Ag-Cu alloy surfaces in an oxidizing environment: a first-principles study

Recent experiments on model catalysts have shown that Ag-Cu alloys have improved selectivity with respect to pure silver for ethylene epoxidation. In this paper we review our first-principles investigations on the (111) surface of this alloy and present new findings on other low index surfaces. We find that, for every surface orientation, the presence of oxygen leads to copper segregation to the surface. Considering the alloy to be in equilibrium with an oxygen atmosphere and accounting for the effect of temperature and pressure, we compute the surface free energy and study the stability of several surface structures. Investigating the dependence of the surface free energy on the surface composition, we construct the phase diagram of the alloy for every surface orientation. Around the temperature, pressure and composition of interest for practical applications, we find that a limited number of structures can be present, including a thin layer of copper oxide on top of the silver surface and copper-free structures. Different surface orientations show a very similar behavior and in particular a single layer with CuO stoichiometry, significantly distorted when compared to a layer of bulk CuO, has a wide range of stability for all orientations. Our results are consistent with, and help explain, recent experimental measurements

First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment

In this paper we investigate by means of first-principles density functional theory calculations the (111) surface of the Ag-Cu alloy under varying conditions of pressure of the surrounding oxygen atmosphere and temperature. This alloy has been recently proposed as a catalyst with improved selectivity for ethylene epoxidation with respect to pure silver, the catalyst commonly used in industrial applications. Here we show that the presence of oxygen leads to copper segregation to the surface. Considering the surface free energy as a function of the surface composition, we construct the convex hull to investigate the stability of various surface structures. By including the dependence of the free surface energy on the oxygen chemical potential, we are able compute the phase diagram of the alloy as a function of temperature, pressure and surface composition. We find that, at temperature and pressure typically used in ethylene epoxidation, a number of structures can be present on the surface of the alloy, including clean Ag(111), thin layers of copper oxide and thick oxide-like structures. These results are consistent with, and help explain, recent experimental results.Comment: 10 pages, 6 figure

Feasibility study of a humidity control and oxygen supply system utilizing a water vapor electrolysis unit

Design and tests of water vapor electrolysis cell for generating and regulating spacecraft oxygen and for controlling humidit

Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This "pre-filling" of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.S.C. and R.W. acknowledge funding from EPSRC (Doctoral training award). R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge and a EU Marie Skłodowska-Curie Individual Fellowship (Global) under grant ARTIST (no. 656870) from the European Union’s Horizon 2020 research and innovation programme. B.C.B. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 656214 - 2DInterFOX. B.C.B and J.C.M. acknowledge support from the Austrian Science Fund (FWF): P25721-N20 and the Austrian Research Promotion Agency (FFG): 848152 - GraphenMoFET. A.C.-V. acknowledges the Conacyt Cambridge Scholarship and Roberto Rocca Fellowship. S.H. acknowledges funding from ERC grant InsituNANO (no. 279342). We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities at the BM20/ROBL beamline. We acknowledge the Helmholtz-Zentrum-Berlin Electron storage ring BESSY II for provision of synchrotron radiation at the ISISS beamline. We thank the ESRF and BESSY staff for continued support of our experiments and valuable discussion.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.nanolett.5b0458

Bulky-yet-flexible carbene ligands and their use in palladium cross-coupling

In recent years, several classes of new N-heterocyclic carbene (NHC) ligands were developed around the concept of flexible steric bulk. The steric hindrance of these ligands brings stability to the active species, while ligand flexibility still allows for the approach of the substrate. In this review, the synthesis of several types of new classes, such as IBiox, cyclic alkyl amino carbenes (CAAC), ITent, and IPr* are discussed, as well as how they move the state-of-the-art in palladium catalyzed cross-coupling forward

