Higher harmonic large-amplitude fourier transformed alternating current voltammetry : analytical attributes derived from studies of the oxidation of ferrocenemethanol and uric acid at a glassy carbon electrode

An analytical evaluation of the higher ac harmonic components derived from large amplitude Fourier transformed voltammetry is provided for the reversible oxidation of ferrocenemethanol (FcMeOH) and oxidation of uric acid by an EEC mechanism in a pH 7.4 phosphate buffer at a glassy carbon (GC) electrode. The small background current in the analytically optimal fifth harmonic is predominantly attributed to faradaic current associated with the presence of electroactive functional groups on the GC electrode surface, rather than to capacitive current which dominates the background in the dc, and the initial three ac harmonics. The detection limits for the dc and the first to fifth harmonic ac components are 1.9, 5.89, 2.1, 2.5, 0.8, and 0.5 µM for FcMeOH, respectively, using a sine wave modulation of 100 mV at 21.46 Hz and a dc sweep rate of 111.76 mV s−1. Analytical performance then progressively deteriorates in the sixth and higher harmonics. For the determination of uric acid, the capacitive background current was enhanced and the reproducibility lowered by the presence of surface active uric acid, but the rapid overall 2e− rather than 1e– electron transfer process gives rise to a significantly enhanced fifth harmonic faradaic current which enabled a detection limit of 0.3 µM to be achieved which is similar to that reported using chemically modified electrodes. Resolution of overlapping voltammetric signals for a mixture of uric acid and dopamine is also achieved using higher fourth or fifth harmonic components, under very low background current conditions. The use of higher fourth and fifth harmonics exhibiting highly favorable faradaic to background (noise) current ratios should therefore be considered in analytical applications under circumstances where the electron transfer rate is fast.

Rapid synthesis of porous honeycomb Cu/Pd through a hydrogen-bubble templating method

A rapid electrochemical method based on using a clean hydrogen-bubble template to form a bimetallic porous honeycomb Cu/Pd structure has been investigated. The addition of palladium salt to a copper-plating bath under conditions of vigorous hydrogen evolution was found to influence the pore size and bulk concentration of copper and palladium in the honeycomb bimetallic structure. The surface was characterised by X-ray photoelectron spectroscopy, which revealed that the surface of honeycomb Cu/Pd was found to be rich with a Cu/Pd alloy. The inclusion of palladium in the bimetallic structure not only influenced the pore size, but also modified the dendritic nature of the internal wall structure of the parent copper material into small nanometre-sized crystallites. The chemical composition of the bimetallic structure and substantial morphology changes were found to significantly influence the surface-enhanced Raman spectroscopic response for immobilised rhodamine B and the hydrogen-evolution reaction. The ability to create free-standing films of this honeycomb material may also have many advantages in the areas of gas- and liquid-phase heterogeneous catalysis.

Formation of nanostructured porous Cu-Au surfaces : the influence of cationic sites on (electro)-catalysis

The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu–Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(I) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu–Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.

Electrochemical formation of porous copper 7, 7, 8, 8-tetracyanoquinodimethane and copper 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyanoquinodimethane honeycomb surfaces with superhydrophobic properties

The electrochemical formation of highly porous CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and CuTCNQF4 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) materials was undertaken via the spontaneous redox reaction between a porous copper template, created using a hydrogen bubbling template technique, and an acetonitrile solution containing TCNQ or TCNQF4. It was found that activation of the surface via vigorous hydrogen evolution that occurs during porous copper deposition and TCNQ mass transport being hindered through the porous network of the copper template influenced the growth of CuTCNQ and CuTCNQF4. This approach resulted in the fabrication of a honeycomb layered type structure where the internal walls consist of very fine crystalline needles or spikes. This combination of microscopic and nanoscopic roughness was found to be extremely beneficial for anti-wetting properties where superhydrophobic materials with contact angles as high as 177° were created. Given that CuTCNQ and CuTCNQF4 have shown potential as molecular based electronic materials in the area of switching and field emission, the creation of a surface that is moisture resistant may be of applied interest.

