Graphene Bridge for Photocatalytic Hydrogen Evolution with Gold Nanocluster Co-Catalysts.

Herein, the UV light photocatalytic activity of an Au101NC-AlSrTiO3-rGO nanocomposite comprising 1 wt% rGO, 0.05 wt% Au101(PPh3)21Cl5 (Au101NC), and AlSrTiO3 evaluated for H2 production. The synthesis of Au101NC-AlSrTiO3-rGO nanocomposite followed two distinct routes: (1) Au101NC was first mixed with AlSrTiO3 followed by the addition of rGO (Au101NC-AlSrTiO3:rGO) and (2) Au101NC was first mixed with rGO followed by the addition of AlSrTiO3 (Au101NC-rGO:AlSrTiO3). Both prepared samples were annealed in air at 210 °C for 15 min. Inductively coupled plasma mass spectrometry and high-resolution scanning transmission electron microscopy showed that the Au101NC adhered almost exclusively to the rGO in the nanocomposite and maintained a size less than 2 nm. Under UV light irradiation, the Au101NC-AlSrTiO3:rGO nanocomposite produced H2 at a rate 12 times greater than Au101NC-AlSrTiO3 and 64 times greater than AlSrTiO3. The enhanced photocatalytic activity is attributed to the small particle size and high loading of Au101NC, which is achieved by non-covalent binding to rGO. These results show that significant improvements can be made to AlSrTiO3-based photocatalysts that use cluster co-catalysts by the addition of rGO as an electron mediator to achieve high cluster loading and limited agglomeration of the clusters.

Au101-rGO nanocomposite: immobilization of phosphine-protected gold nanoclusters on reduced graphene oxide without aggregation.

Graphene supported transition metal clusters are of great interest for potential applications, such as catalysis, due to their unique properties. In this work, a simple approach to deposit Au101(PPh3)21Cl5 (Au101NC) on reduced graphene oxide (rGO) via an ex situ method is presented. Reduction of graphene oxide at native pH (pH ≈ 2) to rGO was performed under aqueous hydrothermal conditions. Decoration of rGO sheets with controlled content of 5 wt% Au was accomplished using only pre-synthesised Au101NC and rGO as precursors and methanol as solvent. High resolution scanning transmission electron microscopy indicated that the cluster size did not change upon deposition with an average diameter of 1.4 ± 0.4 nm. It was determined that the rGO reduction method was crucial to avoid agglomeration, with rGO reduced at pH ≈ 11 resulting in agglomeration. X-ray photoelectron spectroscopy was used to confirm the deposition of Au101NCs and show the presence of triphenyl phosphine ligands, which together with attenuated total reflectance Fourier transform infrared spectroscopy, advocates that the deposition of Au101NCs onto the surface of rGO was facilitated via non-covalent interactions with the phenyl groups of the ligands. Inductively coupled plasma mass spectrometry and thermogravimetric analysis were used to determine the gold loading and both agree with a gold loading of ca. 4.8-5 wt%. The presented simple and mild strategy demonstrates that good compatibility between size-specific phosphine protected gold clusters and rGO can prevent aggregation of the metal clusters. This work contributes towards producing an agglomeration-free synthesis of size-specific ligated gold clusters on rGO that could have wide range of applications.

Activation of Water-Splitting Photocatalysts by Loading with Ultrafine Rh-Cr Mixed-Oxide Cocatalyst Nanoparticles.

The activity of many water-splitting photocatalysts could be improved by the use of RhIII -CrIII mixed oxide (Rh2-x Crx O3 ) particles as cocatalysts. Although further improvement of water-splitting activity could be achieved if the size of the Rh2-x Crx O3 particles was decreased further, it is difficult to load ultrafine (<2 nm) Rh2-x Crx O3 particles onto a photocatalyst by using conventional loading methods. In this study, a new loading method was successfully established and was used to load Rh2-x Crx O3 particles with a size of approximately 1.3 nm and a narrow size distribution onto a BaLa4 Ti4 O15 photocatalyst. The obtained photocatalyst exhibited an apparent quantum yield of 16 %, which is the highest achieved for BaLa4 Ti4 O15 to date. Thus, the developed loading technique of Rh2-x Crx O3 particles is extremely effective at improving the activity of the water-splitting photocatalyst BaLa4 Ti4 O15 . This method is expected to be extended to other advanced water-splitting photocatalysts to achieve higher quantum yields.

