Transport across two interacting quantum dots: Bulk Kondo, Kondo box, and molecular regimes

We analyze the transport properties of a double quantum dot device with both dots coupled to perfect conducting leads and to a finite chain of N noninteracting sites connecting both of them. The interdot chain strongly influences the transport across the system and the local density of states of the dots. We study the case of a small number of sites, so that Kondo box effects are present, varying the coupling between the dots and the chain. For odd N and small coupling between the interdot chain and the dots, a state with two coexisting Kondo regimes develops: the bulk Kondo due to the quantum dots connected to leads and the one produced by the screening of the quantum dot spins by the spin in the finite chain at the Fermi level. As the coupling to the interdot chain increases, there is a crossover to a molecular Kondo effect, due to the screening of the molecule (formed by the finite chain and the quantum dots) spin by the leads. For even N the two Kondo temperatures regime does not develop and the physics is dominated by the usual competition between Kondo and antiferromagnetism between the quantum dots. We finally study how the transport properties are affected as N is increased. For the study we used exact multiconfigurational Lanczos calculations and finite-U slave-boson mean-field theory at T=0. The results obtained with both methods describe qualitatively and also quantitatively the same physics.

Conformational changes of dissolved humic and fulvic superstructures with progressive iron complexation

Conformational changes of a humic acid (HA) and a fulvic acid (FA) induced by iron complexation were followed by high-performance size exclusion chromatography (HPSEC) with both UV–vis and refractive index (RI) detectors. Molecular size distribution was reduced for HA and increased for FA with progressive iron complexation. Since interactions of Fe with humic components are electrostatic, it is likely that the triple-charged Fe ions formed stronger complexes with the more acidic hydrophilic and hydrated FA than with the less acidic and more hydrophobic HA. The large content of ionized carboxyl groups in FA, thus favored the formation of intra- or intermolecular bridges between the negatively charged fulvic acid molecules, and led to more compact and larger size network than for HA. Conversely, iron complexation with HA disrupted the humic conformational arrangements stabilized by only weak hydrophobic bonds into smaller-size aggregates of greater conformational stability due to formation of strong metal complexes. These results confirmed that humic molecules in solution were organized in supramolecular associations of relatively small molecules loosely bound together by dispersive interactions and hydrogen bonds, and they specifically responded to chemical changes brought about by metal additions. The present study revealed the molecular changes occurring in superstructures of natural organic matter when in metal complexes and contributed to understand and predict the environmental behavior in waters and soil of metal complexes with natural organic matter.

Effect of Cyclic Topology on Charge-Transfer Properties of Organic Molecular Semiconductors: The Case of Cycloparaphenylene Molecules

We have studied the role played by cyclic topology on charge-transfer properties of recently synthesized π -conjugated molecules, namely the set of [n]cycloparaphenylene compounds, with n the number of phenylene rings forming the curved nanoring. We estimate the charge-transfer rates for holes and electrons migration within the array of molecules in their crystalline state. The theoretical calculations suggest that increasing the size of the system would help to obtain higher hole and electron charge-transfer rates and that these materials might show an ambipolar behavior in real samples, independently of the different mode of packing followed by the [6]cycloparaphenylene and [12]cycloparaphenylene cases studied.

Effect of the stabilisation time of pitch fibres on the molecular sieve properties of carbon fibres

The stabilisation of pitch fibres (PFs) is the most important step for their subsequent use in the preparation of carbon fibres (CFs) and their resulting characteristics. The present work studies the influence that the stabilisation time has on the porosity of the CFs, and on the subsequent properties as carbon molecular sieve (CMS). The increase of the stabilisation time carried out at 573 K, from 2 to 8 h favours their CMS properties producing a decrease in the microposity accessible to N2, which gets completely blocked after 6 and 8 h, while the narrow microporosity (V-DR CO2) remains accessible. Adsorption kinetic studies with CH4 and CO2 were performed to assess the possibility of using these CFs as CMS by comparing them with Takeda 3A CMS. The results suggest that there is an optimal stabilisation time which allows the preparation of CFs from an abundant raw precursor with properties similar to Takeda 3A CMS.

Microwave-assisted catalysis by iron oxide nanoparticles on MCM-41: Effect of the support morphology

Catalytically active heterogeneous catalysts have been prepared via microwave deposition of iron oxide nanoparticles (0.5–1.2 wt%) on MCM-41 type silica materials with different morphologies (particles, helical and spheres). This methodology leads to iron oxide nanoparticles composed by a mixture of FeO and Fe2O3 species, being the Fe(II)/Fe(III) peak ratio near to 1.11 by XPS. DRUV spectroscopy indicates the presence of tetrahedral coordinated Fe3+ in the silica framework of the three catalysts as well as some extraframework iron species in the catalysts with particle and sphere-like morphologies. The loading of the nanoparticles does neither affect the mesopore arrangement nor the textural properties of the silica supports, as indicated by SAXS and nitrogen adsorption/desorption isotherms. A detailed investigation of the morphology of the supports in various microwave-assisted catalyzed processes shows that helical mesostructures provide optimum catalytic activities and improved reusabilities in the microwave-assisted redox (selective oxidation of benzyl alcohol) catalyzed process probably due to a combination of lower particle size and higher acidity in comparison with the supports with particle and sphere morphology.

Characterization of Carbon Molecular Sieve Membranes Supported on Ceramic Tubes

Carbon molecular sieve membranes have been analyzed in supported and unsupported configurations in this experimental study. The membranes were used to adsorb CO2, N2 and CH4, and their adsorption data were analyzed to establish differences in rate and capacity of adsorption between the two types of samples (supported and unsupported). Experimental results show an important effect of the support, which can be considered as an additional parameter to tailor pore size on these carbon membranes. Immersion calorimetry values were measured by immersing the membranes into liquids of different molecular dimensions (dichloromethane, benzene, n-hexane, 2,2-dimethylbutane). Similarities were found between adsorption and calorimetric analysis. The pore volume of the samples analyzed ranged from 0.016 to 0.263 cm3/g. The effect of the pyrolysis temperature, either 550 or 700 °C, under N2 atmosphere was also analyzed. Quantification of the pore-size distribution of the support was done by liquid-liquid displacement porosimetry. The composite membrane was used for CO2/CH4 separation before and after pore plugging was done. The ideal selectivity factors value (4.47) was over the Knudsen theoretical factor (0.60) for membrane pyrolyzed at 600 °C, which indicates the potential application of these membranes for the separation of low-molecular weight gases.

Electrocatalytic reduction of CO2 to formate using particulate Sn electrodes: Effect of metal loading and particle size

The development of electrochemical processes for the conversion of CO2 into value-added products allows innovative carbon capture & utilization (CCU) instead of carbon capture & storage (CCS). In addition, coupling this conversion with renewable energy sources would make it possible to chemically store electricity from these intermittent renewable sources. The electroreduction of CO2 to formate in aqueous solution has been performed using Sn particles deposited over a carbon support. The effect of the particle size and Sn metal loading has been evaluated using cyclic voltammetry and chronoamperometry. The selected electrode has been tested on an experimental filter-press type cell system for continuous and single pass CO2 electroreduction to obtain formate as main product at ambient pressure and temperature. Experimental results show that using electrodes with 0.75 mg Sn cm−2, 150 nm Sn particles, and working at a current density of 90 mA cm−2, it is possible to achieve rates of formate production over 3.2 mmol m−2 s−1 and faradaic efficiencies around 70% for 90 min of continuous operation. These experimental conditions allow formate concentrations of about 1.5 g L−1 to be obtained on a continuous mode and with a single pass of catholyte through the cell.