Superior piezoelectric composite films : taking advantage of carbon nanomaterials

Piezoelectric composites comprising an active phase of ferroelectric ceramic and a polymer matrix have recently attracted numerous sensory applications. However, it remains a major challenge to further improve their electromechanical response for advanced applications such as precision control and monitoring systems. We hereby investigated the incorporation of graphene platelets (GnPs) and multi-walled carbon nanotubes (MWNTs), each with various weight fractions, into PZT (lead zirconate titanate)/epoxy composites to produce three-phase nanocomposites. The nanocomposite films show markedly improved piezoelectric coefficients and electromechanical responses (50%) besides an enhancement of ~200% in stiffness. Carbon nanomaterials strengthened the impact of electric field on the PZT particles by appropriately raising the electrical conductivity of epoxy. GnPs have been proved far more promising in improving the poling behavior and dynamic response than MWNTs. The superior dynamic sensitivity of GnP-reinforced composite may be caused by GnPs’ high load transfer efficiency arising from their two-dimensional geometry and good compatibility with the matrix. Reduced acoustic impedance mismatch resulted from the improved thermal conductance may also contribute to the higher sensitivity of GnP-reinforced composite. This research pointed out the potential of employing GnPs to develop highly sensitive piezoelectric composites for sensing applications.

Growing biodiverse carbon-rich forests

Regrowing forests on cleared land is a key strategy to achieve both biodiversity conservation and climate change mitigation globally. Maximizing these co-benefits, however, remains theoretically and technically challenging because of the complex relationship between carbon sequestration and biodiversity in forests, the strong influence of climate variability and landscape position on forest development, the large number of restoration strategies possible, and long time-frames needed to declare success. Through the synthesis of three decades of knowledge on forest dynamics and plant functional traits combined with decision science, we demonstrate that we cannot always maximize carbon sequestration by simply increasing the functional trait diversity of trees planted. The relationships between plant functional diversity, carbon sequestration rates above-ground and in the soil are dependent on climate and landscape positions. We show how to manage ‘identities’ and ‘complementarities’ between plant functional traits in order to achieve systematically maximal co-benefits in various climate and landscape contexts. We provide examples of optimal planting and thinning rules that satisfy this ecological strategy and guide the restoration of forests that are rich in both carbon and plant functional diversity. Our framework provides the first mechanistic approach for generating decision-making rules that can be used to manage forests for multiple objectives, and supports joined carbon credit and biodiversity conservation initiatives, such as Reducing Emissions from Deforestation and forest Degradation REDD+. The decision framework can also be linked to species distribution models and socio-economic models in order to find restoration solutions that maximize simultaneously biodiversity, carbon stocks and other ecosystem services across landscapes. Our study provides the foundation for developing and testing cost-effective and adaptable forest management rules to achieve biodiversity, carbon sequestration and other socio-economic co-benefits under global change.

Influence of kaolinite/carbon black hybridization on combustion and thermal decomposition behaviors of NR composites

A series of NR composites filled with modified kaolinite (MK), carbon black (CB) and the hybrid fillercontained MK and CB, were prepared by melt blending. The microstructure, combustion and thermaldecomposition behaviors of NR composites were characterized by TEM, XRD, infrared spectroscopy, conecalorimeter test (CCT) and thermal-gravimetric analysis (TG). The results show that the filler hybridizationcan improve the dispensability and shape of the kaolinite sheets in the rubber matrix and change theinterface bond between kaolinite particles and rubber molecules. NR-3 filled by 10 phr MK and 40 phr CBhas the lowest heat release rate (HRR), mass loss rate (MLR), total heat release (THR), smoke productionrate (SPR) and the highest char residue among all the NR composites. Therefore, the hybridization ofthe carbon black particles with the kaolinite particles can effectively improve the thermal stability andcombustion properties of NR composites.

Correlating flow induced shear stress and chondrocytes activity in micro-porous scaffold using computational fluid dynamics and rapid prototyping

Flow induced shear stress plays an important role in regulating cell growth and distribution in scaffolds. This study sought to correlate wall shear stress and chondrocytes activity for engineering design of micro-porous osteochondral grafts based on the hypothesis that it is possible to capture and discriminate between the transmitted force and cell response at the inner irregularities. Unlike common tissue engineering therapies with perfusion bioreactors in which flow-mediated stress is the controlling parameter, this work assigned the associated stress as a function of porosity to influence in vitro proliferation of chondrocytes. D-optimality criterion was used to accommodate three pore characteristics for appraisal in a mixed level fractional design of experiment (DOE); namely, pore size (4 levels), distribution pattern (2 levels) and density (3 levels). Micro-porous scaffolds (n=12) were fabricated according to the DOE using rapid prototyping of an acrylic-based bio-photopolymer. Computational fluid dynamics (CFD) models were created correspondingly and used on an idealized boundary condition with a Newtonian fluid domain to simulate the dynamic microenvironment inside the pores. In vitro condition was reproduced for the 3D printed constructs seeded by high pellet densities of human chondrocytes and cultured for 72 hours. The results showed that cell proliferation was significantly different in the constructs (p<0.05). Inlet fluid velocity of 3×10-2mms-1 and average shear stress of 5.65×10-2 Pa corresponded with increased cell proliferation for scaffolds with smaller pores in hexagonal pattern and lower densities. Although the analytical solution of a Poiseuille flow inside the pores was found insufficient for the description of the flow profile probably due to the outside flow induced turbulence, it showed that the shear stress would increase with cell growth and decrease with pore size. This correlation demonstrated the basis for determining the relation between the induced stress and chondrocyte activity to optimize microfabrication of engineered cartilaginous constructs.

