Joseph G. Shapter

Phosphorene and Phosphorene-Based Materials - Prospects for Future Applications.

Phosphorene, a single- or few-layered semiconductor material obtained from black phosphorus, has recently been introduced as a new member of the family of two-dimensional (2D) layered materials. Since its discovery, phosphorene has attracted significant attention, and due to its unique properties, is a promising material for many applications including transistors, batteries and photovoltaics (PV). However, based on the current progress in phosphorene production, it is clear that a lot remains to be explored before this material can be used for these applications. After providing a comprehensive overview of recent advancements in phosphorene synthesis, advantages and challenges of the currently available methods for phosphorene production are discussed. An overview of the research progress in the use of phosphorene for a wide range of applications is presented, with a focus on enabling important roles that phosphorene would play in next-generation PV cells. Roadmaps that have the potential to address some of the challenges in phosphorene research are examined because it is clear that the unprecedented chemical, physical and electronic properties of phosphorene and phosphorene-based materials are suitable for various applications, including photovoltaics.

Copper removal using bio-inspired polydopamine coated natural zeolites.

Herein, for the first time, natural clinoptilolite-rich zeolite powders modified with a bio-inspired adhesive, polydopamine (PDA), have been systematically studied as an adsorbent for copper cations (Cu(II)) from aqueous solution. Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) revealed successful grafting of PDA onto the zeolite surface. The effects of pH (2-5.5), PDA treatment time (3-24h), contact time (0 to 24h) and initial Cu(II) ion concentrations (1 to 500mgdm(-3)) on the adsorption of Cu(II) ions were studied using atomic absorption spectroscopy (AAS) and neutron activation analysis (NAA). The adsorption behavior was fitted to a Langmuir isotherm and shown to follow a pseudo-second-order reaction model. The maximum adsorption capacities of Cu(II) were shown to be 14.93mgg(-1) for pristine natural zeolite and 28.58mgg(-1) for PDA treated zeolite powders. This impressive 91.4% increase in Cu(II) ion adsorption capacity is attributed to the chelating ability of the PDA on the zeolite surface. Furthermore studies of recyclability using NAA showed that over 50% of the adsorbed copper could be removed in mild concentrations (0.01M or 0.1M) of either acid or base.

Ruthenium Porphyrin Functionalized Single-Walled Carbon Nanotube Arrays-A Step Toward Light Harvesting Antenna and Multibit Information Storage

Ruthenium porphyrin functionalized single-walled carbon nanotube arrays have been prepared using coordination of the axial position of the metal ion onto 4-aminopyridine preassembled single-walled carbon nanotubes directly anchored to a silicon(100) surface (SWCNTs-Si). The formation of these ruthenium porphyrin functionalized single-walled carbon nanotube array electrodes (RuTPP-SWCNTs-Si) has been monitored using infrared spectroscopy (IR), differential pulse voltammetry (DPV), atomic force microscopy (AFM), laser desorption time-of-flight mass spectroscopy (LDI-TOF-MS), UV-vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. Electrochemical results show two successive one-electron reversible redox waves. The surface concentration of the ruthenium porphyrin molecules is 3.44 x 10 (-8) mol cm (-2). Optical results indicate that the immobilization of ruthenium porphyrin enhances the light absorption of SWCNTs-Si surfaces in the visible light region. Moreover mixed assembly of ferrocene/porphyrin onto carbon nanotube arrays has been achieved by altering the ratio of two redox-active species in the deposition solution. These results suggest the ruthenium porphyrin modified electrodes are excellent candidates for molecular memory devices and light harvesting antennae.

Alginate-graphene oxide hybrid gel beads: An efficient copper adsorbent material

Here we report on the adsorption performance of calcium alginate (Ca-Alg2) and Ca-Alg2 with encapsulated graphene oxide (Ca-Alg2/GO) gel bead adsorbents for the successful removal of Cu(2+) ions from aqueous solution. Different adsorbent doses, Cu(2+) concentrations and contact times were investigated using equilibrium and kinetic studies. The adsorbents were characterized using Fourier transform-infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and focussed ion beam scanning electron microscopy (FIB/SEM). The equilibrium adsorption data were fitted to Langmuir isotherms and the maximum adsorption capacities of the Ca-Alg2 and Ca-Alg2/GO gel beads were found to be 42.7 mg g(-1) and 60.2 mg g(-1), respectively. The equilibrium adsorption data were fitted to a pseudo-second-order kinetic equation showing that the Ca-Alg2 gel beads had a higher kinetic adsorption rate at 0.0425 g mg(-1)min(-1) compared to Ca-Alg2/GO at 0.0179 g mg(-1)min(-1).

Dual Silane Surface Functionalization for the Selective Attachment of Human Neuronal Cells to Porous Silicon

Porous silicon (pSi) surfaces were chemically micropatterned through a combination of photolithography and surface silanization reactions. This patterning technique produces discretely defined regions on a pSi surface functionalized with a specific chemical functionality, and the surrounding surface displays a completely different functionality. The generated chemical patterns were characterized by a combination of IR microscopy and the conjugation of two different fluorescent organic dyes. Finally, the chemically patterned pSi surface was used to direct the attachment of neuronal cells to the surface. This patterning strategy will be useful for the development of high-throughput platforms for investigating cell behavior.

Enhanced adsorption of mercury ions on thiol derivatized single wall carbon nanotubes.