Ultrafiltration Fibers like Bioreactors

A polysulfone ultrafiltration membrane with pectinase physically immobilized on it by a dynamic formation method was used to examine the potential of these reactive membranes in applications involving solutions containing pectin. The effect of various operational parameters such as: pH of enzyme and pectin solutions, NaCl, retentate flow rate, and enzyme (Ce) and substrate (Cp) concentrations on the production of reducing compounds expressed as galacturonic acid (Ca), was investigated. It was found that the maximum Ca values were obtained when: (i) enzyme solution to immobilize, without NaCl, had pH values between 4.2 and 4.6 and enzyme concentration from 5.0 to 7.5 mg/mL; (ii) pectin solution had initial pH values between 4.2 and 5.0 and a concentration of 3 mg/mL; and (iii) retentate flow rate was 0.025 L/minFil: Carrin, Maria Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Ceci, Liliana Noemí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Lozano, Jorge Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentin

Bimetallic Cooperativity in Proton Reduction with an Amido‐Bridged Cobalt Catalyst

The bimetallic catalyst [CoII2(L1)(bpy)2]ClO4 (1), in which L1 is an [NN′2O2] fused ligand, efficiently reduced H+ to H2 in CH3CN in the presence of 100 equiv of HOAc with a turnover number of 18 and a Faradaic efficiency of 94 % after 3 h of bulk electrolysis at −1.6 V (vs. Ag/AgCl). This observation allowed the proposal that this bimetallic cooperativity is associated with distance, angle, and orbital alignment of the two Co centers, as promoted by the unique Co−Namido−Co environment offered by L1. Experimental results revealed that the parent [CoIICoII] complex undergoes two successive metal‐based 1 e− reductions to generate the catalytically active species [CoICoI], and DFT calculations suggested that addition of a proton to one CoI triggers a cooperative 1 e− transfer by each of these CoI centers. This 2 e− transfer is an alternative route to generate a more reactive [CoII(CoII−H−)] hydride, thus avoiding the CoIII−H− required in monometallic species. This [CoII(CoII−H−)] species then accepts another H+ to release H2

Integrated Micro Fuel Processor And Flow Delivery Infrastructure

Apparatus for transporting a fluid, atomizers, reactors, integrated fuel processing apparatus, combinations thereof, methods of atomizing reactants, methods of moving fluids, methods of reverse-flow in a reactor, and combinations thereof, are provided. One exemplary apparatus for transporting a fluid, among others, includes: a channel for receiving a fluid; a sensor for determining an internal condition of the fluid in the channel; and a channel actuator in communication with the sensor for changing a cross-sectional area of the channel based on the internal condition, wherein the change in cross-sectional area controls a parameter selected from a pressure and a fluid flow.Georgia Tech Research Corporatio

An archaeological mystery revealed by radiocarbon dating of cross-flow nanofiltrated amino acids derived from bone collagen, silk, and hair: case study of the bishops Baldwin I and Radbot II from Noyon-Tournai

Excavations in the cathedral of Tournai revealed two sepultures, which were identified by the excavators as those of bishops because of their special location in the cathedral. One burial was assigned to Baldwin I, who died in AD 1068, because (1) a ring with the inscription "BAL" was found and (2) a funeral stone with text was present on top of the grave mentioning the name Baldewinus. The second burial probably belongs to Radbot II, who was the successor of Baldwin I, and died in AD 1098. Both burials contained textiles (silk), the skeleton, a wooden pastoral staff, and human hair was still present on the skull of what was presumed to be Radbot II. All the protein-containing materials were degraded and/or contaminated. Standard sample pretreatment methods were not able to remove all the contaminants. Single and double cross-flow nanofiltration of the hydrolyzed protein-containing materials were performed. The sample quality for radiocarbon dating was improved and C-14 data revealed interesting and surprising results. The C-14 dates of the wooden pastoral staff and permeate femur confirm that the skeleton and tomb belong to bishop Baldwin I. The C-14 dates of hair and permeate skull indicate that the skeleton may indeed belong to bishop Radbot II. The younger C-14 dates of the wooden pastoral staff and silk samples indicate a postburial disturbance of the site burial during the 12th-13th century