Direct Visualisation of the Surface Atomic Active Sites of Carbon-Supported Co3 O4 Nanocrystals via High-Resolution Phase Restoration.

The atomic arrangement of the terminating facets on spinel Co3 O4 nanocrystals is strongly linked to their catalytic performance. However, the spinel crystal structure offers multiple possible surface terminations depending on the synthesis. Thus, understanding the terminating surface atomic structure is essential in developing high-performance Co3 O4 nanocrystals. In this work, we present direct atomic-scale observation of the surface terminations of Co3 O4 nanoparticles supported on hollow carbon spheres (HCSs) using exit wavefunction reconstruction from aberration-corrected transmission electron microscopy focal-series. The restored high-resolution phases show distinct resolved oxygen and cobalt atomic columns. The data show that the structure of {100}, {110}, and {111} facets of spinel Co3 O4 exhibit characteristic active sites for carbon monoxide (CO) adsorption, in agreement with density functional theory calculations. Of these facets, the {100} and {110} surface terminations are better suited for CO adsorption than the {111}. However, the presence of oxygen on the {111} surface termination indicates this facet also plays an essential role in CO adsorption. Our results demonstrate direct evidence of the surface termination atomic structure beyond the assumed stoichiometry of the surface.

The role of oxygen in a carbon source (castor oil versus paraffin oil) in the synthesis of carbon nano-onions.

The role of a carbon source containing oxygen groups on the physicochemical properties of carbon nano-onions (CNOs) was investigated. Two oils, castor oil (with O groups) and paraffin oil (without O groups) were converted to CNOs in gram-scale yields using an open flame pyrolysis procedure. The products were heated under argon at 900 °C for varying times (1 h, 2 h, 3 h), to investigate the temperature dependence on their structural properties. TGA studies indicated different decomposition behaviour for the different samples with the annealed paraffinic CNOs (CNOP) having a higher decomposition temperature (>600 °C) than the castor oil derived CNOs (CNOC) (<600 °C). TEM images revealed formation of typical chain-like quasi-spherical nanostructures with particles size distributions for the CNOP (22-32 ± 7.8 nm) and the CNOC (44-51 ± 9.9 nm) materials. A detailed Raman analysis of the CNOs revealed that the graphicity of the CNOs varied with both the carbon oil source and the annealing time. Deconvolution of the first order Raman spectra revealed changes in the parameters of the major Raman bands that were then correlated with defect density ratios. Finally, bandwidth analysis depicted the dependence of the graphicity of the CNOs with heat treatment. The data thus indicate that the presence of oxygen in the carbon source provides a method for producing different CNOs and that simple procedures can be used to produce these different CNOs.

Importance of Surface Topography in Both Biological Activity and Catalysis of Nanomaterials: Can Catalysis by Design Guide Safe by Design?

It is acknowledged that the physicochemical properties of nanomaterials (NMs) have an impact on their toxicity and, eventually, their pathogenicity. These properties may include the NMs' surface chemical composition, size, shape, surface charge, surface area, and surface coating with ligands (which can carry different functional groups as well as proteins). Nanotopography, defined as the specific surface features at the nanoscopic scale, is not widely acknowledged as an important physicochemical property. It is known that the size and shape of NMs determine their nanotopography which, in turn, determines their surface area and their active sites. Nanotopography may also influence the extent of dissolution of NMs and their ability to adsorb atoms and molecules such as proteins. Consequently, the surface atoms (due to their nanotopography) can influence the orientation of proteins as well as their denaturation. However, although it is of great importance, the role of surface topography (nanotopography) in nanotoxicity is not much considered. Many of the issues that relate to nanotopography have much in common with the fundamental principles underlying classic catalysis. Although these were developed over many decades, there have been recent important and remarkable improvements in the development and study of catalysts. These have been brought about by new techniques that have allowed for study at the nanoscopic scale. Furthermore, the issue of quantum confinement by nanosized particles is now seen as an important issue in studying nanoparticles (NPs). In catalysis, the manipulation of a surface to create active surface sites that enhance interactions with external molecules and atoms has much in common with the interaction of NP surfaces with proteins, viruses, and bacteria with the same active surface sites of NMs. By reviewing the role that surface nanotopography plays in defining many of the NMs' surface properties, it reveals the need for its consideration as an important physicochemical property in descriptive and predictive toxicology. Through the manipulation of surface topography, and by using principles developed in catalysis, it may also be possible to make safe-by-design NMs with a reduction of the surface properties which contribute to their toxicity.

