Surface composition and selectivity of alloy catalysts

A review with 146 ref

The role of carbon-hydrogen bond breaking in the epoxidation of ethylene

No abstract

Chemical Interactions in Multimetal/Zeolite Catalysts

This two-year project has led to a significant improvement in the fundamental understanding of the catalytic action of zeolite-supported redox catalysts. It turned out to be essential that we could combine four strategies for the preparation of catalysts containing transition metal (TM) ions in zeolite cavities: (1) ion exchange from aqueous solution; (2) chemical vapor deposition (CVD) of a volatile halide onto a zeolite in its acidic form; (3) solid state ion exchange; and (4) hydrothermal synthesis of a zeolite having TM ions in its lattice, followed by a treatment transporting these ions to ''guest positions''. Technique (2) enables us to position more TM ions into cavities than permitted by the conventional technique (1).viz one positive charge per Al centered tetrahedron in the zeolite lattice. The additional charge is compensated by ligands to the TM ions, for instance in oxo-ions such as (GaO){sup +} or dinuclear [Cu-O-Cu]{sup 2+}. While technique (3) is preferred over CVD where volatile halides are not available, technique (4) leads to rather isolated ''ex lattice'' oxo-ions. Such oxo-ions tend to be mono-nuclear, in contrast to technique (2) which preferentially creates dinuclear oxo-ions of the same TM element. A favorable element for the present research was that the PI is also actively engaged in a project on the reduction of nitrogen oxides, sponsored by EMSI program of the National Science Foundation and the US Department of Energy, Office of Science. This combination created a unique opportunity to test and analyze catalysts for the one step oxidation of benzene to phenol and compare them with catalysts for the reduction of nitrogen oxides, using hydrocarbons as the reductant. In both projects catalysts have been used which contain Fe ions or oxo-ions in the cavities the zeolite MFI, often called ZSM-5. With Fe as the TM-element and MFI as the host zeolite we found that catalysts with high Fe content, prepared by technique (2) were optimal for the De-NO{sub x} reaction, but extremely unselective for benzene oxidation to phenol. Conversely, the catalysts prepared with (4) had the highest turnover frequency for benzene oxidation, but performed very poorly for NO{sub x} reduction with so-butane. In fact the Fe concentration in the former catalysts were so low that it was necessary to design a special experimental program for the sole purpose of showing that it is really the Fe which catalyzes the benzene oxidation, not some acid center as has been proposed by other authors. For this purpose we used hydrogen sulfide to selectively poison the Fe sites, without deactivating the acidic sites. In addition we could show that the hydrothermal treatment of catalysts prepared by technique (4) is essential to transform iron ions in the zeolite lattice to ''ex lattice ions'' in guest positions. That line of the work required very careful experimentation, because a hydrothermal treatment of a zeolite containing Fe ions in its cavities can also lead to agglomeration of such ions to nano-particles of iron oxide which lowers the selectivity for the desired formation of phenol. This part of the program showed convincingly that indeed Fe is responsible for the benzene oxidation catalysis. The results and conclusion of this work, including the comparison of different catalysts, was published in a number of papers in the scientific literature, listed in the attached list. In these papers also our analysis of the reaction orders and the possible mechanism of the used test reaction are given

Strict Modes Everywhere - Bringing Order into Dynamics of Mechanical Systems by a Potential Compatible with the Geodesic Flow

Strict nonlinear normal modes provide very regular families of oscillations within conservative mechanical systems. However, a strict normal mode will generally be an isolated curve within the configuration space of the system. In this paper, we design a potential that will densely fill the configuration space with strict normal modes such that each configuration belongs to one mode and each mode passes through a common point, the equilibrium. As the potential can be realized by (nonlinear) elastic elements it can be used to execute a variety of periodic trajectories very efficiently. Most of the required torques will come from the elastic elements in the system and not from the actuators. We also design a controller stabilizing the system to a desired target mode and a controller performing swing-up and compensating dissipated energy. Finally, we showcase the approach for a two DoF manipulator. The experiments show that the approach performed well for the example system

EigenMPC: An Eigenmanifold-Inspired Model-Predictive Control Framework for Exciting Efficient Oscillations in Mechanical Systems

This paper proposes a Nonlinear Model-Predictive Control (NMPC) method capable of finding and converging to energy-efficient regular oscillations, which require no control action to be sustained. The approach builds up on the recently developed Eigenmanifold theory, which defines the sets of line-shaped oscillations of a robot as an invariant two-dimensional submanifold of its state space. By defining the control problem as a nonlinear program (NLP), the controller is able to deal with constraints in the state and control variables and be energy-efficient not only in its final trajectory but also during the convergence phase. An initial implementation of this approach is proposed, analyzed, and tested in simulation

Towards Autonomous Robotic Assembly: Using Combined Visual and Tactile Sensing for Adaptive Task Execution

Robotic assembly tasks are typically implemented in static settings in which parts are kept at fixed locations by making use of part holders. Very few works deal with the problem of moving parts in industrial assembly applications. However, having autonomous robots that are able to execute assembly tasks in dynamic environments could lead to more flexible facilities with reduced implementation efforts for individual products. In this paper, we present a general approach towards autonomous robotic assembly that combines visual and intrinsic tactile sensing to continuously track parts within a single Bayesian framework. Based on this, it is possible to implement object-centric assembly skills that are guided by the estimated poses of the parts, including cases where occlusions block the vision system. In particular, we investigate the application of this approach for peg-in-hole assembly. A tilt-and-align strategy is implemented using a Cartesian impedance controller, and combined with an adaptive path executor. Experimental results with multiple part combinations are provided and analyzed in detail

Vanadium oxide monolayer catalysts. I. Preparation, characterization, and thermal stability

Vanadium oxide catalysts of the monolayer type have been prepared by means of chemisorption of vanadate(V)-anions from aqueous solutions and by chemisorption of gaseous V2O3(OH)4. Using Al2O3, Cr2O3, TiO2, CeO2 and ZrO2, catalysts with an approximately complete monomolecular layer of vanadium(V) oxide on the carrier oxides can be prepared, if temperature is not too high. Divalent metal oxides like CdO and ZnO may already form threedimensional surface vanadates at moderate temperature. \ud The thermal stability of a monolayer catalyst is related to the parameter z/a, i. e. the ratio of the carrier cation charge to the sum of ionic radii of carrier cation and oxide anion. Thus, monolayer catalysts will be thermally stable only under the condition that z/a is not too high (aggregated catalyst) nor too small (ternary compound formation)

Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through Molecular Modeling and Combinatorial Methods

