Igor L. Moudrakovski

Bio: Igor L. Moudrakovski is an academic researcher from Max Planck Society. The author has contributed to research in topics: Clathrate hydrate & Hydrate. The author has an hindex of 50, co-authored 178 publications receiving 9052 citations. Previous affiliations of Igor L. Moudrakovski include Dalian Institute of Chemical Physics & University of Calgary.

Tuning clathrate hydrates for hydrogen storage

Abstract: The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework

Abstract: Metal organic frameworks (MOFs) are particularly exciting materials that couple porosity, diversity and crystallinity. But although they have been investigated for a wide range of applications, MOF chemistry focuses almost exclusively on properties intrinsic to the empty frameworks; the use of guest molecules to control functions has been essentially unexamined. Here we report Na(3)(2,4,6-trihydroxy-1,3,5-benzenetrisulfonate) (named β-PCMOF2), a MOF that conducts protons in regular one-dimensional pores lined with sulfonate groups. Proton conduction in β-PCMOF2 was modulated by the controlled loading of 1H-1,2,4-triazole (Tz) guests within the pores and reached 5 × 10(-4) S cm(-1) at 150 °C in anhydrous H(2), as confirmed by electrical measurements in H(2) and D(2), and by solid-state NMR spectroscopy. To confirm its potential as a gas separator membrane, the partially loaded MOF (β-PCMOF2(Tz)(0.45)) was also incorporated into a H(2)/air membrane electrode assembly. The resulting membrane proved to be gas tight, and gave an open circuit voltage of 1.18 V at 100 °C.

Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites

Abstract: The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant 'defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts.

Facile proton conduction via ordered water molecules in a phosphonate metal-organic framework.

Abstract: A new phosphonate metal−organic framework (MOF) with a layered motif but not that of the classical hybrid inorganic−organic solid is presented. Zn3(L)(H2O)2·2H2O (L = [1,3,5-benzenetriphosphonate]6−), henceforth denoted as PCMOF-3, contains a polar interlayer lined with Zn-ligated water molecules and phosphonate oxygen atoms. These groups serve to anchor free water molecules into ordered chains, as observed by X-ray crystallography. The potential for proton conduction via the well-defined interlayer was studied by 2H solid-state NMR spectroscopy and AC impedance spectroscopy. The proton conductivity in H2 was measured as 3.5 × 10−5 S cm−1 at 25 °C and 98% relative humidity. More interestingly, an Arrhenius plot gave a low activation energy of 0.17 eV for proton transfer, corroborating the solid-state NMR data that showed exchange between all deuterium sites in the D2O analogue of PCMOF-3, even at −20 °C.

The Chemistry and Applications of Metal-Organic Frameworks

Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

From Microporous to Mesoporous Molecular-Sieve Materials and Their Use in Catalysis

Abstract: It is possible to say that zeolites are the most widely used catalysts in industry They are crystalline microporous materials which have become extremely successful as catalysts for oil refining, petrochemistry, and organic synthesis in the production of fine and speciality chemicals, particularly when dealing with molecules having kinetic diameters below 10 A The reason for their success in catalysis is related to the following specific features of these materials:1 (1) They have very high surface area and adsorption capacity (2) The adsorption properties of the zeolites can be controlled, and they can be varied from hydrophobic to hydrophilic type materials (3) Active sites, such as acid sites for instance, can be generated in the framework and their strength and concentration can be tailored for a particular application (4) The sizes of their channels and cavities are in the range typical for many molecules of interest (5-12 A), and the strong electric fields2 existing in those micropores together with an electronic confinement of the guest molecules3 are responsible for a preactivation of the reactants (5) Their intricate channel structure allows the zeolites to present different types of shape selectivity, ie, product, reactant, and transition state, which can be used to direct a given catalytic reaction toward the desired product avoiding undesired side reactions (6) All of these properties of zeolites, which are of paramount importance in catalysis and make them attractive choices for the types of processes listed above, are ultimately dependent on the thermal and hydrothermal stability of these materials In the case of zeolites, they can be activated to produce very stable materials not just resistant to heat and steam but also to chemical attacks Avelino Corma Canos was born in Moncofar, Spain, in 1951 He studied chemistry at the Universidad de Valencia (1967−1973) and received his PhD at the Universidad Complutense de Madrid in 1976 He became director of the Instituto de Tecnologia Quimica (UPV-CSIC) at the Universidad Politecnica de Valencia in 1990 His current research field is zeolites as catalysts, covering aspects of synthesis, characterization and reactivity in acid−base and redox catalysis A Corma has written about 250 articles on these subjects in international journals, three books, and a number of reviews and book chapters He is a member of the Editorial Board of Zeolites, Catalysis Review Science and Engineering, Catalysis Letters, Applied Catalysis, Journal of Molecular Catalysis, Research Trends, CaTTech, and Journal of the Chemical Society, Chemical Communications A Corma is coauthor of 20 patents, five of them being for commercial applications He has been awarded with the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) 2373 Chem Rev 1997, 97, 2373−2419

Carbon Dioxide Capture: Prospects for New Materials

Abstract: The escalating level of atmospheric carbon dioxide is one of the most pressing environmental concerns of our age. Carbon capture and storage (CCS) from large point sources such as power plants is one option for reducing anthropogenic CO(2) emissions; however, currently the capture alone will increase the energy requirements of a plant by 25-40%. This Review highlights the challenges for capture technologies which have the greatest likelihood of reducing CO(2) emissions to the atmosphere, namely postcombustion (predominantly CO(2)/N(2) separation), precombustion (CO(2)/H(2)) capture, and natural gas sweetening (CO(2)/CH(4)). The key factor which underlies significant advancements lies in improved materials that perform the separations. In this regard, the most recent developments and emerging concepts in CO(2) separations by solvent absorption, chemical and physical adsorption, and membranes, amongst others, will be discussed, with particular attention on progress in the burgeoning field of metal-organic frameworks.

Principles Of Fluorescence Spectroscopy

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Silica-based mesoporous organic-inorganic hybrid materials.

Abstract: Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.