Hydrogen evolution by a metal-free electrocatalyst

Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.

Baidu’s perfect paradox : free speech and the right to censor

China’s biggest search engine has a constitutional right to filter its search results, a US court found last month. But that’s just the start of the story. Eight New York-based pro-democracy activists sued Baidu Inc in 2011, seeking damages because Baidu prevents their work from showing up in search results. Baidu follows Chinese law that requires it to censor politically sensitive results. But in what the plaintiffs’ lawyer has dubbed a “perfect paradox”, US District Judge Jesse Furman has dismissed the challenge, explaining that to hold Baidu liable for its decisions to censor pro-democracy content would itself infringe the right to free speech.

Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Comparison of 3 accelerometer data reduction approaches, step counts, and 2 self-report measures for estimating physical activity in free-living adults

Background Accelerometers have become one of the most common methods of measuring physical activity (PA). Thus, validity of accelerometer data reduction approaches remains an important research area. Yet, few studies directly compare data reduction approaches and other PA measures in free-living samples. Objective To compare PA estimates provided by 3 accelerometer data reduction approaches, steps, and 2 self-reported estimates: Crouter's 2-regression model, Crouter's refined 2-regression model, the weighted cut-point method adopted in the National Health and Nutrition Examination Survey (NHANES; 2003-2004 and 2005-2006 cycles), steps, IPAQ, and 7-day PA recall. Methods A worksite sample (N = 87) completed online-surveys and wore ActiGraph GT1M accelerometers and pedometers (SW-200) during waking hours for 7 consecutive days. Daily time spent in sedentary, light, moderate, and vigorous intensity activity and percentage of participants meeting PA recommendations were calculated and compared. Results Crouter's 2-regression (161.8 +/- 52.3 minutes/day) and refined 2-regression (137.6 +/- 40.3 minutes/day) models provided significantly higher estimates of moderate and vigorous PA and proportions of those meeting PA recommendations (91% and 92%, respectively) as compared with the NHANES weighted cut-point method (39.5 +/- 20.2 minutes/day, 18%). Differences between other measures were also significant. Conclusions When comparing 3 accelerometer cut-point methods, steps, and self-report measures, estimates of PA participation vary substantially.

Free for all : a case study examining implementation factors of one-to-one device programs

Despite significant investment in school one-to-one device programs, little is known about which aspects of program implementation work and why. Through a comparison of two implementation models, adopter-diffusion and saturation, and using existing data from the One Laptop per Child Australia laptop program, we explored how factors of implementation may affect device diffusion, learning and educational outcomes, and program sustainability in schools. In this article we argue that more focused research into implementation of one-to-one device programs, moving beyond comparisons of “devices versus without devices,” is needed to provide reliable data to inform future program funding and advance this area of research.

The use of uniaxial and triaxial accelerometers to measure children's "free-play" physical activity

In order to effectively measure the physical activity of children, objective monitoring devices must be able to quantify the intermittent and nonlinear movement of free play. The purpose of this study was to investigate the validity of the Computer Science and Applications (CSA) uniaxial accelerometer and the TriTrac-R3D triaxial accelerometer with respect to their ability to measure 8 "free-play" activities of different intensity. The activities ranged from light to very vigorous in intensity and included activities such as throwing and catching, hopscotch, and basketball. Twenty-eight children, ages 9 to 11, wore a CSA and a heart rate monitor while performing the activities. Sixteen children also wore a Tritrac. Counts from the CSA, Tritrac, and heart rates corresponding to the last 3 min of the 5 min spent at each activity were averaged and used in correlation analyses. Across all 8 activities, Tritrac counts were significantly correlated with predicted MET level (r= 0.69) and heart rate (r= 0.73). Correlations between CSA output, predicted MET level (0.43), and heart rate (0.64) were also significant but were lower than those observed for the Tritrac. These data indicate that accelerometers are an appropriate methodology for measuring children's free-play physical activities.

Label-free SERS for natural product provenance

Introduction Natural product provenance is important in the food, beverage and pharmaceutical industries, for consumer confidence and with health implications. Raman spectroscopy has powerful molecular fingerprint abilities. Surface Enhanced Raman Spectroscopy’s (SERS) sharp peaks allow distinction between minimally different molecules, so it should be suitable for this purpose. Methods Naturally caffeinated beverages with Guarana extract, coffee and Red Bull energy drink as a synthetic caffeinated beverage for comparison (20 µL ea.) were reacted 1:1 with Gold nanoparticles functionalised with anti-caffeine antibody (ab15221) (10 minutes), air dried and analysed in a micro-Raman instrument. The spectral data was processed using Principle Component Analysis (PCA). Results The PCA showed Guarana sourced caffeine varied significantly from synthetic caffeine (Red Bull) on component 1 (containing 76.4% of the variance in the data). See figure 1. The coffee containing beverages, and in particular Robert Timms (instant coffee) were very similar on component 1, but the barista espresso showed minor variance on component 1. Both coffee sourced caffeine samples varied with red Bull on component 2, (20% of variance). ************************************************************ Figure 1 PCA comparing a naturally caffeinated beverage containing Guarana with coffee. ************************************************************ Discussion PCA is an unsupervised multivariate statistical method that determines patterns within data. Figure 1 shows Caffeine in Guarana is notably different to synthetic caffeine. Other researchers have revealed that caffeine in Guarana plants is complexed with tannins. Naturally sourced/ lightly processed caffeine (Monster Energy, Espresso) are more inherently different than synthetic (Red Bull) /highly processed (Robert Timms) caffeine, in figure 1, which is consistent with this finding and demonstrates this technique’s applicability. Guarana provenance is important because it is still largely hand produced and its demand is escalating with recognition of its benefits. This could be a powerful technique for Guarana provenance, and may extend to other industries where provenance / authentication are required, e.g. the wine or natural pharmaceuticals industries.

