Separation of CO2/CH4 gas mixtures using nanoporous graphdiyne and boron-graphdiyne membranes: influence of the pore size.

Nanoporous carbon-based membranes have garnered significant interest in gas separation processes owing to their distinct structure and properties. We have investigated the permeation and separation of the mixture of CO2 and CH4 gases through membranes formed by thin layers of porous graphdiyne (GDY) and boron graphdiyne (BGDY) using Density Functional Theory. The main goal is to investigate the effect of the pore size. The interaction of CO2 and CH4 with GDY and BGDY is weak, and this guarantees that those molecules will not be chemically trapped on the surface of the porous membranes. The permeation and separation of CO2 and CH4 through the membranes are significantly influenced by the size of the pores in the layers. The size of the hexagonal pores in BGDY is large in comparison to the size of the two molecules, and the passing of these molecules through the pores is easy because there is no barrier. Then, BGDY is not able to separate CO2 and CH4. In sharp contrast, the size of the triangular pores in GDY is smaller, comparable to the diameter of the two molecules, and this raises an activation barrier for the crossing of the molecules. The height of the barrier for CO2 is one half of that for CH4, the reason being that CO2 is a linear molecule which adopts an orientation perpendicular to the GDY layer to cross the pores, while CH4 has a spherical-like shape, and cannot profit from a favorable orientation. The calculated permeances favor the passing of CO2 through the GDY membrane, and the calculated selectivity for CO2/CH4 mixtures is large. This makes GDY a very promising membrane material for the purification of commercial gases and for the capture of the CO2 component in those gases.

Implantation of Gallium into Layered WS2 Nanostructures is Facilitated by Hydrogenation.

Bombarding WS2 multilayered nanoparticles and nanotubes with focused ion beams of Ga+ ions at high doses, larger than 1016 cm-2, leads to drastic structural changes and melting of the material. At lower doses, when the damage is negligible or significantly smaller, the amount of implanted Ga is very small. A substantial increase in the amount of implanted Ga, and not appreciable structural damage, are observed in nanoparticles previously hydrogenated by a radio-frequency activated hydrogen plasma. Density functional calculations reveal that the implantation of Ga in the spaces between adjacent layers of pristine WS2 nanoparticles is difficult due to the presence of activation barriers. In contrast, in hydrogenated WS2, the hydrogen molecules are able to intercalate in between adjacent layers of the WS2 nanoparticles, giving rise to the expansion of the interlayer distances, that in practice leads to the vanishing of the activation barrier for Ga implantation. This facilitates the implantation of Ga atoms in the irradiation experiments.

Palladium clusters, free and supported on surfaces, and their applications in hydrogen storage.

Palladium is a late transition metal element in the 4d row of the periodic table. Palladium nanoparticles show efficient catalytic activity and selectivity in a number of chemical reactions. In this paper, we review the structural and electronic properties of palladium nanoclusters, both isolated and deposited on the surface of different substrates. Careful experiments and extensive calculations have been performed for small Pd clusters which provide ample information on their properties. Work on large Pd clusters is less abundant and more difficult to perform and interpret. Cluster deposition is a method to modify material surfaces for different applications, and we report the known results for the deposition of Pd clusters on the surfaces of a number of interesting substrates: carbonaceous substrates like graphene and some layered novel materials related to graphene, metal oxide substrates, silicon and silicon-related substrates and metallic alloy substrates. Emphasis is placed on revealing how the structural, electronic and magnetic properties change when the clusters are deposited on the substrate surfaces. Some examples of chemical reactions catalyzed by supported Pd clusters and nanoparticles are reported. An issue discussed in detail is the influence of Pd on the storage of hydrogen in porous materials. Experimental work shows that the amount of stored hydrogen increases when the absorbing material is doped with Pd atoms, clusters and nanoparticles, and a spillover mechanism from the metal particle to the substrate is usually accepted as the explanation. To shed light on this issue, a critical analysis based on density functional simulations of the mechanisms of hydrogen spillover in perfect and defective graphene doped with palladium clusters is presented.

