluate the transport properties and selectivity of silica coated membranes by permeation studies of hydrophobic and hydrophilic organic molecules. The resultant silica/PA membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture, bioreactors, biosensing and drug delivery.

Engineered gold nanotube membranes for molecular separations

An electroless gold deposition method was used to fabricate gold nanotubes within the pores of polycarbonate and porous alumina template membranes. This approach provides control over the pore size of the membrane, with pore sizes being reduced to molecular dimensions. The effect of the pore size and surface chemistry on the transport properties of gold nanotube membranes has been explored. By modifying the membrane with a highly hydrophobic thiol, the separation of hydrophobic and hydrophilic molecules was achieved.

Theory of SERS enhancement: general discussion

Rohit Chikkaraddy opened the discussion of the Introductory Lecture: Regarding quantifying the chemical enhancement, you showed a systematic change in the SERS enhancement for halide substituted molecules due to charge transfer from the metal. Is the extra enhancement due to an inherent increase in the Raman cross-section of the molecule? How do you go about referencing, as the charge transfer changes the vibrational frequency?

Water transport through nanoporous materials: Porous silicon and single walled carbon nanotubes

We report upon the pressure driven water transport through porous silicon (pSi) and single walled carbon nanotube (SWCNT) membranes. Fabrication of the membranes was monitored by AFM and SEM. Water permeability as high as 16926 mm³ cm⁻² s⁻¹ atm⁻¹ is found for the pSi membrane. The SWCNT membrane is built upon the pSi membrane and a water permeability of 0.02 mm³ cm⁻² s⁻¹ atm⁻¹ is achieved. Performance comparisons to similar CNT membranes are made and future improvements to the system are proposed.