Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

Reference LPI-ARTICLE-1999-017View record in Web of Science Record created on 2006-02-21, modified on 2017-05-12

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Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms.

XRD, UV−Vis, EXAFS, XANES, and Raman techniques have been used to study the removal of water molecules coordinated to the Cu(II) framework atoms of the novel HKUST-1 metal-organic framework. The dehydration process preserves the crystalline nature of the material, just causing a reduction of the cell volume due to the shrinking of the [Cu2C4O8] cage. The removal of adsorbed H2O molecule makes the framework Cu(II) sites available for interaction with other probe molecules. In situ IR spectroscopy has evidenced the formation at liquid nitrogen temperature of labile Cu(II)···CO adducts characterized by a ν(C−O) = 2178 cm-1 and at 15 K of Cu(II)···H2 adducts characterized by a ν(H−H) = 4100 cm-1. To the best of our knowledge, we have observed for the first time a clear signal of Cu(II) carbonyl and dihydrogen complexes formed inside a crystalline microporous hosting matrix. The sinking of the oxygens of the carboxyl units, undergone by the Cu(II) framework ions in the dehydration process, is responsible for...

Local Structure of Framework Cu(II) in HKUST-1 Metallorganic Framework: Spectroscopic Characterization upon Activation and Interaction with Adsorbates

The review is a summary and analysis of the data characterizing CO adsorption on surface cationic sites of oxides including supported materials and microporous and mesoporous materials. The contributions of various types of CO bonding to the IR frequency shifts of carbon-bonded molecules are analyzed, namely, the increase of the CO stretching frequency in cases of electrostatic and σ bonding and the decrease of the frequency with π bonding. Polycarbonyls, bridging CO, oxygen-bonded CO, and tilted CO are also considered. The main part of the review is a collection of the experimental results characterizing carbonyls of individual metal ions. The spectral behavior of CO bonded to metal atoms is also assessed in the cases when the metal ions are easily reduced to metal (Cu, Ag, Au, Pd, or Pt) or cationic carbonyls are produced after CO adsorption on supported metals (Ru, Rh, Ir, and Os). The interaction of CO with surface OH groups is also considered. It is demonstrated that IR spectroscopy of adsorbed CO is an efficient methodology to characterize cationic surface sites in terms of their nature, oxidation states, coordination environment and coordinative unsaturation, and location at faces, edges or corners of microcrystallites. When applied to materials with surface hydroxyl groups CO undergoes hydrogen bonding and information can be collected on the proton acid strength.

Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule

Intermolecular interactions between H2 and ligands, metals, and metal–ligand complexes determine the binding affinities of potential hydrogen storage materials (HSM), and thus their extent of potential for practical use. A brief survey of current activity on HSM is given. The key issue of binding strengths is examined from a basic perspective by surveying the distinct classes of interactions (dispersion, electrostatics, orbital interactions) in first a general way, and then in the context of calculated binding affinities for a range of model systems.

Computational studies of molecular hydrogen binding affinities: the role of dispersion forces, electrostatics, and orbital interactions.

Spectra of hydroxyl groups in zeolites in the near-infrared region

A new type of acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to diffuse reflectance i.r. spectroscopy

A DRIFT study of ZnHZSM-5 zeolites with Si/Al ratios of 15 or 41 and a Zn loading of 0.8 wt% revealed a high thermal stability of bridging OH groups that was practically the same as in the pure hydrogen forms. It was concluded that the incipient wetness impregnation of NH4ZSM-5 zeolite with zinc nitrate and the subsequent high-temperature treatment results only in a minor amount of ion exchange. A considerable part of the modifying zinc forms nanometric ZnO clusters inside the channels of the zeolite. The use of the low-temperature adsorption of dihydrogen as a probe indicated the appearance, after high-temperature vacuum pretreatment, of three different Lewis acid sites connected with coordinatively-unsaturated Zn2+ ions. The strongest Lewis sites, with an H–H stretching frequency of adsorbed molecular hydrogen of 3940 cm−1, dissociatively adsorbed hydrogen, methane and propane at both room and elevated temperatures. These sites are represented either by Zn2+ ions on the walls of the main channels of the zeolite (α sites according to Mole et al.) or by Lewis-base pairs on the surface of nanometric clusters of zinc oxide.

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V. Yu. Borovkov

Papers

Spectra of hydroxyl groups in zeolites in the near-infrared region

A new type of acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to diffuse reflectance i.r. spectroscopy

Nature of the sites of dissociative adsorption of dihydrogen and light paraffins in ZnHZSM-5 zeolite prepared by incipient wetness impregnation

Low temperature hydrogen adsorption on sodium forms of faujasites: barometric measurements and drift spectra

Near infrared diffuse reflectance study of high silica containing zeolites