The free encyclopaedia that anyone can edit: the shifting values of Wikipedia editors

Wikipedia is often held up as an example of the potential of the internet to foster open, free and non-commercial collaboration. However such discourses often conflate these values without recognising how they play out in reality in a peer-production community. As Wikipedia is evolving, it is an ideal time to examine these discourses and the tensions that exist between its initial ideals and the reality of commercial activity in the encyclopaedia. Through an analysis of three failed proposals to ban paid advocacy editing in the English language Wikipedia, this paper highlights the shift in values from the early editorial community that forked encyclopaedic content over the threat of commercialisation, to one that today values the freedom that allows anyone to edit the encyclopaedia.

Ultra sensitive label free surface enhanced Raman spectroscopy method for the detection of biomolecules

We present a proof of concept for a novel nanosensor for the detection of ultra-trace amounts of bio-active molecules in complex matrices. The nanosensor is comprised of gold nanoparticles with an ultra-thin silica shell and antibody surface attachment, which allows for the immobilization and direct detection of bio-active molecules by surface enhanced Raman spectroscopy (SERS) without requiring a Raman label. The ultra-thin passive layer (~1.3 nm thickness) prevents competing molecules from binding non-selectively to the gold surface without compromising the signal enhancement. The antibodies attached on the surface of the nanoparticles selectively bind to the target molecule with high affinity. The interaction between the nanosensor and the target analyte result in conformational rearrangements of the antibody binding sites, leading to significant changes in the surface enhanced Raman spectra of the nanoparticles when compared to the spectra of the un-reacted nanoparticles. Nanosensors of this design targeting the bio-active compounds erythropoietin and caffeine were able to detect ultra-trace amounts the analyte to the lower quantification limits of 3.5×10−13 M and 1×10−9 M, respectively.

Vertical graphene gas- and bio-sensors via catalyst-free, reactive plasma reforming of natural honey

A rapid reforming of natural honey exposed to reactive low-temperature Ar + H2 plasmas produced high-quality, ultra-thin vertical graphenes, without any metal catalyst or external heating. This transformation is only possible in the plasma and fails in similar thermal processes. The process is energy-efficient, environmentally benign, and is much cheaper than common synthesis methods based on purified hydrocarbon precursors. The graphenes retain the essential minerals of natural honey, feature reactive open edges and reliable gas- and bio-sensing performance.

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.

Plasma-enabled graded nanotube biosensing arrays on a Si nanodevice platform : catalyst-free integration and in situ detection of nucleation events

Low-temperature plasmas in direct contact with arbitrary, written linear features on a Si wafer enable catalyst-free integration of carbon nanotubes into a Si-based nanodevice platform and in situ resolution of individual nucleation events. The graded nanotube arrays show reliable, reproducible, and competitive performance in electron field emission and biosensing nanodevices.

Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Single-step, catalyst-free plasma-assisted synthesis and growth mechanism of single-crystalline aluminum nitride nanorods

Synthesis of one-dimensional AlN nanostructures commonly requires high process temperatures (>900 °C), metal catalyst, and hazardous gas/powder precursors. We report on a simple, single-step, catalyst-free, plasma-assisted growth of dense patterns of size-uniform single-crystalline AlN nanorods at a low substrate temperature (∼650 °C) without any catalyst or hazardous precursors. This unusual growth mechanism is based on highly effective plasma dissociation of N2 molecules, localized species precipitation on AlN islands, and reduced diffusion on the nitrogen-rich surface. This approach can also be used to produce other high-aspect-ratio oxide and nitride nanostructures for applications in energy conversion, sensing, and optoelectronics. © 2010 American Institute of Physics.

The effect of the nonparabolicity of the free carriers dispersion law on the propagation of surface polaritons in a semiconductor-metal structure

The results of a study on the influence of the nonparabolicity of the free carriers dispersion law on the propagation of surface polaritons (SPs) located near the interface between an n-type semiconductor and a metal arc reported. The semiconductor plasma is assumed to be warm and nonisothermal. The nonparabolicity of the electron dispersion law has two effects. The first one is associated with nonlinear self-interaction of the SPs. The nonlinear dispersion equation and the nonlinear Schrodinger equation for the amplitude of the SP envelope are obtained. The nonlinear evolution of the SP is studied on the base of the above mentioned equations. The second effect results in third harmonics generation. Analysis shows that these third harmonics may appear as a pure surface polariton, a pseudosurface polariton, or a superposition of a volume wave and a SP depending on the wave frequency, electron density and lattice dielectric constant.