Nanoalloys of Metals Which Do Not Form Bulk Alloys: The Case of Ag-Co.

Ag and Co metals do not form macroscopic solid or liquid alloys. However, AgmCon clusters have been produced in dual-target dual-laser vaporization experiments, and the same occurs for other pairs of immiscible metals. We have performed density functional calculations to shed light on this phenomenon. The main result, obtained for clusters with sizes m + n not larger than 11, is that the cohesive energies justify that those clusters can be formed starting from free Ag and Co atoms, which is the case in the vaporization experiments. At the same time, mixing of Ag and Co is difficult even at the nanoscale. This is revealed by the application of several miscibility criteria. Those two features become, nevertheless, compatible in the clusters. Even if the cluster sizes considered are small, the emerging trend becomes clear: Co atoms form a core in the inner part, surrounded by a shell of Ag atoms on the surface. A consequence is that core-shell clusters can be formed from pairs of metals that do not form macroscopic alloys. The magnetic moments µ of the AgmCon clusters are due mainly to the Co atoms, and the presence of Ag induces a reduction in the magnitude of µ.

Reactivity of Cobalt-Fullerene Complexes towards Deuterium.

The adsorption of molecular deuterium (D2 ) onto charged cobalt-fullerene-complexes Con C60 + (n=1-8) is measured experimentally in a few-collision reaction cell. The reactivity is strongly size-dependent, hinting at clustering of the transition metal atoms on the fullerenes. Formation and desorption rate constants are obtained from the pressure-dependent deuterogenation curves. DFT calculations indeed find that this transition metal clustering is energetically more favorable than decorating the fullerene. For n=1, D2 is predicted to bind molecularly and for n=2 dissociative and molecular configurations are quasi-isoenergetic. For n=3-8, dissociation of D2 is thermodynamically preferred. However, reaching the ground state configuration with dissociated deuterium on the timescale of the experiment may be hindered by dissociation barriers.

Dimerization of pentacyclopentacorannulene C30H10 as a strategy to produce C60H20 as a precursor for C60.

The chemical synthesis of C60 fullerene in the laboratory is still a challenge. In order to achieve this goal, we propose a synthetic route based on the dimerization between two pentacyclopentacorannulene (C30H10) fragments employing the Diels-Alder cycloaddition reaction. Density functional calculations indicate that a step wise non-concerted dimerization mechanism of C30H10 is favored over a one stage dimerization. The step wise dimerization implies the sequential formation of 2, 4, 6, and 10 new C-C bonds between the two fragments. This leads to the formation of the Diels-Alder cycloadduct C60H20. The results then suggest the synthesis of C60H20 as a precursor for C60. The synthesis of the analogue C60F20 has already been reported.

Bimetallic Al-Sn clusters: mixing at the nanoscale.

Metals which are not miscible in the bulk solid phase can form clusters at the nanoscale, and a typical example is the Al-Sn system. We have investigated the reasons for the enhanced miscibility occurring at the nanoscale. Density functional calculations have been performed for small AlmSnn clusters at all compositions when the total number of atoms N = m + n is equal to or smaller than N = 6, and for selected compositions for N = 10 and N = 11. The cohesive energies show that the clusters are energetically stable with respect to the separated atoms. Also, after an AlmSnn cluster has formed, its separation into two pure clusters Alm and Snn is energetically forbidden. This justifies the observation that those clusters can form by condensation in gas phase experiments. The different miscibility criteria explored reveal a substantial dependence on the reference state. Between those miscibility criteria, a particularly valuable one consists in studying the substitution reactions in which an Al atom of the gas replaces a Sn atom of the AlmSnn cluster to produce Alm+1Snn-1, or a Sn atom replaces an Al atom to produce Alm-1Snn+1. The conclusion is that substitution reactions enriching the clusters in Sn and depleting the cluster in Al are favorable. However, AlSn10 is an exception to this general trend. This is a special cluster. It readily forms by replacing a Sn atom by an Al atom in Sn11. Also, AlSn10 forms easily by adding an Al atom to Sn10. The geometric structures of Sn11 and Sn10 easily reorganize to form AlSn10 accommodating the Al atom inside a Sn cage. The exceptionally stable character of AlSn10 justifies the identification of AlSn10 as a magic cluster with the highest population in the measured mass spectra of this family. Even if Al and Sn can form clusters, the degree of mixing of these two elements in the clusters is modest, and a tendency for segregation of Al and Sn atoms on different parts of the cluster is incipient.

