High throughput screening of low temperature CO oxidation catalysts using IR thermography

The catalytic oxidation of carbon monoxide to carbon dioxide is an important process used in several areas such as respiratory protection, industrial air purification, automotive emissions control, CO clean-up of flue gases and fuel cells. Research in this area has mainly focused on the improvement of catalytic activity at low temperatures. Numerous catalyst systems have been proposed, including those based on Pt, Pd, Rh, Ru, Au, Ag, and Cu, supported on refractory or reducible carriers or dispersed in perovskites. Well known commercial catalyst formulations for room temperature CO oxidation are based on CuMn2O4 (hopcalite) and CuCoAgMnOx mixed oxides. We have applied high-throughput and combinatorial methodologies to the discovery of more efficient catalysts for low temperature CO oxidation. The screening approach was based on a hierarchy of qualitative and semi-quantitative primary screens for the discovery of hits, and quantitative secondary screens for hit confirmation, lead optimization and scale-up. Parallel IR thermography was the primary screen, allowing one wafer-formatted library of 256 catalysts to be screened in approximately 1 hour. Multi-channel fixed bed reactors equipped with imaging reflection FTIR spectroscopy or GC were used for secondary screening. Novel RuCoCe compositions were discovered and optimized for CO oxidation and the effect of doping was investigated for supported and bulk mixed oxide catalysts. Another family of active hits that compare favorably with the Pt/Al2O3 benchmark is based on RuSn, where Sn can be used as a dopant (e.g. RuSn/SiO2) and/or as a high surface area carrier (e.g., SnO2 or Sn containing mixed metal oxides). Also, RuCu binary compositions were found to be active after a reduction pretreatment with hydrogen.     

Discovery of novel catalytic materials for emissions control using high throughput scanning mass spectrometry

High-throughput approaches were applied to the discovery of more efficient catalysts for various applications in emissions control. The screening approach was based on a hierarchy of qualitative or semi-quantitative primary screens for discovery of hits and quantitative secondary screens for confirmation and scale-up of leads. In this work, primary screening was carried out by fast scanning mass spectrometry (SMS) for NO(x) abatement, low temperature CO oxidation, VOC removal, CO(x) methanation and the water gas shift (WGS) reaction.     

Oxide thin films based on ordered arrays of 1D nanostructure. A possible approach toward bridging material gap in catalysis

TiO(2) thin films based on ordered arrays of 1D nanostructures (nanorods, nanotubes) are proposed as suitable model materials in studies for bridging material and complexity gap in catalysis. The samples were prepared by anodic oxidation of Ti foils. By changing the preparation conditions (pH, procedure of application of the potential), different types of 1D nanostructure and different characteristics of the ordered array of these 1D nanostructures could be obtained. This allows studying the effect of nanodimension and 3D nanoarchitecture on the characteristics and reactivity of these catalysts. It is also shown that TiO(2) thin films characterized by a well-ordered array of titania nanorod behave as photonic materials, thus showing unique properties of light harvesting efficiency.     

Electrocatalytic reduction of CO2 to CO by polypyridyl ruthenium complexes

Electrocatalytic reduction of CO(2) by [Ru(tpy)(bpy)(solvent)](2+) (tpy = 2,2':6',2'-terpyridine, bpy = 2,2'-bipyridine) and its structural analogs is initiated by sequential 1e(-) reductions at the tpy and bpy ligands followed by rate limiting CO(2) addition to give a metallocarboxylate intermediate. It undergoes further reduction and loss of CO.     

Identification of Viscoelastic Properties and Damaging Effects of Highly Extensible Polyurea

The present work aims particular at the experimental identification of the viscoelastic properties of polyurea as well as on the onset of the damage. For the viscoelastic part, several relaxation experiments are performed. From the measured data a general viscoelastic model is derived where we use two different approaches. At first we identify a general Maxwell model (combining spring and damping elements for finite deformations) to use a prony series with N elements, which requires the identification of 2N + 1 parameters. At second, a model of generalized fractional elements [3] is employed. Both approaches are studied in detail and are compared to data from literature; furthermore a comparison concerning the effort is presented. Damaging effects of Polyurea are investigated using tensile tests with and without cyclic loading. In particular we focus on the the onset of damage by cavitation. To this end the recovered specimens were analyzed using a laser microscope; the surfaces of the ruptured areas are compared in terms of quantity and size of voids. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fracture toughness investigations on UHPC by spalling tests

Ultra High Performance Concrete (UHPC) is defined as a new generation of concrete which shows improved performance and higher strength than traditional concrete. This allows to realize slender and much more durable structures and in this way significantly reduces the required resources. Despite its huge potential in construction, technical information about this new type of material is still limited. This contribution presents investigations on the dynamic mechanical behavior and properties of UHPC specimens by spalling experiments. Two different recipes were used to compare the properties. Due to the special specimen geometry (slender cylindrical) a flowable consistency was required to enable a sufficient degassing of the mixtures. For the test, a Split Hopkinson Pressure Bar (SHPB) has been modified and used. A high speed photograph system was focused on the fragmentation process during the test. On the basis of these experiments the dynamic E-moduli as well as the dynamic tensile strength of the UHPC specimens were determined. By observation of the specific crack patterns on each tested specimen and corresponding times, the dynamic fracture energy is calculated. Numerical simulations also were performed and compared to the experimental result. It is concluded that the dynamic tensile strength of the UHPC increases at higher strain rates. The results of the current study provide technical information about fracture and dynamic behavior of UHPC and the obtained values could be used for future computational models. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Full-field swept-source phase microscopy

We present a full-field phase microscopy technique for quantitative nanoscale surface profiling of samples in reflection. This technique utilizes swept-source optical coherence tomography in a full-field common path interferometer for phase-stable cross-sectional acquisition without scanning. Subwavelength variations in surface sample features are measured without interference from spurious reflections by processing the interferometric phase at a selected depth plane, providing a 1.3 nm stability for high signal-to-noise ratio surface features. Nanoscale imaging was demonstrated by measuring the location of receptor sites on a DNA assay biochip and the surface topography of erythrocytes in a blood smear.     

Engineered complex emulsion system: toward modulating the pore length and morphological architecture of mesoporous silicas

In the complex alkane/P123/TEOS/H2O emulsion system, an emulsion engineering method to modulate pore length and morphological architecture of mesoporous materials has been built. With fine tuning of the synthetic parameters (e.g., the composition of the synthetic mixtures, temperature, stirring, etc.), a series of chemically significant mesostructures (i.e., short-pore SBA-15 materials) with tunable pore length and morphological architecture have been successfully constructed. The effects of alkane solubilizates on pore length and particle morphology are discussed. The resulting short-pore materials would have potential applications in the fields of adsorption/separation of biomolecules and inclusion chemistry of guest species, etc.     

Matrix decomposition algorithms for the finite element Galerkin method with piecewise Hermite cubics

Matrix decomposition algorithms (MDAs) employing fast Fourier transforms are developed for the solution of the systems of linear algebraic equations arising when the finite element Galerkin method with piecewise Hermite bicubics is used to solve Poisson’s equation on the unit square. Like their orthogonal spline collocation counterparts, these MDAs, which require O(N ²logN) operations on an N×N uniform partition, are based on knowledge of the solution of a generalized eigenvalue problem associated with the corresponding discretization of a two-point boundary value problem. The eigenvalues and eigenfunctions are determined for various choices of boundary conditions, and numerical results are presented to demonstrate the efficacy of the MDAs. Weiwei Sun was supported in part by a grant from City University of Hong Kong (Project No. CityU 7002110).