UOP LLC, a Honeywell Company, Ford Motor Company, and Striatus, Inc., collaborated with Professor Craig Jensen of the University of Hawaii and Professor Vidvuds Ozolins of University of California, Los Angeles on a multi-year cost-shared program to discover novel complex metal hydrides for hydrogen storage. This innovative program combined sophisticated molecular modeling with high throughput combinatorial experiments to maximize the probability of identifying commercially relevant, economical hydrogen storage materials with broad application. A set of tools was developed to pursue the medium throughput (MT) and high throughput (HT) combinatorial exploratory investigation of novel complex metal hydrides for hydrogen storage. The assay programs consisted of monitoring hydrogen evolution as a function of temperature. This project also incorporated theoretical methods to help select candidate materials families for testing. The Virtual High Throughput Screening served as a virtual laboratory, calculating structures and their properties. First Principles calculations were applied to various systems to examine hydrogen storage reaction pathways and the associated thermodynamics. The experimental program began with the validation of the MT assay tool with NaAlH4/0.02 mole Ti, the state of the art hydrogen storage system given by decomposition of sodium alanate to sodium hydride, aluminum metal, and hydrogen. Once certified, a combinatorial 21-point study of the NaAlH4 â LiAlH4 âMg(AlH4)2 phase diagram was investigated with the MT assay. Stability proved to be a problem as many of the materials decomposed during synthesis, altering the expected assay results. This resulted in repeating the entire experiment with a mild milling approach, which only temporarily increased capacity. NaAlH4 was the best performer in both studies and no new mixed alanates were observed, a result consistent with the VHTS. Powder XRD suggested that the reverse reaction, the regeneration of the alanate from alkali hydride, Al and hydrogen, was hampering reversibility. The reverse reaction was then studied for the same phase diagram, starting with LiH, NaH, and MgH2, and Al. The study was extended to phase diagrams including KH and CaH2 as well. The observed hydrogen storage capacity in the Al hexahydrides was less than 4 wt. %, well short of DOE targets. The HT assay came on line and after certification with studies on NaAlH4, was first applied to the LiNH2 - LiBH4 - MgH2 phase diagram. The 60-point study elucidated trends within the system locating an optimum material of 0.6 LiNH2 â 0.3 MgH2 â 0.1 LiBH4 that stored about 4 wt. % H2 reversibly and operated below 220 °C. Also present was the phase Li4(NH2)3BH4, which had been discovered in the LiNH2 -LiBH4 system. This new ternary formulation performed much better than the well-known 2 LiNH2 â MgH2 system by 50 °C in the HT assay. The Li4(NH2)3BH4 is a low melting ionic liquid under our test conditions and facilitates the phase transformations required in the hydrogen storage reaction, which no longer relies on a higher energy solid state reaction pathway. Further study showed that the 0.6 LiNH2 â 0.3 MgH2 â 0.1 LiBH4 formulation was very stable with respect to ammonia and diborane desorption, the observed desorption was from hydrogen. This result could not have been anticipated and was made possible by the efficiency of HT combinatorial methods. Investigation of the analogous LiNH2 â LiBH4 â CaH2 phase diagram revealed new reversible hydrogen storage materials 0.625 LiBH4 + 0.375 CaH2 and 0.375 LiNH2 + 0.25 LiBH4 + 0.375 CaH2 operating at 1 wt. % reversible hydrogen below 175 °C. Powder x-ray diffraction revealed a new structure for the spent materials which had not been previously observed. While the storage capacity was not impressive, an important aspect is that it boron appears to participate in a low temperature reversible reaction. The last major area of study also focused on activating boron-based materials in order to exploit the tremendous gravimetric capacity of LiBH4. A number of LiNH2 â LiBH4 â transition metal (TM) systems were investigated for the following reasons. No additional leads were discovered in this system. Another major project activity was the assembly of a high throughput synthesis system. The automated synthesizer was set up in a glovebox and was capable of handling liquids and powders and carrying out sealed block syntheses up to 250 °C. Unfortunately, the synthesizer could not handle the delivery of the fine powders required fro hydrogen storage applications. Although the powder delivery system was overhauled and redesigned several times, this problem was never remedied

Segmentation and Coverage Planning of Freeform Geometries for Robotic Surface Finishing

Surface finishing such as grinding or polishing is a time-consuming task, involves health risks for humans and is still largely performed by hand. Due to the high curvatures of complex geometries, different areas of the surface cannot be optimally reached by a simple strategy using a tool with a relatively large and flat finishing disk. In this paper, a planning method is presented that uses a variable contact point on the finishing disk as an additional degree of freedom. Different strategies for covering the workpiece surface are used to optimize the surface finishing process and ensure the coverage of concave areas. Therefore, an automatic segmentation method is developed to find areas with a uniform machining strategy based on the exact tool and workpiece geometry. Further, a method for planning coverage paths is presented, in which the contact area is modeled to realize an adaptive spacing between path lines. The approach was evaluated in simulation and practical experiments on the DLR SARA robot. The results show high coverage for complex freeform geometry and that adaptive spacing can optimize the overall process by reducing uncovered gaps and overlaps between coverage lines

Impedance Control on Arbitrary Surfaces for Ultrasound Scanning using Discrete Differential Geometry

We propose an approach to robotic ultrasound scanning and interaction control with arbitrary surfaces using a passivity-based impedance control scheme. First, we introduce task coordinates depending on the geometry of the surface, which enable hands-on guidance of the robot along the surface, as well as teleoperated and autonomous ultrasound image acquisition. Our coordinates allow controlling the signed distance of the robot to the surface and alignment of the tool to the surface normal using classical impedance control. This corresponds to implicitly obtaining a foliation of parallel surfaces. By setting the desired signed distance negative, i.e., into the surface, we obtain passive contact forces and simultaneously provide an intuitive way to control the maximum penetration depth into the surface. We extend the approach to also incorporate coordinates allowing to control the specific point on the surface and, automatically, on all parallel surfaces. Finally, we demonstrate the performance of the controller on the seven degrees of freedom lightweight robot DLR Miro: the robot tracks complex trajectories while accurately keeping the desired distance to the surface and applying an almost constant contact force. Finally, we compare the approach to the state of the art