Improved Application of Carbon Nanotube Atomic Force Microscopy Probes Using PeakForce Tapping Mode.

In this work PeakForce tapping (PFT) imaging was demonstrated with carbon nanotube atomic force microscopy (CNT-AFM) probes; this imaging mode shows great promise for providing simple, stable imaging with CNT-AFM probes, which can be difficult to apply. The PFT mode is used with CNT-AFM probes to demonstrate high resolution imaging on samples with features in the nanometre range, including a Nioprobe calibration sample and gold nanoparticles on silicon, in order to demonstrate the modes imaging effectiveness, and to also aid in determining the diameter of very thin CNT-AFM probes. In addition to stable operation, the PFT mode is shown to eliminate "ringing" artefacts that often affect CNT-AFM probes in tapping mode near steep vertical step edges. This will allow for the characterization of high aspect ratio structures using CNT-AFM probes, an exercise which has previously been challenging with the standard tapping mode.

Measuring the Density of States of the Inner and Outer Wall of Double-Walled Carbon Nanotubes.

The combination of ultraviolet photoelectron spectroscopy and metastable helium induced electron spectroscopy is used to determine the density of states of the inner and outer coaxial carbon nanotubes. Ultraviolet photoelectron spectroscopy typically measures the density of states across the entire carbon nanotube, while metastable helium induced electron spectroscopy measures the density of states of the outermost layer alone. The use of double-walled carbon nanotubes in electronic devices allows for the outer wall to be functionalised whilst the inner wall remains defect free and the density of states is kept intact for electron transport. Separating the information of the inner and outer walls enables development of double-walled carbon nanotubes to be independent, such that the charge transport of the inner wall is maintained and confirmed whilst the outer wall is modified for functional purposes.

Efficiency Improvement Using Molybdenum Disulphide Interlayers in Single-Wall Carbon Nanotube/Silicon Solar Cells.

Molybdenum disulphide (MoS2) is one of the most studied and widely applied nanomaterials from the layered transition-metal dichalcogenides (TMDs) semiconductor family. MoS2 has a large carrier diffusion length and a high carrier mobility. Combining a layered structure of single-wall carbon nanotube (SWCNT) and MoS2 with n-type silicon (n-Si) provided novel SWCNT/n-Si photovoltaic devices. The solar cell has a layered structure with Si covered first by a thin layer of MoS2 flakes and then a SWCNT film. The films were examined using scanning electron microscopy, atomic force microscopy and Raman spectroscopy. The MoS2 flake thickness ranged from 5 to 90 nm while the nanosheet’s lateral dimensions size ranged up to 1 μm². This insertion of MoS2 improved the photoconversion efficiency (PCE) of the SWCNT/n-Si solar cells by approximately a factor of 2.

Direct-Patterning SWCNTs Using Dip Pen Nanolithography for SWCNT/Silicon Solar Cells.

Dip pen nanolithography (DPN) is used to pattern single-walled carbon nanotube (SWCNT) lines between the n-type Si and SWCNT film in SWCNT/Si solar cells. The SWCNT ink composition, loading, and DPN pretreatment are optimized to improve patterning. This improved DPN technique is then used to successfully pattern >1 mm long SWCNT lines consistently. This is a 20-fold increase in the previously reported direct-patterning of SWCNT lines using the DPN technique, and demonstrates the scalability of the technique to pattern larger areas. The degree of the uniformity of SWCNTs in these lines is further characterized by Raman spectroscopy and scanning electron microscopy. The patterned SWCNT lines are used as thin conductive pathways in SWCNT/Si solar cells, similar to front contact electrodes. The critical parameters of these solar cells are measured and compared to control cells without SWCNT lines. The addition of SWCNT lines increases power conversion efficiency by 40% (relative). Importantly, the SWCNT lines reduce average series resistance by 44%, and consequently increase average fill factor by 24%.

