Two linear beetle-type scanning tunneling microscopes

Two beetle-type scanning tunneling microscopes are described. Both designs have the thermal stability of the Besocke beetle and the simplicity of the Wilms beetle. Moreover, sample holders were designed that also allow both semiconductor wafers and metal single crystals to be studied. The coarse approach is a linear motion of the beetle towards the sample using inertial slip–stick motion. Ten wires are required to control the position of the beetle and scanner and measure the tunneling current. The two beetles were built with different sized piezolegs, and the vibrational properties of both beetles were studied in detail. It was found, in agreement with previous work, that the beetle bending mode is the lowest principal eigenmode. However, in contrast to previous vibrational studies of beetle-type scanning tunneling microscopes, we found that the beetles did not have the “rattling” modes that are thought to arise from the beetle sliding or rocking between surface asperities on the raceway. The mass of our beetles is 3–4 times larger than the mass of beetles where rattling modes have been observed. We conjecture that the mass of our beetles is above a “critical beetle mass.” This is defined to be the beetle mass that attenuates the rattling modes by elastically deforming the contact region to the extent that the rattling modes cannot be identified as distinct modes in cross-coupling measurements.

Organic–inorganic bismuth (III)-based material: A lead-free, air-stable and solution-processable light-absorber beyond organolead perovskites

Methylammonium bismuth (III) iodide single crystals and films have been developed and investigated. We have further presented the first demonstration of using this organic–inorganic bismuth-based material to replace lead/tin-based perovskite materials in solution-processable solar cells. The organic–inorganic bismuth-based material has advantages of non-toxicity, ambient stability, and low-temperature solution-processability, which provides a promising solution to address the toxicity and stability challenges in organolead- and organotin-based perovskite solar cells. We also demonstrated that trivalent metal cation-based organic–inorganic hybrid materials can exhibit photovoltaic effect, which may inspire more research work on developing and applying organic-inorganic hybrid materials beyond divalent metal cations (Pb (II) and Sn (II)) for solar energy applications.

Predicting active material utilisation in LiFePO4 electrodes using a multi-scale mathematical model

A mathematical model is developed to simulate the discharge of a LiFePO4 cathode. This model contains 3 size scales, which match with experimental observations present in the literature on the multi-scale nature of LiFePO4 material. A shrinking-core is used on the smallest scale to represent the phase-transition of LiFePO4 during discharge. The model is then validated against existing experimental data and this validated model is then used to investigate parameters that influence active material utilisation. Specifically the size and composition of agglomerates of LiFePO4 crystals is discussed, and we investigate and quantify the relative effects that the ionic and electronic conductivities within the oxide have on oxide utilisation. We find that agglomerates of crystals can be tolerated under low discharge rates. The role of the electrolyte in limiting (cathodic) discharge is also discussed, and we show that electrolyte transport does limit performance at high discharge rates, confirming the conclusions of recent literature.

Electrocrystallization of phase I, CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ•- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to −0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.

Reduction of Au3+ ions by activated surface atoms of platinum

In this work it is demonstrated that Pt electrodes can be activated by cathodic polarisation in the hydrogen evolution region which makes it prone to oxidation at potentials below that of bulk oxide formation. When an activated Pt electrode is placed in an aqueous HAuCl4 solution the electroless deposition of Au onto the surface of the electrode is observed and confirmed by cyclic voltammetry and XPS measurements. It is demonstrated that the oxidation of active Pt surface atoms provides the driving force for the spontaneous reduction of Au3+ ions into metallic Au to generate a Pt/Au surface which is highly active for the electro-oxidation of ethanol.

Combination therapy with gefitinib and rofecoxib in patients with platinum-pretreated relapsed non-small-cell lung cancer

Purpose: In non-small-cell lung cancer (NSCLC), the epidermal growth factor receptor (EGFR) and cyclooxygenase-2 (COX-2) play major roles in tumorigenesis. This phase I/II study evaluated combined therapy with the EGFR tyrosine kinase inhibitor (TKI) gefitinib and the COX-2 inhibitor rofecoxib in platinum-pretreated, relapsed, metastatic NSCLC (n = 45). Patients and Methods: Gefitinib 250 mg/d was combined with rofecoxib (dose escalated from 12.5 to 25 to 50 mg/d through three cohorts, each n = 6). Because the rofecoxib maximum-tolerated dose was not reached, the 50 mg/d cohort was expanded for efficacy evaluation (n = 33). Results: Among the 42 assessable patients, there was one complete response (CR) and two partial responses (PRs) and 12 patients with stable disease (SD); disease control rate was 35.7% (95% CI, 21.6% to 52.0%). Median time to tumor progression was 55 days (95% CI, 47 to 70 days), and median survival was 144 days (95% CI, 103 to 190 days). In a pilot study, matrix-assisted laser desorption/ionization (MALDI) proteomics analysis of baseline serum samples could distinguish patients with an objective response from those with SD or progressive disease (PD), and those with disease control (CR, PR, and SD) from those with PD. The regimen was generally well tolerated, with predictable toxicities including skin rash and diarrhea. Conclusion: Gefitinib combined with rofecoxib provided disease control equivalent to that expected with single-agent gefitinib and was generally well tolerated. Baseline serum proteomics may help identify those patients most likely to benefit from EGFR TKIs. © 2007 by American Society of Clinical Oncology.

