Optimization of sol-immobilized bimetallic Au–Pd/TiO2 catalysts: reduction of 4-nitrophenol to 4-aminophenol for wastewater remediation

A sol-immobilization method is used to synthesize a series of highly active and stable AuxPd1−x/TiO2 catalysts (where x = 0, 0.13, 0.25, 0.5, 0.75, 0.87 and 1) for wastewater remediation. The catalytic performance of the materials was evaluated for the catalytic reduction of 4-nitrophenol, a model wastewater contaminant, using NaBH4 as the reducing agent under mild reaction conditions. Reaction parameters such as substrate/metal and substrate/reducing agent molar ratios, reaction temperature and stirring rate were investigated. Structure-activity correlations were studied using a number of complementary techniques including X-ray powder diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. The sol-immobilization route provides very small Au–Pd alloyed nanoparticles, with the highest catalytic performance shown by the Au0.5Pd0.5/TiO2 catalyst.This article is part of a discussion meeting issue ‘Science to enable the circular economy’

Energetic impact of size-selected metal cluster ions on graphite

We have investigated the impact of size-selected metal cluster ions (Agn-) on a covalently bonded substrate (graphite) over the energy range 15–1500 eV by a combination of scanning tunneling microscopy and molecular dynamics simulations. The key result is that the fate of the cluster (penetration into the surface versus diffusion and aggregation on the surface), at intermediate energies, depends on the lateral localization of the cluster kinetic energy at specific surface sites and thus, for small clusters, on the orientation of the cluster and the target substrate site

Shallow implantation of 'size-selected' Ag clusters into graphite

We have investigated the implantation of AgN (N = 20–200) clusters into a graphite substrate over the range of energies (E) 0.75–6 keV using molecular dynamics simulations. We find that after implantation the silver clusters remain coherent, albeit amorphous, and rest at the bottom of an open tunnel in the graphite created by the impact. It is found that the implantation depth of the clusters varies linearly as E/N2/3. We conclude that the cluster is decelerated by a constant force proportional to its cross-sectional area. We also identify a threshold energy for surface penetration associated with elastic compression of the graphite substrate

Photoinjector design for the LCLS

The design of the Linac Coherent Light Source assumes that a low-emittance, 1-nC, 10-ps beam will be available for injection into the 15-GeV linac. The proposed rf photocathode injector that will provide a 150-MeV beam with rms normalized emittances of 1 mm in both the transverse and longitudinal dimensions is based on a 1.6-cell S-band rf gun that is equipped with an emittance compensating solenoid. The booster accelerator is positioned at the beam waist coinciding with the first emittance maximum and is provided with an accelerating gradient of ~25 MeV/m, i.e., the "new working point." The uv pulses required for cathode excitation will be generated by tripling the output of a Ti:sapphire laser system consisting of a highly stable cw mode-locked oscillator and two bow-tie amplifiers pumped by a pair of Q-switched Nd:YAG lasers. The large bandwidth of the Ti:sapphire system accommodates the desired temporal pulse shaping. Details of the design and the supporting simulations are presented.Comment: 13 pages (double spaced), 4 figures, contributed to The 23rd International Free Electron Laser Conference, Darmstadt, Germany, 20-24 August 200

Scaling relations for implantation of size-selected Au, Ag, and Si clusters into graphite

The deposition of size-selected clusters represents a new route to the fabrication of truly nanometer-scale surface architectures, e.g., nanopores. We report a systematic experimental study, coupled with molecular dynamics simulations, of the implantation depths of size-selected Au7, Ag7, and Si7 clusters in the model graphite substrate. For impact energies between 1.0 and 5.5 keV, we find that the implantation depth scales linearly with the momentum of the clusters for all three types of cluster. This “universal” behavior is consistent with a (viscous) retarding force proportional to the velocity of the cluster, akin to Stokes’s law

Sodium atoms and clusters on graphite: a density functional study

Sodium atoms and clusters (N<5) on graphite (0001) are studied using density functional theory, pseudopotentials and periodic boundary conditions. A single Na atom is observed to bind at a hollow site 2.45 A above the surface with an adsorption energy of 0.51 eV. The small diffusion barrier of 0.06 eV indicates a flat potential energy surface. Increased Na coverage results in a weak adsorbate-substrate interaction, which is evident in the larger separation from the surface in the cases of Na_3, Na_4, Na_5, and the (2x2) Na overlayer. The binding is weak for Na_2, which has a full valence electron shell. The presence of substrate modifies the structures of Na_3, Na_4, and Na_5 significantly, and both Na_4 and Na_5 are distorted from planarity. The calculated formation energies suggest that clustering of atoms is energetically favorable, and that the open shell clusters (e.g. Na_3 and Na_5) can be more abundant on graphite than in the gas phase. Analysis of the lateral charge density distributions of Na and Na_3 shows a charge transfer of about 0.5 electrons in both cases.Comment: 20 pages, 6 figure

Isotope shift calculations for atoms with one valence electron

This work presents a method for the ab initio calculation of isotope shift in atoms and ions with one valence electron above closed shells. As a zero approximation we use relativistic Hartree-Fock and then calculate correlation corrections. The main motivation for developing the method comes from the need to analyse whether different isotope abundances in early universe can contribute to the observed anomalies in quasar absorption spectra. The current best explanation for these anomalies is the assumption that the fine structure constant, alpha, was smaller at early epoch. We test the isotope shift method by comparing the calculated and experimental isotope shift for the alkali and alkali-like atoms Na, MgII, K, CaII and BaII. The agreement is found to be good. We then calculate the isotope shift for some astronomically relevant transitions in SiII and SiIV, MgII, ZnII and GeII.Comment: 11 page

Susceptibility and dilution effects of the kagome bi-layer geometrically frustrated network. A Ga-NMR study of SrCr_(9p)Ga_(12-9p)O_(19)

We present an extensive gallium NMR study of the geometrically frustrated kagome bi-layer compound SrCr_(9p)Ga_(12-9p)O_(19) (Cr^3+, S=3/2) over a broad Cr-concentration range (.72<p<.95). This allows us to probe locally the kagome bi-layer susceptibility and separate the intrinsic properties due to the geometric frustration from those related to the site dilution. Our major findings are: 1) The intrinsic kagome bi-layer susceptibility exhibits a maximum in temperature at 40-50 K and is robust to a dilution as high as ~20%. The maximum reveals the development of short range antiferromagnetic correlations; 2) At low-T, a highly dynamical state induces a strong wipe-out of the NMR intensity, regardless of dilution; 3) The low-T upturn observed in the macroscopic susceptibility is associated to paramagnetic defects which stem from the dilution of the kagome bi-layer. The low-T analysis of the NMR lineshape suggests that the defect can be associated with a staggered spin-response to the vacancies on the kagome bi-layer. This, altogether with the maximum in the kagome bi-layer susceptibility, is very similar to what is observed in most low-dimensional antiferromagnetic correlated systems; 4) The spin glass-like freezing observed at T_g=2-4 K is not driven by the dilution-induced defects.Comment: 19 pages, 19 figures, revised version resubmitted to PRB Minor modifications: Fig.11 and discussion in Sec.V on the NMR shif

Longitudinal Proton Polarization in the Cooler

This research was sponsored by the National Science Foundation Grant NSF PHY-931478