Electrocatalytic Activity of a 2D Phosphorene-Based Heteroelectrocatalyst for Photoelectrochemical Cells.

Research into efficient synthesis, fundamental properties, and potential applications of phosphorene is currently the subject of intense investigation. Herein, solution-processed phosphorene or few-layer black phosphorus (FL-BP) sheets are prepared using a microwave exfoliation method and used in photoelectrochemical cells. Based on experimental and theoretical (DFT) studies, the FL-BP sheets are found to act as catalytically active sites and show excellent electrocatalytic activity for triiodide reduction in dye-sensitized solar cells. Importantly, the device fabricated based on the newly designed cobalt sulfide (CoSx ) decorated nitrogen and sulfur co-doped carbon nanotube heteroelectrocatalyst coated with FL-BP (FL-BP@N,S-doped CNTs-CoSx ) displayed an impressive photovoltaic efficiency of 8.31 %, outperforming expensive platinum based cells. This work paves the way for using phosphorene-based electrocatalysts for next-generation energy-storage systems.

Solution Based Methods for the Fabrication of Carbon Nanotube Modified Atomic Force Microscopy Probes.

High aspect ratio carbon nanotubes are ideal candidates to improve the resolution and lifetime of atomic force microscopy (AFM) probes. Here, we present simple methods for the preparation of carbon nanotube modified AFM probes utilising solvent evaporation or dielectrophoresis. Scanning electron microscopy (SEM) of the modified probes shows that the carbon nanotubes attach to the probe apex as fibres and display a high aspect ratio. Many of the probes made in this manner were initially found to exhibit anomalous feedback characteristics during scanning, which rendered them unsuitable for imaging. However, we further developed and demonstrated a simple method to stabilise the carbon nanotube fibres by scanning with high force in tapping mode, which either shortens or straightens the carbon fibre, resulting in stable and high quality imaging AFM imaging.

Single-Walled Carbon Nanotubes Enhance the Efficiency and Stability of Mesoscopic Perovskite Solar Cells.

Carbon nanotubes are 1D nanocarbons with excellent properties and have been extensively used in various electronic and optoelectronic device applications including solar cells. Herein, we report a significant enhancement in the efficiency and stability of perovskite solar cells (PSCs) by employing single-walled carbon nanotubes (SWCNTs) in the mesoporous photoelectrode. It was found that SWCNTs provide both rapid electron transfer and advantageously shifts the conduction band minimum of the TiO2 photoelectrode and thus enhances all photovoltaic parameters of PSCs. The TiO2-SWCNTs photoelectrode based PSC device exhibited a power conversion efficiency (PCE) of up to 16.11%, while the device fabricated without SWCNTs displayed an efficiency of 13.53%. More importantly, we found that the SWCNTs in the TiO2 nanoparticles (TiO2 NPs) based photoelectrode suppress the hysteresis behavior and significantly enhance both the light and long-term storage stability of the PSC devices. The present work provides important guidance for future investigations in utilizing carbonaceous materials for solar cells.

Carbon Nanotubes in TiO2 Nanofiber Photoelectrodes for High-Performance Perovskite Solar Cells.

1D semiconducting oxides are unique structures that have been widely used for photovoltaic (PV) devices due to their capability to provide a direct pathway for charge transport. In addition, carbon nanotubes (CNTs) have played multifunctional roles in a range of PV cells because of their fascinating properties. Herein, the influence of CNTs on the PV performance of 1D titanium dioxide nanofiber (TiO2 NF) photoelectrode perovskite solar cells (PSCs) is systematically explored. Among the different types of CNTs, single-walled CNTs (SWCNTs) incorporated in the TiO2 NF photoelectrode PSCs show a significant enhancement (≈40%) in the power conversion efficiency (PCE) as compared to control cells. SWCNTs incorporated in TiO2 NFs provide a fast electron transfer within the photoelectrode, resulting in an increase in the short-circuit current (Jsc) value. On the basis of our theoretical calculations, the improved open-circuit voltage (Voc) of the cells can be attributed to a shift in energy level of the photoelectrodes after the introduction of SWCNTs. Furthermore, it is found that the incorporation of SWCNTs into TiO2 NFs reduces the hysteresis effect and improves the stability of the PSC devices. In this study, the best performing PSC device constructed with SWCNT structures achieves a PCE of 14.03%.