Voltammetric, spectroscopic, and microscopic investigations of electrocrystallized forms of semiconducting AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) exhibiting different morphologies and colors

Chemically synthesized AgTCNQ exists in two forms that differ in their morphologies (needles and microcrystals) and colors (red and blue). It is now shown that both forms exhibit essentially indistinguishable X-ray diffraction, spectroscopic, and thermochemical data, implying that they are not separate phases, as implied in some literature. Electrochemical reduction of TCNQ((MeCN)) in the presence of Ag+((MeCN)) generates both red and blue AgTCNQ. On glassy carbon, platinum, or indium tin oxide electrodes and at relatively positive deposition potentials, slow growth of high aspect ratio, red needle AgTCNQ crystals occurs. After longer times and at more negative deposition potentials, blue microcrystalline AgTCNQ thin films are favored. Blue AgTCNQ is postulated to be generated via reduction of a Ag+\[(TCNQ(center dot-))(TCNQ)]((MeCN)) intermediate. At even more negative potentials, Ag-(metal) formation inhibits further growth of AgTCNQ. On a gold electrode, Ag-(metal)) deposition occurs at more positive potentials than on the other electrode materials examined. However, surface plasmon resonance data indicate (hat a small potential region is available between the stripping of Ag-(metal)) and the oxidation of TCNQ(center dot-)(MeCN) back to TCNQ(MeCN) where AgTCNQ may form. AgTCNQ in both the red and blue forms also can be prepared electrochemically on a TCNQ((s)) modified electrode in -0.1 M AgNO3(aq) where deposition of Ag(m,,,I) onto the TCNQ((s)) crystals allows a charge transfer process to occur. However, the morphology formed in this solid-solid phase transformation is more difficult to control.

Structure-controlled, vertical graphene-based, binder-free electrodes from plasma-reformed butter enhance supercapacitor performance

Vertical graphene nanosheets (VGNS) hold great promise for high-performance supercapacitors owing to their excellent electrical transport property, large surface area and in particular, an inherent three-dimensional, open network structure. However, it remains challenging to materialise the VGNS-based supercapacitors due to their poor specific capacitance, high temperature processing, poor binding to electrode support materials, uncontrollable microstructure, and non-cost effective way of fabrication. Here we use a single-step, fast, scalable, and environmentally-benign plasma-enabled method to fabricate VGNS using cheap and spreadable natural fatty precursor butter, and demonstrate the controllability over the degree of graphitization and the density of VGNS edge planes. Our VGNS employed as binder-free supercapacitor electrodes exhibit high specific capacitance up to 230 F g−1 at a scan rate of 10 mV s−1 and >99% capacitance retention after 1,500 charge-discharge cycles at a high current density, when the optimum combination of graphitic structure and edge plane effects is utilised. The energy storage performance can be further enhanced by forming stable hybrid MnO2/VGNS nano-architectures which synergistically combine the advantages from both VGNS and MnO2. This deterministic and plasma-unique way of fabricating VGNS may open a new avenue for producing functional nanomaterials for advanced energy storage devices.

Planar silver nanowire, carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/squ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω−1 is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.

Pathway to high throughput, low cost indium-free transparent electrodes

A roll-to-roll compatible, high throughput process is reported for the production of highly conductive, transparent planar electrode comprising an interwoven network of silver nanowires and single walled carbon nanotubes imbedded into poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). The planar electrode has a sheet resistance of between 4 and 7 Ω □−1 and a transmission of >86% between 800 and 400 nm with a figure of merit of between 344 and 400 Ω−1. The nanocomposite electrode is highly flexible and retains a low sheet resistance after bending at a radius of 5 mm for up to 500 times without loss. Organic photovoltaic devices containing the planar nanocomposite electrodes had efficiencies of ∼90% of control devices that used indium tin oxide as the transparent conducting electrode.

Single atom (Pd/Pt) supported on graphitic carbon nitride as efficient photocatalyst for visible-light reduction of carbon dioxide

Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.