Unravelling the transport mechanism of pore-filled membranes for hydrogen separation

The permeation characteristics of palladium pore filled (PF) membranes have been investigated with gas permeation and structural characterization of the membranes. PF membranes have been prepared by filling with Pd the nanoporous γ-Al2O3/YSZ (or pure YSZ) layer supported onto porous α-Al2O3 and ZrO2. The number of nanoporous layers and the applied vacuum level during the electroless plating process have been studied. Gas permeation properties of the PF membranes have been determined in a temperature range of 300-550 °C. The measured hydrogen permeances have been found to be lower than previously reported for similar membranes. It has been found that the hydrogen fluxes do not depend on the thickness of the nanoporous layers (γ-Al2O3/YSZ or pure YSZ) or on the vacuum pump employed for filling with Pd. The physicochemical characterization performed showed that the palladium deposited does not form a percolated network across the mesoporous layer(s), leading to low hydrogen permeances and thus low H2/N2 perm-selectivities.The presented work is funded within FERRET project as part of European Union’s Seventh Framework Programme (FP7/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement n° 621181. The Talos TEM was funded as part of HEFCE funding in the UK Research Partnership Investment Funding (UKRPIF) Manchester RPIF Round 2

Geometric phases for non-degenerate and degenerate mixed states

This paper focuses on the geometric phase of general mixed states under unitary evolution. Here we analyze both non-degenerate as well as degenerate states. Starting with the non-degenerate case, we show that the usual procedure of subtracting the dynamical phase from the total phase to yield the geometric phase for pure states, does not hold for mixed states. To this end, we furnish an expression for the geometric phase that is gauge invariant. The parallelity conditions are shown to be easily derivable from this expression. We also extend our formalism to states that exhibit degeneracies. Here with the holonomy taking on a non-abelian character, we provide an expression for the geometric phase that is manifestly gauge invariant. As in the case of the non-degenerate case, the form also displays the parallelity conditions clearly. Finally, we furnish explicit examples of the geometric phases for both the non-degenerate as well as degenerate mixed states.Comment: 23 page

Facile synthesis of single atom electrocatalysts via a condensation-carbonization process

The general and cost-effective synthesis of single atom electrocatalysts (SAECs) still remains a great challenge. Herein, we report a general synthetic protocol for the synthesis of SAECs via a simple condensation-carbonization process, in which furfural and cyanamide were condensation polymerized in the presence of polystyrene nanospheres and metal ions, followed by a pyrolysis to N-doped carbon nanosheets (NCNSs) supported SAECs. Six types of SAECs containing platinum, palladium, gold, nickel, cobalt and iron were synthesized to demonstrate the generality of the synthesis protocol. This methodology affords a facile solution to the trade-off between support conductivity and metal loading of SAECs by optimizing the ratio of carbon/nitrogen precursors, i.e., furfural furfuryl and cyanamide. The presence of single metal atoms was confirmed by high-angle annular dark field scanning transmission electron microscopy and X-ray absorption fine structure measurements. The three-dimensional distribution of single platinum atoms was vividly revealed by depth profile analysis in the scanning transmission electron microscope. The resulting SAECs showed excellent performance for glycerol electro-oxidation and water splitting in alkaline solutions. Notably, Pt/NCNs possessed an unprecedent mass-normalized current density of 5.3 A per milligram of platinum, which is 32 times that of the commercial Pt/C catalyst. Density functional theory calculations were conducted to reveal the adsorption behavior of glycerol over the SAECs. Using Ni/NCNSs and Co/NCNSs as anodic and cathodic electrocatalysts, we constructed a solar panel powered electrolytic cell for overall water splitting, leading to an overall energy efficiency of 8.8%, which has been among one of the largest solar-to-hydrogen conversion efficiencies reported in the literature

Hemoglobin-derived Fe-Nx-S species supported by bamboo-shaped carbon nanotubes as efficient electrocatalysts for the oxygen evolution reaction

