Applicability of molecular simulations for modelling the adsorption of the greenhouse gas CF4 on carbons

Tetrafluoromethane, CF4, is powerful greenhouse gas, and the possibility of storing it in microporous carbon has been widely studied. In this paper we show, for the first time, that the results of molecular simulations can be very helpful in the study of CF4 adsorption. Moreover, experimental data fit to the results collected from simulations. We explain the meaning of the empirical parameters of the supercritical Dubinin–Astakhov model proposed by Ozawa and finally the meaning of the parameter k of the empirical relation proposed by Amankwah and Schwarz.

Cooperative metal-ligand-induced properties of heteroleptic copper(I) xanthate/dithiocarbamate PPh3 complexes

Four new heteroleptic mononuclear complexes, [Cu(PPh3)2L1](1) {L1 = (C9H11O2CS2), [2-(4-methoxyphenyl)ethyl]xanthate}, [Cu(PPh3)2L2] (2) [L2 = (C6H7OCS2), benzylxanthate], [Cu(PPh3)2L3] (3) [L3 = (C5H9OCS2), (cyclobutylmethyl)xanthate] and [Cu(PPh3)2L4] (4) [L4 = (NC13H13NCS2), N-benzyl-N-(4-pyridylmethyl)dithiocarbamate], have been synthesized and characterized by using microanalysis, IR, UV/Vis, 1H, 13C and 31P NMR spectroscopy and X-ray crystallography; their photoluminescent behaviour and molecular electrical conductivity have been investigated. CuI possesses four-coordinate distorted tetrahedral geometry in all the complexes. All are weakly conducting and exhibit semiconductor behaviour in the studied 303363 K temperature range. Complex 4 shows striking luminescent behaviour emitting bluish green light at 480 nm in CH2Cl2 solution at room temperature

Monometallic salts derived from complex anions of group 10 metal ions with p-tolylsulfonyldithiocarbimate ligand: Synthesis, characterization and properties

New monometallic complex salts of the form X-2[M(L)(2)] [M = Ni2+, X = (CH3)(2)NH2+(1); M = Ni2+, X = (CH3)(4)N+ (2); M = Ni2+, X = (C2H5)(4)N+(3); M = Ni2+, X = (C3H7)(4)N+(4); M = Ni2+; X = (C6H13)(4)N+) (5); M = Pd2+,X = (CH3)(2)NH2+(6); M = Pd2+, X= (C2H5)(4)N+(7); M = Pd2+, X= (C3H7)(4)N+(8); M = Pd2+, X = (C6H13)(4)N+ (9); M = Pt2+, X = (CH3)(2)NH2+(10); L = p-tolylsulfonyldithiocarbimate (CH3C6H4SO2N=CS22 )] have been prepared and characterized by elemental analysis, IR, H-1 and C-13 NMR and UV-Vis spectroscopy; 1, 3, 4 and 5 by X-ray crystallography. In 1, 3, 4 and 5, the Ni atom is four coordinate with a square planar environment being bonded to four sulfur atoms from two bidentate ligands. All the salts are weakly conducting (sigma(rt) = 10 (7) to 10 (14) Scm (1)) because of the lack of significant S center dot center dot center dot S intermolecular interactions between complex anions [M(L)(2)](2) in the solid state however, they show behavior of semiconductors in the temperature range 353-453 K. All the Pd(II) and Pt(II) salts exhibited phtotolumeniscent emissions near visible region in solution at room temperature.

A very rare self-assembled ribbon of fused cyclic water pentamers encapsulated in a Cu-II based metal-organic framework

A metal organic framework of Cu-II, tartarate (tar) and 2,2'-bipyridyl (2,2'-bipy)], {[Cu(tar)(2,2'-bipy)]center dot 5H(2)O}(n)} (1) has been synthesized at the mild ambient condition and characterized by single crystal X-ray crystallography. In the compound, the Cu(2,2'-bipy) entities are bridged by tartarate ions which are coordinated to Cu-II by both hydroxyl and monodentate carboxylate oxygen to form a one-dimensional chain. The non-coordinated water molecules form ID water chains by edge-sharing cyclic water pentamers along with dangling water dimers. It shows reversible water expulsion upon heating. The water chains join the ID coordination polymeric chains to a 31) network through hydrogen-bond interactions.