Effect of Gold Nanospheres and Nanodots on the Performance of PEDOT:PSS Solar Cells.

Gold nanospheres were synthesized using a modified Turkevich method (d = 14±4 nm, λmax = 531 nm), while gold nanodots made of spheres (5±2 nm) and non-spherical nanodots (aspect ratio of 1.7±0.4) were synthesized using a modified seed mediated method. The spherical gold nanodots exhibited a transverse excitation mode at 525 nm while the non-spherical gold nanodots showed an additional longitudinal excitation mode observed in the UV-vis spectrum at 794 nm. The gold nanodots also exhibited a surface enhanced Raman effect which significantly influenced the electronic properties of the photovoltaic device. The incorporation of Au nanospheres in a PEDOT:PSS hole transport layer increased the photovoltaic device efficiency by 51%. This was attributed to a decrease in the series resistance which improved the hole transport pathways in the PEDOT:PSS and enhanced the current density of the photovoltaic device. In contrast, incorporation of spherical and non-spherical gold nanodots into the PEDOT:PSS hole transport layer resulted in a decrease in current density and a consequent decrease in efficiency. This can be attributed to the electron-hole recombination and accumulation of space charges by the non-spherical gold nanodots in PEDOT:PSS resulting in an increased series resistance and leakage currents and hence a reduced device performance. Thus, the morphological, structural and opto-electrical properties of the gold nanospheres and nanodots influenced the device performance of the PEDOT:PSS solar cells.

Single-step synthesis of crystalline h-BN quantum- and nanodots embedded in boron carbon nitride films.

Herein we report on the synthesis and characterization of novel crystalline hexagonal boron nitride (h-BN) quantum- and nanodots embedded in large-area boron carbon nitride (BCN) films. The films were grown on a Cu substrate by an atmospheric pressure chemical vapour deposition technique. Methane, ammonia, and boric acid were used as precursors for C, N and B to grow these few atomic layer thick uniform films. We observed that both the size of the h-BN quantum/nanodots and thickness of the BCN films were influenced by the vaporization temperature of boric acid as well as the H3BO3 (g) flux over the Cu substrate. These growth conditions were easily achieved by changing the position of the solid boric acid in the reactor with respect to the Cu substrate. Atomic force microscope (AFM) and TEM analyses show a variation in the h-BN dot size distribution, ranging from nanodots (∼224 nm) to quantum dots (∼11 nm) as the B-source is placed further away from the Cu foil. The distance between the B-source and the Cu foil gave an increase in the C atomic composition (42 at% C-65 at% C) and a decrease in both B and N contents (18 at% B and 14 at% N to 8 at% B and 7 at% N). UV-vis absorption spectra showed a higher band gap energy for the quantum dots (5.90 eV) in comparison with the nanodots (5.68 eV) due to a quantum confinement effect. The results indicated that the position of the B-source and its reaction with ammonia plays a significant role in controlling the nucleation of the h-BN quantum- and nanodots. The films are proposed to be used in solar cells. A mechanism to explain the growth of h-BN quantum/nanodots in BCN films is reported.

Nitrogen-doped, boron-doped and undoped multiwalled carbon nanotube/polymer composites in WORM memory devices.

We report the preparation of write-once-read-many times memory devices using composites of carbon nanotubes and poly(vinyl phenol) sandwiched between Al electrodes. Three types of nanotubes (undoped multiwalled carbon nanotubes, nitrogen-doped multiwalled carbon nanotubes and boron-doped multiwalled carbon nanotubes) are investigated for this application. The OFF to ON state switching threshold is only slightly dependent on nanotube type, but the ON/OFF current ratio depends on both nanotube type and concentration and varies up to 10(6), decreasing for nanotube concentrations larger than 0.50 wt% in the composite.

Application of gallium nitride nanostructures and nitrogen doped carbon spheres as supports for the hydrogenation of cinnamaldehyde.