Herein, we report a facile route to synthesize isolated single iron atoms on nitrogen-sulfur-codoped carbon matrix via a direct pyrolysis process in which hemoglobin, a by-product of the meat industry, was utilized as a precursor for iron, nitrogen and sulfur while bamboo-shaped carbon nanotubes served as a support owing to their excellent conductivity and numerous defects. The resulting metal-nitrogen complexed carbon showed outstanding catalytic performance for the oxygen evolution reaction (OER) in alkaline solutions. At an overpotential of 380 mV, the optimal sample yielded a current density of 83.6 mA cm−2, which is 2.5 times that of benchmark IrO2 (32.8 mA cm−2), rendering it as one of the best OER catalysts reported so far. It also showed negligible activity decay in alkaline solutions during long-term durability tests. Control experiments and X-ray absorption fine structure analyses revealed that Fe-Nx species in the samples are the active sites for OER. Further density functional theory calculations indicated that the presence of sulfur in the carbon matrix modified the electronic structures of active species, thereby leading to the superior activity of the sample

CO2 hydrogenation to methanol on intermetallic PdGa and PdIn catalysts and the effect of Zn co-deposition

The behaviour of Pd deposited on Ga2O3 and In2O3 by CVI is compared for the hydrogenation of CO2 to methanol. Ga2O3 alone is inactive, but In2O3 has good conversion, and selectivity as high as 89 % to CH3OH. The addition of Pd to the catalysts had relatively little effect for In2O3, but in contrast, the addition of Pd to Ga2O3, has a very big effect, inducing high activity and selectivity to methanol. Both oxides form Pd intermetallics - Pd2In3 and Pd2Ga. However, for the In catalysts there is also a thick (∼3 nm) overlayer of the oxide, while for the Ga catalyst there was no such overlayer. Hence this is why addition of Pd to the Indium catalysts has relatively little effect on performance compared with Ga. Furthermore, the effect of Pd and Zn co-deposition on Ga₂O₃ and In₂O₃ was investigated, as well as the effect of the support morphology. Upon co-deposition of Pd and Zn, and after reduction, the Pd2In3 catalyst remains phase stable, whereas the Pd2Ga alloy is replaced by PdZn, and is improved in methanol yield

The critical role of βPdZn alloy in Pd/ZnO catalysts for the hydrogenation of carbon dioxide to methanol

The rise in atmospheric CO2 concentration and the concomitant rise in global surface temperature have prompted massive research effort in designing catalytic routes to utilize CO2 as a feedstock. Prime among these is the hydrogenation of CO2 to make methanol, which is a key commodity chemical intermediate, a hydrogen storage molecule, and a possible future fuel for transport sectors that cannot be electrified. Pd/ZnO has been identified as an effective candidate as a catalyst for this reaction, yet there has been no attempt to gain a fundamental understanding of how this catalyst works and more importantly to establish specific design criteria for CO2 hydrogenation catalysts. Here, we show that Pd/ZnO catalysts have the same metal particle composition, irrespective of the different synthesis procedures and types of ZnO used here. We demonstrate that all of these Pd/ZnO catalysts exhibit the same activity trend. In all cases, the β-PdZn 1:1 alloy is produced and dictates the catalysis. This conclusion is further supported by the relationship between conversion and selectivity and their small variation with ZnO surface area in the range 6–80 m2g–1. Without alloying with Zn, Pd is a reverse water-gas shift catalyst and when supported on alumina and silica is much less active for CO2 conversion to methanol than on ZnO. Our approach is applicable to the discovery and design of improved catalysts for CO2 hydrogenation and will aid future catalyst discovery

Search for direct production of charginos and neutralinos in events with three leptons and missing transverse momentum in √s = 7 TeV pp collisions with the ATLAS detector

