Function Of Ion Charge Research Articles

Activity of calcined Ag,Cu,Au/TiO2 catalysts in the dehydrogenation/dehydration of ethanol

The catalytic activity of the anatase TiO2 and Mz+/TiO2 with supported ions Mz+ = Ag+, Cu2+, Au3+ in vapor phase conversions of ethanol is investigated at temperatures of 100–400°C. It is shown that the yields of acetaldehyde and ethylene decline for the most active catalyst Cu2+/TiO2 but increase for TiO2 and Ag/TiO2. The drop in the activation energy of the dehydrogenation reaction over calcined samples is linearly correlated with the one in the reduction potential of Mz+ to Cu+, Au+, Ag0 and the ionic radius of Mz+ in the crystal. The energies of activation for ethylene formation change in the series TiO2 > Au3+ > Cu2+ >Ag+ and TiO2 ≈ Cu2+ ≈ Ag+ > Au3+ for the calcined samples. The rate of pyridine adsorption, considered as an indicator of the activity of acid sites, is a linear function of ion charge +z = 1, 2, 3, and slows by two-thirds after calcination.

Applications of polarizable continuum models to determine accurate solution-phase thermochemical values across a broad range of cation charge - the case of U(III-VI).

Contributing factors to the solution-phase correction to the free energy of the molecular clusters U(H2O)n(3+/4+) and UO2(H2O)m(1+/2+) (n = 8, 9, 30, 41, 77; m = 4, 5, 30, 41, 77) have been examined as a function of cavity type in the integrated-equation-formalism-protocol (IEF) and SMD polarizable continuum models (PCMs). It is observed that the free energy correction, Gcorr, does not smoothly converge to zero as the number of explicitly solvating water molecules approaches the bulk limit, and the convergence behavior varies significantly with cavity and model. The rates of convergence of the gas-phase hydration energy, ΔGhyd, wherein the bare metal ion is inserted into a molecular water cluster and ΔGcorr for the reaction exhibit wide variations as a function of ion charge, cavity, and model. This is the likely source of previously reported discrepancies in predicted free energies of solvation for metal ions when using different PCM cavities and/or models. The cancellation of errors in ΔGhyd and ΔGcorr is optimal for clusters consisting of only a second solvation shell of explicit water molecules (n = m = 30). The UFF cavity within IEF, in particular, exhibits the most consistent cancellation of errors when using a molecular cluster consisting of a second shell of solvating water for all oxidation states of uranium, leading to accurate free energies of solvation ΔGsolv for these species.

Ion Transport in Sulfonated Nanoporous Colloidal Films

The surface of self-assembled nanoporous silica colloidal crystalline films comprised of 184-nm-diameter silica spheres has been sulfonated using 1,3-propanesultone. The transport of ions through the sulfonated films has been studied using cyclic voltammetry in water as a function of ion charge, pH, and solution ionic strength. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. This behavior is pH-dependent and is due to electrostatic repulsion/attraction that can be modulated by changing the ionic strength of the contacting solution.

Low- and medium-mass ion acceleration driven by petawatt laser plasma interactions

An experimental investigation of low- and medium-mass ion acceleration from resistively heated thin foil targets, irradiated by picosecond laser pulses at intensities up to 5 × 1020 W cm−2, is reported. It is found that the spectral distributions of ions, up to multi-MeV/nucleon energies, accelerated from the rear surface of the target are broadly consistent with previously reported measurements made at intensities up to 5 × 1019 W cm−2. Properties of the backward-directed beams of ions accelerated from the target front surface are also measured, and it is found that, compared with the rear surface, higher ion numbers and charges, and similar ion energies are produced. Additionally, the scaling of the maximum ion energy as a function of ion charge and laser intensity are measured and compared with the predictions of a numerical model.