Hydrogen quenches the size effects in carbon clusters.

A characteristic fingerprint of atomic clusters is that their properties can vary in a non-smooth way with the cluster size N. This is illustrated herein by studying the cluster size dependence of several properties of neutral CN and cationic C+N carbon clusters: C-C bond lengths, cluster structure, intrinsic cluster stability, ionization energy, and spatial distribution of the reactivity index for charge exchange with electrophiles. Nonetheless, clusters can lose the size dependence of their properties by interaction with other chemical species, which is rationalized in this study by analyzing carbon clusters fully saturated with hydrogen to form linear alkanes, CNH2N+2. In all cases, the lowest energy structures are zigzagging linear chains, the variations of C-C bond lengths and angles with alkane size are very minor and smooth, the stability function shows practically no structure as a function of the alkane size, the ionization energies just decrease smoothly with alkane size, and the spatial distribution of the reactivity index is analogous and highly delocalized in all the alkanes. In summary, the interaction of carbon clusters with hydrogen to form alkanes quenches all the size-dependent features that the carbon clusters originally owned. The arrival at the quenching of the size effects follows an involved path. In each CNHn family with fixed N, the values of the properties of the molecules like the ionization potential, the electron affinity, and others show sizable oscillations as the number of hydrogen atoms grows from the pure carbon cluster to the alkane.

An improved descriptor of cluster stability: application to small carbon clusters.

The mass spectra of gas-phase clusters in cluster beams have a rich structure where the relative heights of the peaks compared to peaks corresponding to the clusters of neighboring sizes reveal the stability of the clusters as a function of size N. In an analysis of the published mass spectrum of carbon cluster cations CN+ with N ≤ 16 we have employed the most common descriptor of cluster stability, which is based on the comparison of the total energy of the cluster of size N with the averaged energies of clusters with sizes N + 1 and N - 1. These energies have been obtained from density functional calculations. The comparison between the stability function and the mass spectrum leaves some experimental features unexplained; in particular, the correlation with the detailed variation of the height of the mass peaks as a function of size N is not satisfactory. We then propose a novel stability descriptor which improves the features substantially, in particular the correlation with the detailed variation of the height of the mass peaks. The new stability index is based on the comparison of the atom-evaporation energy of the cluster of size N with the averaged atom-evaporation energies of clusters with sizes N + 1 and N - 1. The substantial improvement achieved is attributed to the fact that evaporation energies are quantities directly connected with the processes controlling the cluster abundances in the beam.

Theoretical study of the adsorption of hydrogen on cobalt clusters.