This paper reports on the synthesis and use of nanostructures of gallium nitride (GaN NSs) and nitrogen doped carbon spheres (NCSs) as support materials for the hydrogenation of cinnamaldehyde. This study provides the first investigation of GaN as a catalyst support in hydrogenation reactions. The GaN NSs were synthesized via chemical vapour deposition (CVD) in a double stage furnace (750 degrees C) while NCSs were made by CVD in a single stage furnace (950 degrees C) respectively. TEM analysis revealed that the GaN NSs were rod-like with average diameters of 200 nm, while the NCSs were solid with smoother surfaces, and with diameters of 450 nm. Pd nanoparticles (1 and 3% loadings) were uniformly dispersed on acid functionalized GaN NSs and NCS. The Pd nanoparticles had average diameters that were influenced by the type of support material used. The GaN NSs and NCSs were tested for the selective hydrogenation of cinnamaldehyde in isopropanol at 40 and 60 degrees C under atmospheric pressure. A comparative study of the activity of the nanostructured materials revealed that the order of catalyst activity was 3% Pd/GaN > 3% Pd/NCSs > 1% Pd/NCSs > 1% Pd/GaN. However, 100% selectivity to hydrocinnamaldehyde (HCALD) was obtained with 1% Pd/GaN at reasonable conversion rates.

Functionalized spherical carbon nanostructure/poly(vinylphenol) composites for application in low power consumption write-once-read-many times memories.

We apply functionalized carbon nanoshell and carbon sphere based composites in poly(vinylphenol) matrix in write-once-read-many-times memory elements. The devices based on carbon nanoshells show an ON/OFF current ratio of 10(5) and long-term information retention. The functionalized carbon nanoshells and carbon spheres show improved dispersion in the poly(vinylphenol) matrix, allowing the preparation of homogeneous films even at the submicrometer scale. The low ON current allows low power operation, dissipating less than 10(-4) J per square meter device active area during the write operation, which is the most energy consuming one.

Catalyst Design: Counter Anion Effect on Ni Nanocatalysts Anchored on Hollow Carbon Spheres.

Herein, the influence of the counter anion on the structural properties of hollow carbon spheres (HCS) support was investigated by varying the nickel metal precursor salts applied. TEM and SEM micrographs revealed the dimensional dependence of the HCS shell on the Ni precursor salt, as evidenced by thick (~42 nm) and thin (~23 nm) shells for the acetate and chloride-based salts, respectively. Importantly, the effect of the precursor salt on the textural properties of the HCS nanosupports (~565 m2/gNi(acet)) and ~607 m2/gNiCl), influenced the growth of the Ni nanoparticles, viz for the acetate-(ca 6.4 nm)- and chloride (ca 12 nm)-based salts, respectively. Further, XRD and PDF analysis showed the dependence of the reduction mechanism relating to nickel and the interaction of the nickel-carbon support on the type of counter anion used. Despite the well-known significance of the counter anion on the size and crystallinity of Ni nanoparticles, little is known about the influence of such counter anions on the physicochemical properties of the carbon support. Through this study, we highlight the importance of the choice of the Ni-salt on the size of Ni in Ni-carbon-based nanocatalysts.

The Transformation of 0-D Carbon Dots into 1-, 2- and 3-D Carbon Allotropes: A Minireview.

Carbon dots (CDs) represent a relatively new type of carbon allotrope with a 0-D structure and with nanoparticle sizes < 10 nm. A large number of research articles have been published on the synthesis, characteristics, mechanisms and applications of this carbon allotrope. Many of these articles have also shown that CDs can be synthesized from "bottom-up" and "top-down" methods. The "top-down" methods are dominated by the breaking down of large carbon structures such as fullerene, graphene, carbon black and carbon nanotubes into the CDs. What is less known is that CDs also have the potential to be used as carbon substrates for the synthesis of larger carbon structures such as 1-D carbon nanotubes, 2-D or 3-D graphene-based nanosheets and 3-D porous carbon frameworks. Herein, we present a review of the synthesis strategies used to convert the 0-D carbons into these higher-dimensional carbons. The methods involve the use of catalysts or thermal procedures to generate the larger structures. The surface functional groups on the CDs, typically containing nitrogen and oxygen, appear to be important in the process of creating the larger carbon structures that typically are formed via the generation of covalent bonds. The CD building blocks can also 'aggregate' to form so called supra-CDs. The mechanism for the formation of the structures made from CDs, the physical properties of the CDs and their applications (for example in energy devices and as reagents for use in medicinal fields) will also be discussed. We hope that this review will serve to provide valuable insights into this area of CD research and a novel viewpoint on the exploration of CDs.