A search for the direct production of charginos and neutralinos in final states with three electrons or muons and missing transverse momentum is presented. The analysis is based on 4.7 fb−1 of proton–proton collision data delivered by the Large Hadron Collider and recorded with the ATLAS detector. Observations are consistent with Standard Model expectations in three signal regions that are either depleted or enriched in Z-boson decays. Upper limits at 95% confidence level are set in R-parity conserving phenomenological minimal supersymmetric models and in simplified models, significantly extending previous results

Jet size dependence of single jet suppression in lead-lead collisions at sqrt(s(NN)) = 2.76 TeV with the ATLAS detector at the LHC

Measurements of inclusive jet suppression in heavy ion collisions at the LHC provide direct sensitivity to the physics of jet quenching. In a sample of lead-lead collisions at sqrt(s) = 2.76 TeV corresponding to an integrated luminosity of approximately 7 inverse microbarns, ATLAS has measured jets with a calorimeter over the pseudorapidity interval |eta| < 2.1 and over the transverse momentum range 38 < pT < 210 GeV. Jets were reconstructed using the anti-kt algorithm with values for the distance parameter that determines the nominal jet radius of R = 0.2, 0.3, 0.4 and 0.5. The centrality dependence of the jet yield is characterized by the jet "central-to-peripheral ratio," Rcp. Jet production is found to be suppressed by approximately a factor of two in the 10% most central collisions relative to peripheral collisions. Rcp varies smoothly with centrality as characterized by the number of participating nucleons. The observed suppression is only weakly dependent on jet radius and transverse momentum. These results provide the first direct measurement of inclusive jet suppression in heavy ion collisions and complement previous measurements of dijet transverse energy imbalance at the LHC.Comment: 15 pages plus author list (30 pages total), 8 figures, 2 tables, submitted to Physics Letters B. All figures including auxiliary figures are available at http://atlas.web.cern.ch/Atlas/GROUPS/PHYSICS/PAPERS/HION-2011-02

Measurement of the polarisation of W bosons produced with large transverse momentum in pp collisions at sqrt(s) = 7 TeV with the ATLAS experiment

This paper describes an analysis of the angular distribution of W->enu and W->munu decays, using data from pp collisions at sqrt(s) = 7 TeV recorded with the ATLAS detector at the LHC in 2010, corresponding to an integrated luminosity of about 35 pb^-1. Using the decay lepton transverse momentum and the missing transverse energy, the W decay angular distribution projected onto the transverse plane is obtained and analysed in terms of helicity fractions f0, fL and fR over two ranges of W transverse momentum (ptw): 35 < ptw < 50 GeV and ptw > 50 GeV. Good agreement is found with theoretical predictions. For ptw > 50 GeV, the values of f0 and fL-fR, averaged over charge and lepton flavour, are measured to be : f0 = 0.127 +/- 0.030 +/- 0.108 and fL-fR = 0.252 +/- 0.017 +/- 0.030, where the first uncertainties are statistical, and the second include all systematic effects.Comment: 19 pages plus author list (34 pages total), 9 figures, 11 tables, revised author list, matches European Journal of Physics C versio

Observation of a new chi_b state in radiative transitions to Upsilon(1S) and Upsilon(2S) at ATLAS

The chi_b(nP) quarkonium states are produced in proton-proton collisions at the Large Hadron Collider (LHC) at sqrt(s) = 7 TeV and recorded by the ATLAS detector. Using a data sample corresponding to an integrated luminosity of 4.4 fb^-1, these states are reconstructed through their radiative decays to Upsilon(1S,2S) with Upsilon->mu+mu-. In addition to the mass peaks corresponding to the decay modes chi_b(1P,2P)->Upsilon(1S)gamma, a new structure centered at a mass of 10.530+/-0.005 (stat.)+/-0.009 (syst.) GeV is also observed, in both the Upsilon(1S)gamma and Upsilon(2S)gamma decay modes. This is interpreted as the chi_b(3P) system.Comment: 5 pages plus author list (18 pages total), 2 figures, 1 table, corrected author list, matches final version in Physical Review Letter