Adsorption and Desorption of Single-Stranded DNA from Single-Walled Carbon Nanotubes.

The chemical affinity of single-stranded DNA (ssDNA) to adsorb to the surface of single-walled carbon nanotubes (SWCNTs) is used for SWCNT purification, separation and in bio-devices. Despite the popularity of research on SWCNT-ssDNA conjugates, very little work has studied the removal of adsorbed ssDNA on SWCNTs. This paper reports a comprehensive study of biological, physical and chemical treatments for the removal of ssDNA from SWCNT-ssDNA suspensions. These include enzymatic cleavage, heat treatment under vacuum up to 400 °C, chemical treatments with high or low pH, oxidizing conditions, and high-ionic-strength solvents. Complimentary characterization techniques including fluorescence from a DNA-intercalating dye (YO-PRO-1) and photoelectron spectroscopy are used to exhaustively study and compare the methods investigated. Enzyme treatment is found to remove the phosphate backbone only, leaving nucleosides adsorbed to SWCNTs. Heating in inert atmosphere is ineffective at removing ssDNA. Acid, base and oxidative treatment are found to be effective for the removal of ssDNA from SWCNTs. Where possible the mechanism of desorption is described and from the findings suggestions for "best practices" are provided.

A virtual instrument to standardise the calibration of atomic force microscope cantilevers.

Atomic force microscope (AFM) users often calibrate the spring constants of cantilevers using functionality built into individual instruments. This calibration is performed without reference to a global standard, hindering the robust comparison of force measurements reported by different laboratories. Here, we describe a virtual instrument (an internet-based initiative) whereby users from all laboratories can instantly and quantitatively compare their calibration measurements to those of others-standardising AFM force measurements-and simultaneously enabling non-invasive calibration of AFM cantilevers of any geometry. This global calibration initiative requires no additional instrumentation or data processing on the part of the user. It utilises a single website where users upload currently available data. A proof-of-principle demonstration of this initiative is presented using measured data from five independent laboratories across three countries, which also allows for an assessment of current calibration.

Carbon nanotube modified probes for stable and high sensitivity conductive atomic force microscopy.

Conductive atomic force microscopy (C-AFM) is used to characterise the nanoscale electrical properties of many conducting and semiconducting materials. We investigate the effect of single walled carbon nanotube (SWCNT) modification of commercial Pt/Ir cantilevers on the sensitivity and image stability during C-AFM imaging. Pt/Ir cantilevers were modified with small bundles of SWCNTs via a manual attachment procedure and secured with a conductive platinum pad. AFM images of topography and current were collected from heterogeneous polymer and nanomaterial samples using both standard and SWCNT modified cantilevers. Typically, achieving a good current image comes at the cost of reduced feedback stability. In part, this is due to electrostatic interaction and increased tip wear upon applying a bias between the tip and the sample. The SWCNT modified tips displayed superior current sensitivity and feedback stability which, combined with superior wear resistance of SWCNTs, is a significant advancement for C-AFM.

Plasma enhanced vortex fluidic device manipulation of graphene oxide.

A vortex fluid device (VFD) with non-thermal plasma liquid processing within dynamic thin films has been developed. This plasma-liquid microfluidic platform facilitates chemical processing which is demonstrated through the manipulation of the morphology and chemical character of colloidal graphene oxide in water.

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.

Aligned Carbon Nanotube Thin Films from Liquid Crystal Polyelectrolyte Inks.