Platinum Nanocatalysts Supported on Defective Hollow Carbon Spheres: Oxygen Reduction Reaction Durability Studies.

The durability and long-term applicability of catalysts are critical parameters for the commercialization and adoption of fuel cells. Even though a few studies have been conducted on hollow carbon spheres (HCSs) as supports for Pt in oxygen reduction reactions (ORR) catalysis, in-depth durability studies have not been conducted thus far. In this study, Pt/HCSs and Pt/nitrogen-doped HCSs (Pt/NHCSs) were prepared using a reflux deposition technique. Small Pt particles were formed with deposition on the outside of the shell and inside the pores of the shell. The new catalysts demonstrated high activity (>380 µA cm-2 and 240 mA g-1) surpassing the commercial Pt/C by more than 10%. The catalysts demonstrated excellent durability compared to a commercial Pt/C in load cycling, experiencing less than 50% changes in the mass-specific activity (MA) and surface area-specific activity (SA). In stop-start durability cycling, the new materials demonstrated high stability with more than 50% retention of electrochemical active surface areas (ECSAs). The results can be rationalised by the high BET surface areas coupled with an array of meso and micropores that led to Pt confinement. Further, pair distribution function (PDF) analysis of the catalysts confirmed that the nitrogen and oxygen functional groups, as well as the shell curvature/roughness provided defects and nucleation sites for the deposition of the small Pt nanoparticles. The balance between graphitic and diamond-like carbon was critical for the electronic conductivity and to provide strong Pt-support anchoring.

From 0D to 2D: N-doped carbon nanosheets for detection of alcohol-based chemical vapours.

The application of N-doped carbon nanosheets, with and without embedded carbon dots, as active materials for the room temperature chemoresistive detection of methanol and/or ethanol is presented. The new carbons were made by converting 0D N-doped carbon dots (NCDs) to 2D nitrogen-doped carbon nanosheets by heat treatment (200-700 °C). The nanosheets exhibited a lateral size of ∼3 µm and a thickness of ∼12 nm at the highest annealing temperature. Both Raman and TEM analyses showed morphological transitions of the dots to the sheets, whilst XPS analysis revealed transformation of the N-bonding states with increasing temperature. PDF analysis confirmed the presence of defective carbon sheets. Room temperature screening of the chemical vapours of two alcohols (methanol and ethanol), revealed that the structure and the type of N-configuration influenced the detection of the chemical vapours. For instance, the lateral size of the nanosheets and the high charge density N-configurations promoted detection of both methanol and ethanol vapours at good sensitivity (-16.8 × 10-5 ppm-1 EtOH and 1.2 × 10-5 ppm-1 MeOH) and low LoD (∼44 ppmEtOH and ∼30.3 ppmMeOH) values. The study showed that the composite nature as well as the large basal area of the carbon nanosheets enabled generation of adequate defective sites that facilitated easy adsorption of the VOC analyte molecules, thereby eliminating the need to use conducting polymers or the formation of porous molecular frameworks for the alcohol detection.

Composites of polyvinyl alcohol and carbon (coils, undoped and nitrogen doped multiwalled carbon nanotubes) as ethanol, methanol and toluene vapor sensors.

We investigate the chemical sensing behavior of composites prepared with polyvinyl alcohol and carbon materials (undoped multiwalled carbon nanotubes, nitrogen-doped multiwalled carbon nanotubes and carbon nanocoils). We determine the sensitivity of thin films of these composites for ethanol, methanol and toluene vapor, comparing their conductance and capacitance responses. The composite that exhibits highest sensitivity depends on specific vapor, vapor concentration and measured electrical response, showing that the interactivity of the carbon structure with chemical species depend on structural specificities of the carbon structure and doping.

AC-conductance and capacitance measurements for ethanol vapor detection using carbon nanotube-polyvinyl alcohol composite based devices.