Adsorption and dissociation of molecular hydrogen on transition metal clusters are basic processes of broad technological application in fields such as catalysis, hydrogenation reactions, hydrogen fuel cells, hydrogen storage, etc. Here we focus on two cobalt clusters, Co6 and Co13, and use the density functional formalism to investigate: (i) the mechanisms for adsorption and dissociation of hydrogen, and (ii) the competition between the two processes as the amount of hydrogen increases towards cluster saturation. The dissociative adsorption of hydrogen is the preferred adsorption channel for low coverage. Each individual H atom binds to the cluster with an ionic type of bonding, similar to that in metal hydrides. The electronic levels of the H atoms hybridize with the deepest levels of the Co cluster, leading to the stabilization of the system. In contrast H2 binds to the cluster with a weak covalent type of bond and the electronic density of the molecule becomes polarized. The electronic levels of the molecule are deeper than those of the Co cluster and do not hybridize with them, which explains the weak bonding of the molecule to the cluster. Interestingly, the high magnetic moments of the Co clusters do not change when H2 is adsorbed in molecular form, but the magnetic moments decrease by two Bohr magnetons upon dissociative adsorption of the molecule. Adsorption and dissociation of H2 on Co6 and Co13 exhibit similar features, although the adsorption energies on Co13 are stronger. Saturation of Co6 with hydrogen has been also investigated. Co6 can adsorb up to four H2 molecules in the dissociated form. Additional hydrogen is adsorbed in molecular form leading to a saturated cluster with sixteen hydrogen molecules, four dissociated and twelve molecular. This limit corresponds to a content of 8.4 wt% of hydrogen in the Co cluster, which is promising for the purpose of hydrogen storage.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS2 multilayers and nanotubes. We find that H2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H2 on the surface of WS2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H2 between adjacent planar WS2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H2 monolayer adsorbed on top of the first WS2 layer of a WS2 multilayer system strongly facilitates the intercalation of H2 between WS2 layers underneath. This opens up an additional gate to intercalation processes.

Hydrogen Chemical Configuration and Thermal Stability in Tungsten Disulfide Nanoparticles Exposed to Hydrogen Plasma.

The chemical configuration and interaction mechanism of hydrogen adsorbed in inorganic nanoparticles of WS2 are investigated. Our recent approaches of using hydrogen activated by either microwave or radiofrequency plasma dramatically increased the efficiency of its adsorption on the nanoparticles surface. In the current work we make an emphasis on elucidation of the chemical configuration of the adsorbed hydrogen. This configuration is of primary importance as it affects its adsorption stability and possibility of release. To get insight on the chemical configuration, we combined the experimental analysis methods with theoretical modeling based on the density functional theory (DFT). Micro-Raman spectroscopy was used as a primary tool to elucidate chemical bonding of hydrogen and to distinguish between chemi- and physisorption. Hydrogen adsorbed in molecular form (H2) was clearly identified in all the plasma-hydrogenated WS2 nanoparticles samples. It was shown that the adsorbed hydrogen is generally stable under high vacuum conditions at room temperature, which implies its stability at the ambient atmosphere. A DFT model was developed to simulate the adsorption of hydrogen in the WS2 nanoparticles. This model considers various adsorption sites and identifies the preferential locations of the adsorbed hydrogen in several WS2 structures, demonstrating good concordance between theory and experiment and providing tools for optimizing of hydrogen exposure conditions and the type of substrate materials.

Controlling the Adsorption of Carbon Monoxide on Platinum Clusters by Dopant-Induced Electronic Structure Modification.

A major drawback of state-of-the-art proton exchange membrane fuel cells is the CO poisoning of platinum catalysts. It is known that CO poisoning is reduced if platinum alloys are used, but the underlying mechanism therefore is still under debate. We study the influence of dopant atoms on the CO adsorption on small platinum clusters using mass spectrometry experiments and density functional calculations. A significant reduction in the reactivity for Nb- and Mo-doped clusters is attributed to electron transfer from those highly coordinated dopants to the Pt atoms and the concomitant lower CO binding energies. On the other hand Sn and Ag dopants have a lower Pt coordination and have a limited effect on the CO adsorption. Analysis of the density of states demonstrates a correlation of dopant-induced changes in the electronic structure with the enhanced tolerance to CO poisoning.

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH2, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF3, CHO, CN, NO2). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO2 substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

From graphene oxide to pristine graphene: revealing the inner workings of the full structural restoration.