Adhesive characteristics of low dimensional carbon nanomaterial on actin

The biosafety of carbon nanomaterial needs to be critically evaluated with both experimental and theoretical validations before extensive biomedical applications. In this letter, we present an analysis of the binding ability of two dimensional monolayer carbon nanomaterial on actin by molecular simulation to understand their adhesive characteristics on F-actin cytoskeleton. The modelling results indicate that the positively charged carbon nanomaterial has higher binding stability on actin. Compared to crystalline graphene, graphene oxide shows higher binding influence on actin when carrying positive surface charge. This theoretical investigation provides insights into the sensitivity of actin-related cellular activities on carbon nanomaterial.

Carbon dioxide capture and gas separation on B80 fullerene

Exploring advanced materials for efficient capture and separation of CO2 is important for CO2 reduction and fuel purification. In this study, we have carried out first-principles density functional theory calculations to investigate CO2, N2, CH4, and H2 adsorption on the amphoteric regioselective B80 fullerene. Based on our calculations, we find that CO2 molecules form strong interactions with the basic sites of the B80 by Lewis acid–base interactions, while there are only weak bindings between the other three gases (N2, CH4, and H2) and the B80 adsorbent. The study also provides insight into the reaction mechanism of capture and separation of CO2 using the electron deficient B80 fullerene.

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

Electrocatalytically switchable CO2 capture : first principle computational exploration of carbon nanotubes with pyridinic nitrogen

Carbon nanotubes with specific nitrogen doping are proposed for controllable, highly selective, and reversible CO2 capture. Using density functional theory incorporating long-range dispersion corrections, we investigated the adsorption behavior of CO2 on (7,7) single-walled carbon nanotubes (CNTs) with several nitrogen doping configurations and varying charge states. Pyridinic-nitrogen incorporation in CNTs is found to induce an increasing CO2 adsorption strength with electron injecting, leading to a highly selective CO2 adsorption in comparison with N2. This functionality could induce intrinsically reversible CO2 adsorption as capture/release can be controlled by switching the charge carrying state of the system on/off. This phenomenon is verified for a number of different models and theoretical methods, with clear ramifications for the possibility of implementation with a broader class of graphene-based materials. A scheme for the implementation of this remarkable reversible electrocatalytic CO2-capture phenomenon is considered.

Emissions trading and the GATS financial services provisions : a case study of the Australian carbon pricing mechanism

Purpose The purpose of this paper is to determine whether greenhouse gas (GHG) tradeable instruments will be classified as financial products within the scope of the World Trade Organization (WTO) law and to explore the implications of this finding. Design/methodology/approach This purpose is achieved through examination of the units of the Australian Carbon Pricing Mechanism (CPM), namely eligible emissions units. These units are analysed through the lens of the definition of financial products provided in the General Agreement for Trade in Services (the GATS). Findings This paper finds that eligible emissions units will be classified as financial instruments, and therefore the provisions that govern their trade will be regulated by the GATS. Considering this, this paper explores the limitations that are introduced by the Australian legislation on the trade of eligible emissions units. Research limitations/implications This paper is limited in its analysis to the Australian CPM. In order to draw conclusions on the issues raised by this analysis it is necessary to consider the WTO requirements against an operating emissions trading scheme. The Australian CPM presents a contemporary model of an appropriate scheme. Originality/value The findings in this paper are crucial in a GHG constrained society. This is because emissions trading schemes are becoming popular measures for pricing GHG emissions, and for this reason the units that are traded and surrendered for emissions liabilities must be classified appropriately on a global scale. Failing to do this could result in differential treatment that may be contrary to the intentions of important global agreements, such as the WTO covered agreements.