Single walled carbon nanotube thin films are fabricated by solution shearing from high concentration sodium nanotubide polyelectrolyte inks. The solutions are produced by simple stirring of the nanotubes with elemental sodium in dimethylacetamide, and the nanotubes are thus not subject to any sonication-induced damage. At such elevated concentrations (∼4 mg mL(-1)), the solutions exist in the liquid crystal phase and during deposition this order is transferred to the films, which are well aligned in the direction of shear with a 2D nematic order parameter of ∼0.7 determined by polarized absorption measurements. Compared to similarly formed films made from superacids, the polyelectrolyte films contain smaller bundles and a much narrower distribution of bundle diameters. After p-doping with an organic oxidizer, the films exhibit a very high DC electrical to optical conductivity ratio of σ(DC)/σ(OP) ∼ 35, corresponding to a calculated DC conductivity of over 7000 S cm(-1). When very thin (T550 ∼ 96%), smooth (RMS roughness, R(q) ∼ 2.2 nm), and highly aligned films made via this new route are used as the front electrodes of carbon nanotube-silicon solar cells, the power conversion efficiency is almost an order of magnitude greater than that obtained when using the much rougher (R(q) ∼ 20-30 nm) and less conductive (peak σ(DC)/σ(OP) ∼ 2.5) films formed by common vacuum filtration of the same starting material, and having the same transmittance.

Application and future challenges of functional nanocarbon hybrids.

Hybridizing nanocarbons, such as carbon nanotubes (CNTs) or graphene, with an active material is a powerful strategy towards designing next-generation functional materials for environmental and sustainable energy applications. While research on nanocomposites, created by dispersing the nanocarbon into polymer or ceramic matrices, began almost immediately after the popularization of CNTs and graphene in 1991 and 2004, respectively, nanocarbon hybrids are a relatively recent addition to the family of composite materials. In contrast to nanocomposites, which typically combine the intrinsic properties of both compounds, nanocarbon hybrids additionally provide access to both a large surface area required for gas/liquid-solid interactions and an extended interface, through which charge and energy transfer processes create synergistic effects that result in unique properties and superior performance. This progress report looks at the history of research on nanocarbons (fullerenes, CNTs and graphene) and their composites and hybrids, presents the origin of synergistic effects, reviews the most intriguing results on nanocarbon hybrid performance in heterogeneous catalysis, electrocatalysis, photocatalysis, batteries, supercapacitors, photovoltaics and sensors, and discusses remaining challenges and future research directions.

Improved field emission stability from single-walled carbon nanotubes chemically attached to silicon.

Here, we demonstrate the simple fabrication of a single-walled carbon nanotube (SWCNT) field emission electrode which shows excellent field emission characteristics and remarkable field emission stability without requiring posttreatment. Chemically functionalized SWCNTs were chemically attached to a silicon substrate. The chemical attachment led to vertical alignment of SWCNTs on the surface. Field emission sweeps and Fowler-Nordheim plots showed that the Si-SWCNT electrodes field emit with a low turn-on electric field of 1.5 V µm-1 and high electric field enhancement factor of 3,965. The Si-SWCNT electrodes were shown to maintain a current density of >740 µA cm-2 for 15 h with negligible change in applied voltage. The results indicate that adhesion strength between the SWCNTs and substrate is a much greater factor in field emission stability than previously reported.

Micropatterned arrays of porous silicon: toward sensory biointerfaces.

We describe the fabrication of arrays of porous silicon spots by means of photolithography where a positive photoresist serves as a mask during the anodization process. In particular, photoluminescent arrays and porous silicon spots suitable for further chemical modification and the attachment of human cells were created. The produced arrays of porous silicon were chemically modified by means of a thermal hydrosilylation reaction that facilitated immobilization of the fluorescent dye lissamine, and alternatively, the cell adhesion peptide arginine-glycine-aspartic acid-serine. The latter modification enabled the selective attachment of human lens epithelial cells on the peptide functionalized regions of the patterns. This type of surface patterning, using etched porous silicon arrays functionalized with biological recognition elements, presents a new format of interfacing porous silicon with mammalian cells. Porous silicon arrays with photoluminescent properties produced by this patterning strategy also have potential applications as platforms for in situ monitoring of cell behavior.