Syntheses, crystal structures and properties of sterically congested heteroleptic complexes of group 10 metal ions with p-tolylsulfonyl dithiocarbimate and 1,2-bis (diphenylphosphino) ethane

Three novel heteroleptic complexes of the type cis- [ML(dppe)] [M = Ni(II), Pd(II), Pt(II); L = p-tolylsulfonyl dithiocarbimate; dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared and characterized. X-ray crystallography revealed the close proximity of one of the ortho phenyl protons of the dppe ligand to the metal in the Ni(II) complex showing existence of the less common C-H center dot center dot center dot Ni anagostic interactions observed for the first time in the dithio-phosphine mixed-ligand systems. The platinum complex showed a strong photoluminescence emission near visible region in CH(2)Cl(2) solution.

Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.

Survival, reproduction and population growth of the bee pollinator, Osmia rufa (Hymenoptera: Megachilidae), along gradients of heavy metal pollution

1. Bees are one of the most important groups of pollinators in the temperate zone. Although heavy metal pollution is recognised to be a problem affecting large parts of the European Union, we currently lack insights into the effects of heavy metals on wild bee survival and reproduction. 2. We investigated the impact of heavy metal pollution on the wild bee Osmia rufa (Hymenoptera: Megachilidae) by comparing their survival, reproduction and population dynamics along two independent gradients of heavy metal pollution, one in Poland and the other in the United Kingdom. We used trap nests to evaluate the response of fitness and survival parameters of O. rufa. To quantify the levels of pollution, we directly measured the heavy metal concentration in provisions collected by O. rufa. 3. We found that with increasing heavy metal concentration, there was a steady decrease in number of brood cells constructed by females and an increase in the proportion of dead offspring. In the most polluted site, there were typically 3–4 cells per female with 50–60% dead offspring, whereas in unpolluted sites there were 8 to 10 cells per female and only 10–30% dead offspring. Moreover, the bee population growth rate (R0) decreased along the heavy metal pollution gradients. In unpolluted sites, R0 was above 1, whereas in contaminated sites, the values tended to be below 1. 4. Our findings reveal a negative relationship between heavy metal pollution and several fitness parameters of the wild bee O. rufa, and highlight a mechanism whereby the detrimental effects of heavy metal pollution may severely impact wild bee communities.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

Lithium and oxygen adsorption at the b-MnO2 (110) surface

The adsorption and co-adsorption of lithium and oxygen at the surface of rutile-like manganese dioxide(b-MnO2), which are important in the context of Li–air batteries, are investigated using density functional theory. In the absence of lithium, the most stable surface of b-MnO2, the (110), adsorbs oxygen in the form of peroxo groups bridging between two manganese cations. Conversely, in the absence of excess oxygen, lithium atoms adsorb on the (110) surface at two different sites, which are both tricoordinated to surface oxygen anions, and the adsorption always involves the transfer of one electron from the adatom to one of the five-coordinated manganese cations at the surface, creating (formally) Li+ and Mn3+ species. The co-adsorption of lithium and oxygen leads to the formation of a surface oxide, involving the dissociation of the O2 molecule, where the O adatoms saturate the coordination of surface Mn cations and also bind to the Li adatoms. This process is energetically more favourable than the formation of gas-phase lithium peroxide (Li2O2) monomers, but less favourable than the formation of Li2O2 bulk. These results suggest that the presence of b-MnO2 in the cathode of a nonaqueous Li–O2 battery lowers the energy for the initial reduction of oxygen during cell discharge.

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.

Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

Style and substance: some metal figurines from south-west Britain

A hoard found in Southbroom, Devizes in 1714 contained a group of copper-alloy figurines executed in both classical and local styles and depicting deities belonging to the Graeco-Roman and Gallo-Roman pantheons. The deities in a local style appear to form part of a larger tradition of figurines, predominantly found in the South-West, which are characterised both by a similar artistic style and by the use of Gallo-Roman symbolism and deities, such as the torc, ram-horned snake, carnivorous dog and Sucellus. The unique composition of the hoard in comparison with other hoards of similar date provides insights into the beliefs of Roman Britain.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.