We report the preparation of inexpensive ethanol sensor devices using multiwalled carbon nanotube-polyvinyl alcohol composite films deposited onto interdigitated electrodes patterned on phenolite substrates. We investigate the frequency dependent response of the device conductance and capacitance showing that higher sensitivity is obtained at higher frequency if the conductance is used as sensing parameter. In the case of capacitance measurements, higher sensitivity is obtained at low frequency. Ethanol detection at a concentration of 300 ppm in air is demonstrated. More than 80% of the sensor conductance and capacitance variation response occurs in less than 20 s.

Microwave-assisted synthesis of titania-amorphous carbon nanotubes/amorphous nitrogen-doped carbon nanotubes nanohybrids for photocatalytic degradation of textile wastewater.

The synthesis of TiO2 nanohybrids fabricated using amorphous carbon nanotubes (aCNTs) and amorphous nitrogen doped carbon nanotubes (aNCNTs) via a microwave-assisted hydrothermal method is reported. The photocatalytic removal of Reactive Red 120 (RR 120) and organics from industrial textile wastewater using these nanohybrids is discussed. The synthesis process was shown to promote the removal of nano graphitic flakes from the outer walls of the aNCNTs and aCNTs and subsequent incorporation of these carbonaceous materials into TiO2 nanocrystals as such enabling a stronger interaction between the TiO2 and the carbonaceous material. This enabled the production of a surface plasmon resonance on the TiO2 and NTiO2 nanocrystals. The carbon residue was confirmed to be aCNTs and aNCNTs by TGA and DTA analyses. XPS analysis for the TiO2-aNCNT nanohybrids confirmed the C and N doping of TiO2 due to the amorphous residues from the aNCNTs. In addition, XPS and FTIR spectroscopic analysis confirmed the presence of surface oxygen-based groups. TEM micrograph analysis showed that aCNTs and aNCNTs promote the formation of monodispersed and small TiO2 particles; all below 7.4 nm. The NTiO2-aNCNT nanohybrids have the lowest energy band gap at 2.97 eV and the lowest PL intensity. The TiO2-aNCNT nanohybrids had superior adsorptive (98.2%) and photocatalytic (99%) removal for 20 ppm RR 120 dye solution at k 1app 3.44 × 10-2 min-1. Lastly, all the nanohybrids demonstrate the formation of visible-light absorbing intermediates from VAT-dyed textile wastewater. The work demonstrates the possibility of the use of these nanohybrids to derive new products through photocatalytic nanohybrids.

Oxidation of Benzyl Alcohol Using Cobalt Oxide Supported Inside and Outside Hollow Carbon Spheres.

Cobalt oxide nanoparticles (6 nm) supported both inside and outside of hollow carbon spheres (HCSs) were synthesized by using two different polymer templates. The oxidation of benzyl alcohol was used as a model reaction to evaluate the catalysts. PXRD studies indicated that the Co oxidation state varied for the different catalysts due to reduction of the Co by the carbon, and a metal oxidation step prior to the benzyl alcohol oxidation enhanced the catalytic activity. The metal loading influenced the catalytic efficiency, and the activity decreased with increasing metal loading, possibly due to pore filling effects. The catalysts showed similar activity and selectivity (to benzaldehyde) whether placed inside or outside the HCS (63 % selectivity at 50 % conversion). No poisoning was observed due to product build up in the HCS.

A facile procedure to shorten multiwalled carbon nanotubes.

Multi-walled carbon nanotubes (MWCNTs) with > 95% purity were synthesized over a Fe-Co/CaCO3 catalyst using chemical vapour deposition (CVD). Both the CNT yield and the outer diameters increased with time on line in the presence of acetylene. More significantly, the tubes were reduced in length and became stub-like with time. TEM analysis revealed that the CNTs commenced shortening after 2 h of reaction time. Reagent residues (e.g., Ca, CaO, OH/COOH groups and Fe-Co oxides) were found not to influence the CNT bond breaking reaction. CNT growth over Fe-Co supported on silica or CaCO3-Ca3(PO4)2 gave similar results. Further, MWCNTs produced by a floating catalyst method, carbon helices produced from Fe-Co-In/A2O3, and N doped CNTs also revealed tube shortening as a function of reaction time under a flow of acetylene. It is thus apparent that MWCNTs can readily be shortened by the facile procedure of depositing carbon from excess C2H2 on the outer walls of CNTs.