Thiol-derivatized single walled carbon nanotube (SWCNT-SH) powders were synthesized by reacting acid-cut SWCNTs with cysteamine hydrochloride using carbodiimide coupling. Infrared (IR) spectroscopy, Raman spectroscopy and thermogravimetric analysis confirmed the successful functionalization of the SWCNTs. SWCNT-SH powders exhibited a threefold higher adsorption capacity for Hg(II) ions compared to pristine SWCNTs, and a fourfold higher adsorption capacity compared to activated carbon. The influence of adsorption time, pH, initial metal concentration and adsorbent dose on Hg(II) ion removal was investigated. The maximum adsorption capacity of the SWCNT-SH powders was estimated by using equilibrium isotherms, such as Freundlich and Langmuir, and the maximum adsorption capacity of the SWCNT-SH powder was found to be 131 mg/g. A first-order rate model was employed to describe the kinetic adsorption process of Hg(II) ions onto the SWCNT-SH powders. Desorption studies revealed that Hg(II) ions could be easily removed from the SWCNT-SH powders by altering the pH. Further, the adsorption efficiency of recovered SWCNT-SH powders was retained up to 91%, even after 5 adsorption/desorption cycles.

Carbon Nanotubes for Dye‐Sensitized Solar Cells

As one type of emerging photovoltaic cell, dye-sensitized solar cells (DSSCs) are an attractive potential source of renewable energy due to their eco-friendliness, ease of fabrication, and cost effectiveness. However, in DSSCs, the rarity and high cost of some electrode materials (transparent conducting oxide and platinum) and the inefficient performance caused by slow electron transport, poor light-harvesting efficiency, and significant charge recombination are critical issues. Recent research has shown that carbon nanotubes (CNTs) are promising candidates to overcome these issues due to their unique electrical, optical, chemical, physical, as well as catalytic properties. This article provides a comprehensive review of the research that has focused on the application of CNTs and their hybrids in transparent conducting electrodes (TCEs), in semiconducting layers, and in counter electrodes of DSSCs. At the end of this review, some important research directions for the future use of CNTs in DSSCs are also provided.

Accurate thickness measurement of graphene

Graphene has emerged as a material with a vast variety of applications. The electronic, optical and mechanical properties of graphene are strongly influenced by the number of layers present in a sample. As a result, the dimensional characterization of graphene films is crucial, especially with the continued development of new synthesis methods and applications. A number of techniques exist to determine the thickness of graphene films including optical contrast, Raman scattering and scanning probe microscopy techniques. Atomic force microscopy (AFM), in particular, is used extensively since it provides three-dimensional images that enable the measurement of the lateral dimensions of graphene films as well as the thickness, and by extension the number of layers present. However, in the literature AFM has proven to be inaccurate with a wide range of measured values for single layer graphene thickness reported (between 0.4 and 1.7 nm). This discrepancy has been attributed to tip-surface interactions, image feedback settings and surface chemistry. In this work, we use standard and carbon nanotube modified AFM probes and a relatively new AFM imaging mode known as PeakForce tapping mode to establish a protocol that will allow users to accurately determine the thickness of graphene films. In particular, the error in measuring the first layer is reduced from 0.1-1.3 nm to 0.1-0.3 nm. Furthermore, in the process we establish that the graphene-substrate adsorbate layer and imaging force, in particular the pressure the tip exerts on the surface, are crucial components in the accurate measurement of graphene using AFM. These findings can be applied to other 2D materials.

Supramolecular construction of vesicles based on core-substituted naphthalene diimide appended with triethyleneglycol motifs

The self-assembly of core-substituted naphthalene diimides bearing triethylene glycol motifs leads to the formation of stable vesicles in DMSO and CHCl(3)/MeOH (6 : 4, v/v) solvents. The vesicles were evaluated by means of UV/vis and fluorescence spectroscopy, transmission electron microscopy, atomic force microscopy and dynamic light scattering.

Direct attachment of well-aligned single-walled carbon nanotube architectures to silicon (100) surfaces : a simple approach for device assembly

A new approach for the attachment of vertically-aligned shortened carbon nanotube architectures to a silicon (100) substrate by chemical anchoring directly to the surface has been demonstrated for the first time. The ordered assembly of single-walled carbon nanotubes (SWCNTs) was accomplished by hydroxylating the silicon surface followed by a condensation reaction with carboxylic acid functionalised SWCNTs. This new nanostructure has been characterised by X-ray photoelectron, Raman and Fourier transform infrared (FTIR) spectroscopy as well as scanning electron and atomic force microscopy. The assembly behaviour of SWCNTs onto the silicon surface shows a fast initial step producing isolated functionalised carbon nanotubes or nanotube bundles anchored to the silicon surface followed by a slower step where the adsorbed nanotubes grow into larger aggregates via van der Waals interactions between adsorbed and solvated nanotubes. The electrochemical and optical properties of the SWCNTs directly attached to silicon have also been investigated. These new nanostructures are excellent electrochemical electrodes. They also fluoresce in the wavelength range 650-800 nm. The successful attachment of the SWCNTs directly to silicon provides a simple, new avenue for fabrication and development of silicon-based nanoelectronic, nano-optoelectronic and sensing devices. Compared to existing techniques, this new approach has several advantages including low operating temperature, low cost and the possibility of further modification.