Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface

Synthesis of Supported Pd-0 Nanoparticles from a Single-Site Pd2+ Surface Complex by Alkene Reduction

A surface metal-organic complex, (-AlOx)Pd(acac) (acac = acetylacetonate), is prepared by chemically grafting the precursor Pd(acac)(2) onto gamma-Al2O3 in toluene at 25 degrees C. The resulting surface complex is characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and dynamic nuclear polarization surface-enhanced solid-state nuclear magnetic resonance spectroscopy (DNP SENS). This surface complex is a precursor in the direct synthesis of size-controlled Pd nanoparticles under mild reductive conditions and in the absence of additional stabilizers or pretreatments. Indeed, upon exposure to gaseous ethylene or liquid 1-octene at 25 degrees C, the Pd2+ species is reduced to form Pd-0 nanoparticles with a mean diameter of 4.3 +/- 0.6 nm, as determined by scanning transmission electron microscopy (STEM). These nanoparticles are catalytically relevant using the aerobic 1-phenylethanol oxidation as a probe reaction, with rates comparable to a conventional Pd/Al2O3 catalyst but without an induction period. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction mass spectrometry (TPR-MS) reveal that the surface complex reduction with ethylene coproduces H-2, acetylene, and 1,3-butadiene. This process reasonably proceeds via an olefin activation/coordination/insertion pathway, followed by beta-hydride elimination to generate free Pd-0. The well-defined nature of the single-site supported Pd2+ precursor provides direct mechanistic insights into this unusual and likely general reductive process

Epitaxial Stabilization of Face Selective Catalysts

Abstract Selective, active, and robust catalysts are necessary for the efficient utilization of new feedstocks. Faceselective catalysts can precisely modify catalytic properties, but are often unstable under reaction conditions, changing shape and losing selectivity. Herein we report a method for synthesizing stable heterogeneous catalysts in which the morphology and selectivity can be tuned precisely and predictably. Using nanocrystal supports, we epitaxially stabilize specific active phase morphologies. This changes the distribution of active sites of different coordination, which have correspondingly different catalytic properties. Specifically, we utilize the different interfacial free-energies between perovskite titanate nanocube supports with different crystal lattice dimensions and a platinum active phase. By substituting different sized cations into the support, we change the lattice mismatch between the support and the active phase, thereby changing the interfacial free-energy, and stabilizing the active phase in different morphologies in a predictable manner. We correlate these changes in active phase atomic coordination with changes in catalytic performance (activity and selectivity), using the hydrogenation of acrolein as a test reaction. The method is general and can be applied to many nanocrystal supports and active phase combinations. Keywords Epitaxy Á Perovskite Á Platinum Á Heterogeneous catalysis Á Hydrogenation Á Acrolein Controlling the morphology of catalytic metal nanoparticles has incredible potential for improving selectivity and yield. This is because catalytic properties often depend upon the coordination of active site atoms We have recently observed that oriented oxide nanocrystal supports can epitaxially stabilize a specific orientation and morphology of the active phas

Synthesis-Dependent First-Order Raman Scattering in SrTiO 3 Nanocubes at Room Temperature

Raman spectroscopy was used to demonstrate that the lattice dynamics of SrTiO 3 (STO) nanoparticles strongly depends on their microstructure, which is in turn determined by the synthetic approach employed. First-order Raman modes are observed at room temperature in STO single-crystalline nanocubes with average edge lengths of 60 and 120 nm, obtained via sol-precipitation coupled with hydrothermal synthesis and a molten salt procedure, respectively. First-order Raman scattering arises from local loss of inversion symmetry caused by surface frozen dipoles, oxygen vacancies, and impurities incorporated into the host lattice. The presence of polar domains is suggested by the pronounced Fano asymmetry of the peak corresponding to the TO2 polar phonon, which does not vanish at room temperature. These noncentrosymmetric domains will likely influence the dielectric response of these nanoparticles

Ethics review as a component of institutional approval for a multicentre continuous quality improvement project: the investigator's perspective

BACKGROUND: For ethical approval of a multicentre study in Canada, investigators must apply separately to individual Research Ethics Boards (REBs). In principle, the protection of human research subjects is of utmost importance. However, in practice, the process of multicentre ethics review can be time consuming and costly, requiring duplication of effort for researchers and REBs. We used our experience with ethical review of The Canadian Perinatal Network (CPN), to gain insight into the Canadian system. METHODS: The applications forms of 16 different REBs were abstracted for a list of standardized items. The application process across sites was compared. Correspondence between the REB and the investigators was documented in order to construct a timeline to approval, identify the specific issues raised by each board, and describe how they were resolved. RESULTS: Each REB had a different application form. Most (n = 9) had a two or three step application process. Overall, it took a median of 31 days (range 2-174 days) to receive an initial response from the REB. Approval took a median of 42 days (range 4-443 days). Privacy and consent were the two major issues raised. Several additional minor or administrative issues were raised which delayed approval. CONCLUSIONS: For CPN, the Canadian REB process of ethical review proved challenging. REBs acted independently and without unified application forms or submission procedures. We call for a critical examination of the ethical, privacy and institutional review processes in Canada, to determine the best way to undertake multicentre review

Synthesis and Understanding of Novel Catalysts

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supported metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts

2014 Chemical Reactions at Surfaces Gordon Research Conference and Gordon Research Seminar (April 28-May 3, 2013 - Les Diablerets Conference Center, Les Diablerets, Switzerland)

presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments