Atomic adsorption on graphene with a single vacancy: systematic DFT study through the periodic table of elements.

Vacancies in graphene present sites of altered chemical reactivity and open possibilities to tune graphene properties by defect engineering. The understanding of chemical reactivity of such defects is essential for successful implementation of carbon materials in advanced technologies. We report the results of a systematic DFT study of atomic adsorption on graphene with a single vacancy for the elements of rows 1-6 of the periodic table of elements (PTE), excluding lanthanides. The calculations have been performed using the PBE, long-range dispersion interaction-corrected PBE (PBE+D2 and PBE+D3) and non-local vdW-DF2 functionals. We find that most elements strongly bind to the vacancy, except for the elements of groups 11 and 12, and noble gases, for which the contribution of dispersion interaction to bonding is most significant. The strength of the interaction with the vacancy correlates with the cohesive energy of the elements in their stable phases: the higher the cohesive energy is, the stronger bonding to the vacancy can be expected. As most atoms can be trapped at the SV site we have calculated the potentials of dissolution and found that in most cases the metals adsorbed at the vacancy are more "noble" than they are in their corresponding stable phases.

Lattice mismatch as the descriptor of segregation, stability and reactivity of supported thin catalyst films.

The increasing demand and high prices of advanced catalysts motivate a constant search for novel active materials with reduced contents of noble metals. The development of thin films and core-shell catalysts seems to be a promising strategy along this path. Using density functional theory we have analyzed a number of surface properties of supported bimetallic thin films with the composition A3B (where A = Pt and Pd, and B = Cu, Ag and Au). We focus on the surface segregation, dissolution stability and surface electronic structure. We also address the chemisorption properties of Pd3Au thin films supported by different substrates, by probing the surface reactivity with CO. We find a strong influence of the support in the case of mono- and bilayers, while the surface strain seems to be the predominant factor in determining the surface properties of supported trilayers and thicker films. In particular, we show that the studied properties of the supported trilayers can be predicted from the lattice mismatch between the overlayer and the support. Namely, if the strain dependence of the corresponding quantities for pure strained surfaces is known, the properties of strained supported trilayers can be reliably estimated. The obtained results can be used in the design of novel catalysts and predictions of the surface properties of supported ultrathin catalyst layers.

Electrochemical tuning of capacitive response of graphene oxide.

The increasing energy demands of modern society require a deep understanding of the properties of energy storage materials, as well as the tuning of their performance. We show that the capacitance of graphene oxide (GO) can be precisely tuned using a simple electrochemical reduction route. In situ resistance measurements, in combination with cyclic voltammetry measurements and Raman spectroscopy, have shown that upon reduction GO is irreversibly deoxygenated, which is further accompanied by structural ordering and an increase in electrical conductivity. The capacitance is maximized when the concentration of oxygen functional groups is properly balanced with the conductivity. Any further reduction and deoxygenation leads to a gradual loss of capacitance. The observed trend is independent of the preparation route and the exact chemical and structural properties of GO. It is proposed that an improvement in the capacitive properties of any GO can be achieved by optimization of its reduction conditions.

A DFT study of the interplay between dopants and oxygen functional groups over the graphene basal plane - implications in energy-related applications.

Understanding the ways graphene can be functionalized is of great importance for many contemporary technologies. Using density functional theory calculations we investigate how vacancy formation and substitutional doping by B, N, P and S affect the oxidizability and reactivity of the graphene basal plane. We find that the presence of these defects enhances the reactivity of graphene. In particular, these sites act as strong attractors for OH groups, suggesting that the oxidation of graphene could start at these sites or that these sites are the most difficult to reduce. Scaling between the OH and H adsorption energies is found on both reduced and oxidized doped graphene surfaces. Using the O2 molecule as a probe we show that a proper modelling of doped graphene materials has to take into account the presence of oxygen functional groups.

Improved catalysts for hydrogen evolution reaction in alkaline solutions through the electrochemical formation of nickel-reduced graphene oxide interface.

H2 production via water electrolysis plays an important role in hydrogen economy. Hence, novel cheap electrocatalysts for the hydrogen evolution reaction (HER) are constantly needed. Here, we describe a simple method for the preparation of composite catalysts for H2 evolution, consisting in simultaneous reduction of the graphene oxide film, and electrochemical deposition of Ni on its surface. The obtained composites (Ni@rGO), compared to pure electrodeposited Ni, show an improved electrocatalytic activity towards HER in alkaline media. We found that the activity of the Ni@rGO catalysts depends on the surface composition (Ni vs. C mole ratio) and on the level of structural disorder of the rGO support. We suggest that HER activity is improved via Hads spillover from the Ni particles to the rGO support, where quick recombination to molecular hydrogen is favored. A deeper insight into such a mechanism of H2 production was achieved by kinetic Monte-Carlo simulations. These simulations enabled the reproduction of experimentally observed trends under the assumption that the support can act as a Hads acceptor. We expect that the proposed procedure for the production of novel HER catalysts could be generalized and lead to the development of a new generation of HER catalysts by tailoring the catalyst/support interface.

A general view on the reactivity of the oxygen-functionalized graphene basal plane.

In this contribution we inspect the adsorption of H, OH, Cl and Pt on oxidized graphene using DFT calculations. The introduction of epoxy and hydroxyl groups on the graphene basal plane significantly alters its chemisorption properties, which can be attributed to the deformation of the basal plane and the type and distribution of these groups. We show that a general scaling relation exists between the hydrogen binding energies and the binding energies of other investigated adsorbates, which allows for a simple probing of the reactivity of oxidized graphene with only one adsorbate. The electronic states of carbon atoms located within the 2 eV interval below the Fermi level are found to be responsible for the interaction of the basal plane with the chosen adsorbates. The number of electronic states situated in this energy interval is shown to correlate with hydrogen binding energies.

Thermal stability and nonisothermal kinetics of Folnak degradation process.

AIM: The purpose of this article is to investigate the thermal stability and nonisothermal kinetics of Folnak drug degradation process using different thermoanalytical techniques. METHODS: The nonisothermal degradation of Folnak powder samples was investigated by simultaneous thermogravimetry-differential thermal analysis, in the temperature range from ambient to 810 degrees C. RESULTS: It was found that the degradation proceeds through five reaction stages, which include the dehydration, the melting process of excipients, the decomposition of folic acid, corn starch, and saccharose. The presence of compounds such as excipients increases the thermal stability of the drug and some kind of solid-solid and/or solid-gas interaction occurs. CONCLUSION: It was concluded that the main degradation stage of Folnak sample represents the decomposition of folic acid. It was established that the folic acid decomposition cannot be explained by simple reaction order model (n = 1) but with the complex reaction mechanism that includes higher reaction orders (n > 1). The isothermal predictions of the folic acid decomposition at four different temperatures (T(iso) = 180 degrees C, 200 degrees C, 220 degrees C, and 260 degrees C) were established. It was concluded that the shapes of conversion curves at lower temperatures (180-200 degrees C) were similar, whereas they became more complex with further temperature increase because of the complexity of the decomposition reaction.

Carbon-Supported Mo2C for Oxygen Reduction Reaction Electrocatalysis.

Molybdenum carbide (Mo2C)-based electrocatalysts were prepared using two different carbon supports, commercial carbon nanotubes (CNTs) and synthesised carbon xerogel (CXG), to be studied from the point of view of both capacitive and electrocatalytic properties. Cation type (K+ or Na+) in the alkaline electrolyte solution did not affect the rate of formation of the electrical double layer at a low scan rate of 10 mV s-1. Conversely, the different mobility of these cations through the electrolyte was found to be crucial for the rate of double-layer formation at higher scan rates. Molybdenum carbide supported on carbon xerogel (Mo2C/CXG) showed ca. 3 times higher double-layer capacity amounting to 75 mF cm-2 compared to molybdenum carbide supported on carbon nanotubes (Mo2C/CNT) with a value of 23 mF cm-2 due to having more than double the surface area size. The electrocatalytic properties of carbon-supported molybdenum carbides for the oxygen reduction reaction in alkaline media were evaluated using linear scan voltammetry with a rotating disk electrode. The studied materials demonstrated good electrocatalytic performance with Mo2C/CXG delivering higher current densities at more positive onset and half-wave potential. The number of electrons exchanged during oxygen reduction reaction (ORR) was calculated to be 3, suggesting a combination of four- and two-electron mechanism.

Synthesis and characterization of self-assembled polyaniline nanotubes/silica nanocomposites.

Self-assembled semiconducting, paramagnetic polyaniline nanotubes have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of colloidal silica particles of an average diameter approximately 12 nm, without added acid. The electrical conductivity of polyaniline nanotubes/silica nanocomposites is in the range (3.3-4.0)x10(-3) S cm(-1). The presence of paramagnetic polaronic emeraldine salt form of polyaniline and phenazine units in nanocomposites was proved by FTIR, Raman, and EPR spectroscopies. The influence of the initial silica/aniline weight ratio on the morphology of polyaniline/silica nanocomposites was studied by scanning and transmission electron microscopies. Nanocomposites synthesized by using the initial weight ratio silica/aniline

Conducting carbonized polyaniline nanotubes.

