Effects of HNO3 molecular doping in graphene/Si Schottky barrier solar cells

Schottky barrier solar cells based on graphene/n-silicon heterojunction have been fabricated and characterized and the effect of graphene molecular doping by HNO3 on the solar cells performances have been analyzed. Different doping conditions and thermal annealing processes have been tested to asses and optimize the stability of the devices. The PCE of the cells increases after the treatment by HNO3 and reaches 5% in devices treated at 200 °C immediately before the exposition to the oxidant. Up to now our devices retain about 80% of efficiency over a period of two weeks, which represents a good stability result for similar devices.

Vibrational spectroscopy of the borate mineral priceite : implications for the molecular structure

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm−1 are assigned to the BO stretching vibration of the B10O19 units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm−1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm−1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm−1 together with bands at 689, 697, 736, and 602 cm−1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm−1 with a distinct shoulder at 3568 cm−1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm−1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.

Temperature and strain-rate dependent fracture strength of graphynes

Graphyne is an allotrope of graphene. The mechanical properties of graphynes (α-, β-, γ- and 6,6,12-graphynes) under uniaxial tension deformation at different temperatures and strain rates are studied using molecular dynamics simulations. It is found that graphynes are more sensitive to temperature changes than graphene in terms of fracture strength and Young's modulus. The temperature sensitivity of the different graphynes is proportionally related to the percentage of acetylenic linkages in their structures, with the α-graphyne (having 100% of acetylenic linkages) being most sensitive to temperature. For the same graphyne, temperature exerts a more pronounced effect on the Young's modulus than fracture strength, which is different from that of graphene. The mechanical properties of graphynes are also sensitive to strain rate, in particular at higher temperatures.

Surface plasmon-enhanced zeolite catalysis under light irradiation and its correlation with molecular polarity of reactants

Enhanced catalytic performance of zeoltes via the plasmonic effect of gold nanoparticles has been discovered to be closely correlated with the molecular polarity of reactants. The intensified polarised electrostatic field of Na+ in NaY plays a critical role in stretching the C=O bond of aldehydes to improve the reaction rate.

A constitutive model for mechanical response characterization of pumpkin peel and flesh tissues under tensile and compressive loadings

Enhancing quality of food products and reducing volume of waste during mechanical operations of food industry requires a comprehensive knowledge of material response under loadings. While research has focused on mechanical response of food material, the volume of waste after harvesting and during processing stages is still considerably high in both developing and developed countries. This research aims to develop and evaluate a constitutive model of mechanical response of tough skinned vegetables under postharvest and processing operations. The model focuses on both tensile and compressive properties of pumpkin flesh and peel tissues where the behaviours of these tissues vary depending on various factors such as rheological response and cellular structure. Both elastic and plastic response of tissue were considered in the modelling process and finite elasticity combined with pseudo elasticity theory was applied to generate the model. The outcomes were then validated using the published results of experimental work on pumpkin flesh and peel under uniaxial tensile and compression. The constitutive coefficients for peel under tensile test was α = 25.66 and β = −18.48 Mpa and for flesh α = −5.29 and β = 5.27 Mpa. under compression the constitutive coefficients were α = 4.74 and β = −1.71 Mpa for peel and α = 0.76 and β = −1.86 Mpa for flesh samples. Constitutive curves predicted the values of force precisely and close to the experimental values. The curves were fit for whole stress versus strain curve as well as a section of curve up to bio yield point. The modelling outputs had presented good agreement with the empirical values and the constructive curves exhibited a very similar pattern to the experimental curves. The presented constitutive model can be applied next to other agricultural materials under loading in future.

A review of pedestrian group dynamics and methodologies in modelling pedestrian group behaviours

Observations conducted by researchers revealed that the group interaction within crowds is a common phenomenon and has great influence on pedestrian behaviour. However, most research currently undertaken by various researchers failed to consider the group dynamics when developing pedestrian flow models. This paper presented a critical review of pedestrian models that incorporates group behaviour. Models reviewed in this paper are mainly created by microscopic modelling approaches such as social force, cellular automata, and agent-based method. The purpose of this literature review is to improve the understanding of group dynamics among pedestrians and highlight the need for considering group dynamics when developing pedestrian simulation models.

Theoretical modelling of momentum transfer function of bi-disperse porous media

The aim of this paper is to obtain the momentum transfer coefficient between the two phases, denoted by f and p, occupying a bi-disperse porous medium by mapping the available experimental data to the theoretical model proposed by Nield and Kuznetsov. Data pertinent to plate-fin heat exchangers, as bi-disperse porous media, were used. The measured pressure drops for such heat exchangers are then used to give the overall permeability which is linked to the porosity and permeability of each phase as well as the interfacial momentum transfer coefficient between the two phases. Accordingly, numerical values are obtained for the momentum transfer coefficient for three different fin spacing values considered in the heat exchanger experiments.