High temperature annealing is the only method known to date that allows the complete repair of a defective lattice of graphenes derived from graphite oxide, but most of the relevant aspects of such restoration processes are poorly understood. Here, we investigate both experimentally (scanning probe microscopy) and theoretically (molecular dynamics simulations) the thermal evolution of individual graphene oxide sheets, which is rationalized on the basis of the generation and the dynamics of atomic vacancies in the carbon lattice. For unreduced and mildly reduced graphene oxide sheets, the amount of generated vacancies was so large that they disintegrated at 1773-2073 K. By contrast, highly reduced sheets survived annealing and their structure could be completely restored at 2073 K. For the latter, a minor atomic-sized defect with six-fold symmetry was observed and ascribed to a stable cluster of nitrogen dopants. The thermal behavior of the sheets was significantly altered when they were supported on a vacancy-decorated graphite substrate, as well as for the overlapped/stacked sheets. In these cases, a net transfer of carbon atoms between neighboring sheets via atomic vacancies takes place, affording an additional healing process. Direct evidence of sheet coalescence with the step edge of the graphite substrate was also gathered from experiments and theory.

Elimination vs substitution reaction. A dichotomy between Brønsted-Lowry and Lewis basicity.

The Brønsted-Lowry and Lewis basicity dichotomy in the elimination vs substitution reaction competition is analyzed in terms of a novel Brønsted-Lowry-Lewis basicity ωp/e. This new index unifies the dichotomy and explains the competition between elimination and substitution mechanisms of alkyl centers with para-substituted phenols.

Protophilicity index and protofelicity equalization principle: new measures of Brønsted-Lowry-Lewis acid-base interactions.

The simultaneous contributions of proton and electron transfer to the Brønsted-Lowry and Lewis acid-base properties of a set of p-substituted phenols are reported in this work. As a result of the analysis, a novel protophilicity index considered as the second-order energy change of a Brønsted-Lowry base as it is saturated with protons, a combined Brønsted-Lowry-Lewis acidity index (with a corresponding basicity index), and a protofelicity equalization principle (a parallel of the electronegativity equalization principle) are presented.

Comment on "The diatomic dication CuZn2+ in the gas phase" [J. Chem. Phys. 135, 034306 (2011)].

In this Comment, the density functional theory (DFT) calculations carried out by Diez et al. [J. Chem. Phys. 135, 034306 (2011)] are revised within the framework of the coupled-cluster single double triple method. These more sophisticated calculations allow us to show that the (2)Σ(+) electronic ground state of CuZn(2+), characterized as the metastable ground state by DFT calculations, is a repulsive state instead. The (2)Δ and (2)Π metastable states of CuZn(2+), on the other hand, should be responsible for the formation mechanism of the dication through the near-resonant electron transfer CuZn(+) + Ar(+) → CuZn(2+) + Ar reaction.

Growth of fullerene fragments using the Diels-Alder cycloaddition reaction: first step towards a C60 synthesis by dimerization.

Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

Simulated porosity and electronic structure of nanoporous carbons.

Nanoporous carbon refers to a broad class of materials characterized by nanometer-size pores, densities lower than water, large specific surface areas, and high porosities. These materials find applications in nanocatalysis and gas adsorption, among others. The porosity structure, that determines the properties and functionalities of these materials, is still not characterized in detail. Here, we reveal the detail porosity structure and the electronic properties of a type of nanoporous carbons, the so called carbide derived carbons (CDCs), through a simulation scheme that combines large simulation cells and long time scales at the empirical level with first-principles density functional calculations. We show that the carbon network consists in one layer thick nanographenes interconnected among them. The presence of specific defects in the carbon layers (heptagons and octagons) yields to open pores. These defects are not completely removed through annealing at high temperatures. We also suggest that, in contrast with graphene which is a zero-gap semiconductor, these materials would have a metallic character, since they develop an electronic band around the Fermi level. This band arises from the electronic states localized at the edges of the nanographene layers.