Conducting nitrogen-containing carbon nanotubes were synthesized by the carbonization of self-assembled polyaniline nanotubes protonated with sulfuric acid. Carbonization was carried out in a nitrogen atmosphere at a heating rate of 10 degrees C min(-1) up to a maximum temperature of 800 degrees C. The carbonized polyaniline nanotubes which have a typical outer diameter of 100-260 nm, with an inner diameter of 20-170 nm and a length extending from 0.5 to 0.8 microm, accompanied with very thin nanotubes with outer diameters of 8-14 nm, inner diameters 3.0-4.5 nm and length extending from 0.3 to 1.0 microm, were observed by scanning and transmission electron microscopies. Elemental analysis showed 9 wt% of nitrogen in the carbonized product. Conductivity of the nanotubular PANI precursor, amounting to 0.04 S cm(-1), increased to 0.7 S cm(-1) upon carbonization. Molecular structure of carbonized polyaniline nanotubes has been analyzed by FTIR and Raman spectroscopies, and their paramagnetic characteristics were compared with the starting PANI nanotubes by EPR spectroscopy.

Electrochemical and density functional theory study on the reactivity of fisetin and its radicals: implications on in vitro antioxidant activity.

Antioxidative properties of naturally occurring flavon-3-ol, fisetin, were examined by both cyclic voltammetry and quantum-chemical based calculations. The three voltametrically detectable consecutive steps, reflected the fisetin molecular structure, catecholic structural unit in the ring B, C3-OH, and C7-OH groups in the rings C and A. Oxidation potential values, used as quantitative parameter in determining its oxidation capability, indicated good antioxidative properties found with this molecule. Oxidation of the C3'C4' dixydroxy moiety at the B ring occurred first at the lowest positive potentials. The first oxidation step induced fast intramolecular transformations in which the C3 hydroxy group disappeared and the product of this transformation participated in the second oxidation step. The highest potential of oxidation was attributed to the oxidation of C7 hydroxy group. The structural and electronic features of fisetin were investigated at the B3LYP/6-311++G** level of theory. Particularly, the interest was focused on the C3' and C4'-OH sites in the B ring and on C3-OH site in the C ring. The calculated bond dissociation enthalpy values for all OH sites of fisetin clearly indicated the importance of the B ring and C3' and C4'-OH group. The importance of keto-enol tautomerism has also been considered. The analysis also included the Mulliken spin density distribution for the radicals formed after H removal on each OH site. The results showed the higher values of the BDE on the C7-OH and C3-OH sites.

DFT study of adsorption of hydrogen and carbon monoxide on PtxBi1-x/Pt(111) bimetallic overlayers: correlation to surface electronic properties.

Analysis of the electronic properties of Pt(x)Bi(1-x)/Pt(111) bimetallic overlayers was performed by DFT calculation. The positions of the d-band centers and band widths were correlated using a triangular band model. In addition, the adsorption of hydrogen atoms as well as CO tolerance of selected Pt(x)Bi(1-x)/Pt(111) bimetallic overlayers were analysed. Excellent correlation was obtained of the adsorption energies of H and CO with d-band centers of platinum atoms on the studied surfaces. The red shift of Pt-H stretching vibration of adsorbed hydrogen, and decrease of work function upon adsorption of H were predicted. Analysis of hydrogen and CO chemisorption by means of the difference of the projected density of states was performed in order to identify d-states involved in bonding. The results obtained by calculations were compared with the experimental ones, where available.

Synthesis and characterization of conducting self-assembled polyaniline nanotubes/zeolite nanocomposite.

Self-assembled conducting, paramagnetic polyaniline nanotubes have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of zeolite HZSM-5, without added acid. The influence of initial zeolite/aniline weight ratio on the conductivity, molecular and supramolecular structure, paramagnetic characteristics, thermal stability, and specific surface area of polyaniline/zeolite composites was studied. The conducting (approximately 10(-2) S cm(-1)), semiconducting (3 x 10(-5) S cm(-1)), and nonconducting (5 x 10(-9) S cm(-1)) composites are produced using the zeolite/aniline weight ratios 1, 5, and 10, respectively. The coexistence of polyaniline nanotubes, which have a typical outer diameter of 70-170 nm and an inner diameter of 5-50 nm, accompanied by nanorods with a diameter of 60-100 nm and polyaniline/zeolite mesoporous aggregates, distinct from the morphology of microporous zeolite HZSM-5, was proved in the conducting nanocomposite by scanning and transmission electron microscopies. FTIR spectroscopy confirmed the presence of polyaniline in the form of conducting emeraldine salt and suggested significant interaction of polyaniline with zeolite. The evolution of molecular and supramolecular structure of polyaniline in the presence of zeolite was discussed.