Formation of carbon nanoscrolls from graphene nanoribbons : a molecular dynamics study

Carbon nanoscrolls (CNSs) are one of the carbon-based nanomaterials similar to carbon nanotubes (CNTs) but are not widely studied in spite of their great potential applications. Their practical applications are hindered by the challenging fabrication of the CNSs. A physical approach has been proposed recently to fabricate the CNS by rolling up a monolayer graphene nanoribbon (GNR) around a CNT driven by the interaction energy between them. In this study, we perform extensive molecular dynamics (MD) simulations to investigate the various factors that impact the formation of the CNS from GNR. Our simulation results show that the formation of the CNS is sensitive to the length of the CNT and temperature. When the GNR is functionalized with hydrogen, the formation of the CNS is determined by the density and distribution of the hydrogen atoms. Graphyne, the allotrope of graphene, is inferior to graphene in the formation of the CNS due to the weaker bonds and the associated smaller atom density. The mechanism behind the rolling of GNR into CNS lies in the balance between the GNR–CNT van der Waals (vdW) interactions and the strain energy of GNR. The present work reveals new important insights and provides useful guidelines for the fabrication of the CNS.

A poroviscohyperelastic model for numerical analysis of mechanical behavior of single chondrocyte

The aim of this paper is to utilize a poroviscohyperelastic (PVHE) model which is developed based on the porohyperelastic (PHE) model to explore the mechanical deformation properties of single chondrocytes. Both creep and relaxation responses are investigated by using FEM models of micropipette aspiration and AFM experiments, respectively. The newly developed PVHE model is compared thoroughly with the SnHS and PHE models. It has been found that the PVHE can accurately capture both creep and stress relaxation behaviors of chondrocytes better than other two models. Hence, the PVHE is a promising model to investigate mechanical properties of single chondrocytes.

Molecular camouflage : making use of protecting groups to control the self-assembly of inorganic janus particles onto metal–chalcogenide nanotubes by Pearson Hardness

Hard and soft: Binding of inorganic Pt@Fe3O4 Janus particles to WS2 nanotubes through their Pt or Fe3O4 domains is governed by the difference in Pearson hardness: the soft Pt block has a higher sulfur affinity than the harder magnetite face; thus the binding proceeds preferentially through the Pt face. This binding preference can be reversed by masking the Pt face with an organic protecting group.

Influences of molecular structure on co-crystallization of polypyridyl metal complexes.

Heteroleptic complexes of the type \[RuL2L′](PF6)2 (L, L′ = combinations of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy)) were found to cocrystallize with \[Ni(phen)3](PF6)2 to produce cocrystals of \[Ni(phen)3]x\[RuL2L′]1–x(PF6)2. In this report we show that the ability of the complexes to cocrystallize is influenced by the number of common ligands between complexes in solution. Supramolecular selection is a phenomenon caused by molecular recognition through which cocrystals can grow from the same solution but contain different ratios of the molecular components. It was found that systems where L = phen displayed less supramolecular selection than systems where L = bipy. With increasing supramolecular selection, the composition of cocrystals was found to vary significantly from the initial relative concentration in the cocrystallizing solution, and therefore it was increasingly difficult to control the final composition of the resultant cocrystals. Consequently, modulation of concentration-dependent properties such as phase was also found to be less predictable with increasing supramolecular selection. Notwithstanding the complication afforded by the presence of supramolecular selection, our results reaffirm the robustness of the \[M(phen)3](PF6)2 structure because it was maintained even when ca. 90% of the complexes in the cocrystals were \[Ru(phen)(bipy)2](PF6)2, which in its pure form is not isomorphous with \[M(phen)3](PF6)2. Experiments between complexes without common ligands, i.e., \[Ru(bipy)3](PF6)2 cocrystallized with \[Ni(phen)3](PF6)2, were found to approach the limit to which molecular recognition processes can be confused into cocrystallizing different molecules to form single cocrystals. For these systems the result was the formation of block-shaped crystals skewered by a needle-shaped crystals.

Review-evaluating the molecular assays for measuring the oxidative potential of particulate matter

Several cell-free assays are currently used to quantify and detect the Reactive Oxygen Species (ROS). All of them have certain limitations, do not provide direct comparison of results and, to date, none of these assays have been acknowledged as the most suitable acellular assay and none has yet been adopted for investigation of potential PM toxicity. These assays include DTT, ascorbic acid, DCFHDA and PFN assays which have been used in measurements of the particles generated from various combustion sources such as diesel engine, wood smoke (or biomass burning) and cigarette smoke, as well as for outdoor measurements. All the probes use different units for expressing redox properties of PM. Also, their reactivity is being triggered by different types of ROS. This limits the direct comparison of the results that are reporting the toxicity of the same aerosol type measured with various probes. This study is evaluating and comparing the various assays in order to develop deeper understanding of their capabilities, selectivity as well as improve understanding of the underlying chemical mechanisms. Keywords: DTT, DCFH-DA, PFN, BPEA-nit, Ascorbic acid, oxidative potential

Energetic and thermal properties of tilt grain boundaries in graphene/hexagonal boron nitride heterostructures

Graphene/hexagonal boron nitride (G/h-BN) heterostructure has attracted tremendous research efforts owing to its great potential for applications in nano-scale electronic devices. In such hybrid materials, tilt grain boundaries (GBs) between graphene and h-BN grains may have unique physical properties, which have not been well understood. Here we have conducted non-equilibrium molecular dynamics simulations to study the energetic and thermal properties of tilt GBs in G/h-BN heterostructures. The effect of misorientation angles of tilt GBs on both GB energy and interfacial thermal conductance are investigated.

Facile dearomatisation of porphyrins using palladium-catalysed hydrazination: the 5,15-diiminoporphodimethenes and their redox products

The synthesis, electronic absorption and 1H NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also characterised, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum.