RESUMEN

Water influences critically the kinetics of the autocatalytic conversion of methanol to hydrocarbons in acid zeolites. At very low conversions but otherwise typical reaction conditions, the initiation of the reaction is delayed in presence of H2O. In absence of hydrocarbons, the main reactions are the methanol and dimethyl ether (DME) interconversion and the formation of a C1 reactive mixture-which in turn initiates the formation of first hydrocarbons in the zeolite pores. We conclude that the dominant reactions for the formation of a reactive C1 pool at this stage involve hydrogen transfer from both MeOH and DME to surface methoxy groups, leading to methane and formaldehyde in a 1:1 stoichiometry. While formaldehyde reacts further to other C1 intermediates and initiates the formation of first C-C bonds, CH4 is not reacting. The hydride transfer to methoxy groups is the rate-determining step in the initiation of the conversion of methanol and DME to hydrocarbons. Thus, CH4 formation rates at very low conversions, i.e., in the initiation stage before autocatalysis starts, are used to gauge the formation rates of first hydrocarbons. Kinetics, in good agreement with theoretical calculations, show surprisingly that hydrogen transfer from DME to methoxy species is 10 times faster than hydrogen transfer from methanol. This difference in reactivity causes the observed faster formation of hydrocarbons in dry feeds, when the concentration of methanol is lower than in presence of water. Importantly, the kinetic analysis of CH4 formation rates provides a unique quantitative parameter to characterize the activity of catalysts in the methanol-to-hydrocarbon process.

RESUMEN

Formaldehyde is an important intermediate product in the catalytic conversion of methanol to olefins (MTO). Here we show that formaldehyde is present during MTO with an average concentration of ~0.2 C% across the ZSM-5 catalyst bed up to a MeOH conversion of 70%. It condenses with acetic acid or methyl acetate, the carbonylation product of MeOH and DME, into unsaturated carboxylate or carboxylic acid, which decarboxylates into the first olefin. By tracing its reaction pathways of 13C-labeled formaldehyde, it is shown that formaldehyde reacts with alkenes via Prins reaction into dienes and finally to aromatics. Because its rate is one order of magnitude higher than that of hydrogen transfer between alkenes on ZSM-5, the Prins reaction is concluded to be the major reaction route from formaldehyde to produce dienes and aromatics. In consequence, formaldehyde increases the yield of ethene by enhancing the contribution of aromatic cycle.

RESUMEN

Hydrogen transfer is the major route in catalytic conversion of methanol to olefins (MTO) for the formation of nonolefinic byproducts, including alkanes and aromatics. Two separate, noninterlinked hydrogen transfer pathways have been identified. In the absence of methanol, hydrogen transfer occurs between olefins and naphthenes via protonation of the olefin and the transfer of the hydride to the carbenium ion. A hitherto unidentified hydride transfer pathway involving Lewis and Brønsted acid sites dominates as long as methanol is present in the reacting mixture, leading to aromatics and alkanes. Experiments with purely Lewis acidic ZSM-5 showed that methanol and propene react on Lewis acid sites to HCHO and propane. In turn, HCHO reacts with olefins stepwise to aromatic molecules on Brønsted acid sites. The aromatic molecules formed at Brønsted acid sites have a high tendency to convert to irreversibly adsorbed carbonaceous deposits and are responsible for the critical deactivation in the methanol to olefin process.

RESUMEN

The elementary reactions leading to the formation of the first carbon-carbon bond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol(-1) for the formation of the first C-C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms.

RESUMEN

Crystal structures of two metal-organic frameworks (MFU-1 and MFU-2) are presented, both of which contain redox-active Co(II) centres coordinated by linear 1,4-bis[(3,5-dimethyl)pyrazol-4-yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert-butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU-1, MFU-2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure-reactivity relationships in the future design of redox-active metal-organic frameworks. Mechanistic details for oxidation reactions employing tert-butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K-edge X-ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O(2) were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature-programmed oxidation (TPO). Solution impregnation of MFU-1 with a co-catalyst (N-hydroxyphthalimide) led to NHPI@MFU-1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.

Asunto(s)

Cobalto/química , Modelos Moleculares , Compuestos Organometálicos/química , Ftalimidas/química , Pirazoles/química , Catálisis , Cristalografía por Rayos X , Conformación Molecular , Oxidación-Reducción , Espectrofotometría Infrarroja , Espectrofotometría Ultravioleta , Termodinámica , Espectroscopía de Absorción de Rayos X

RESUMEN

The syntheses of Kuratowski-type pentanuclear clusters featuring {MZn(4)Cl(4)} cores (M(II) = Ru or Zn) that incorporate triazolate ligands are described. The coordination compounds are characterized by single-crystal X-ray diffraction, X-ray powder diffraction (XRD), FTIR- and UV-vis spectroscopy. [Ru(II)Zn(4)Cl(4)(Me(2)bta)(6)]·2DMF (Me(2)bta(-) = 5,6-dimethyl-1,2,3-benzotriazolate) (1) crystallizes in the cubic system, while [Zn(5)Cl(4)(ta)(6)] (ta(-) = 1,2,3-triazolate) (3) crystallizes in the tetragonal system. Both compounds feature structurally similar cluster topologies in which the central octahedrally coordinated metal ion is coordinated to six triazolate ligands. Each triazolate ligand is coordinated with two zinc ions (µ(3)-bridging mode), leading altogether to a pentanuclear cluster of T(d) point group symmetry. Photophysical investigations reveal that compound [Zn(5)Cl(4)(Me(2)bta)(6)]·2DMF (2) shows a short-lived excited electronic state, which can be populated with high quantum yield. The isostructural compound [Ru(II)Zn(4)Cl(4)(Me(2)bta)(6)]·2DMF (1), on the other hand, shows a long-lived photoexcited state, owing to an internal singlet to triplet conversion of the electronic states, as revealed by time-resolved fluorescence spectroscopy. Insights gained from these studies open up novel design strategies towards photocatalytically active metal-organic frameworks incorporating photoactive Kuratowski-type secondary building units such as MFU-4 (Metal-Organic Framework Ulm University-4).

RESUMEN

A highly porous member of isoreticular MFU-4-type frameworks, [Zn(5)Cl(4)(BTDD)(3)] (MFU-4l(arge)) (H(2)-BTDD=bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), has been synthesized using ZnCl(2) and H(2)-BTDD in N,N-dimethylformamide as a solvent. MFU-4l represents the first example of MFU-4-type frameworks featuring large pore apertures of 9.1 Å. Here, MFU-4l serves as a reference compound to evaluate the origin of unique and specific gas-sorption properties of MFU-4, reported previously. The latter framework features narrow-sized pores of 2.5 Å that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.g., argon or nitrogen) are excluded from uptake. The crystal structure of MFU-4l has been solved ab initio by direct methods from 3D electron-diffraction data acquired from a single nanosized crystal through automated electron diffraction tomography (ADT) in combination with electron-beam precession. Independently, it has been solved using powder X-ray diffraction. Thermogravimetric analysis (TGA) and variable-temperature X-ray powder diffraction (XRPD) experiments carried out on MFU-4l indicate that it is stable up to 500 °C (N(2) atmosphere) and up to 350 °C in air. The framework adsorbs 4 wt % hydrogen at 20 bar and 77 K, which is twice the amount compared to MFU-4. The isosteric heat of adsorption starts for low surface coverage at 5 kJ mol(-1) and decreases to 3.5 kJ mol(-1) at higher H(2) uptake. In contrast, MFU-4 possesses a nearly constant isosteric heat of adsorption of ca. 7 kJ mol(-1) over a wide range of surface coverage. Moreover, MFU-4 exhibits a H(2) desorption maximum at 71 K, which is the highest temperature ever measured for hydrogen physisorbed on metal-organic frameworks (MOFs).

RESUMEN

Fusion of pentanuclear Kuratowski-type coordination units leads to homo- and heterononanuclear coordination compounds, two of which are presented, having structural formulae [Zn(9)Cl(6)(OMe(2)bta)(12)]·DMF (1), and [Fe(II)(3)Zn(6)Cl(6)(OMe(2)bta)(12)]·DMF (2), respectively; (OMe(2)btaH = 5,6-dimethoxy-1,2,3-benzotriazole; DMF = N,N'-dimethylformamide). Single crystal X-ray structure analyses reveal the presence of {M(3)Zn(6)L(12)}(6+) cores (M = Zn or Fe(II); L = 5,6-dimethoxy-1,2,3-benzotriazolate) in which the M(II) ions are bridged by µ(3)-OMe(2)bta ligands. In both compounds, the six peripheral Zn ions are tetracoordinated, whereas the remaining three metal ions M are hexacoordinated. The charge of each {M(3)Zn(6)L(12)}(6+) moiety is balanced by six chloride anions that are monodentately bound to the peripheral Zn ions. Based on differences in experimental Fe-N-donor bond lengths (deduced from single crystal data of 2 recorded at 223 K), two out of three Fe(II) ions are found in a high-spin (HS) state, whereas one Fe(II) ion shows a low-spin (LS) state. The assignment of different energetic ground states of Fe(II) ions is corroborated by spectroscopic studies: Both solid-state and solution UV-Vis spectra of 2 (at ambient temperature) display absorption bands owing to the presence of both HS and LS Fe(II) ions. Removal of occluded DMF molecules from the crystal lattices of 1 and 2 in high vacuum leads to fully desolvated powders, termed hereafter 1a and 2a, respectively. Mössbauer studies on 2a show that all three Fe(II) ions are in HS state at 160 K, and upon cooling to 7 K, the central Fe(II) ion undergoes a HS→LS transition while the HS states of the other Fe(II) ions remains unchanged. The cyclic voltammogram of 2 (chloroform solution) exhibits a single reversible oxidation regardless of different Fe(II) spin states in the nonanuclear core of 2.

RESUMEN

Homo- and heteropentanuclear coordination compounds [MZn(4)Cl(4)(L)(6)] (M(II) = Zn, Fe, Co, Ni, or Cu; L = 5,6-dimethyl-1,2,3-benzotriazolate) were prepared containing mu(3)-bridging N-donor ligands (1,2,3-benzotriazolate), which are structurally related to the fundamental secondary building unit of Metal-organic Framework Ulm University-4 (MFU-4). The unique topology of these T(d)-symmetrical compounds is characterized by the nonplanar K(3,3) graph, introduced into graph theory by the mathematician Casimir Kuratowski in 1930. The following "Kuratowski-type" compounds were investigated by single-crystal X-ray structure analysis: [MZn(4)Cl(4)(Me(2)bta)(6)].2DMF (M(II) = Zn, Fe, Co, and Cu; DMF = N,N'-dimethylformamide) and [MZn(4)Cl(4)(Me(2)bta)(6)].2C(6)H(5)Br (M(II) = Co and Ni; C(6)H(5)Br = bromobenzene). The mu(3)-bridging benzotriazolate ligands span the edges of an imaginary tetrahedron, in the center of which a redox-active octahedrally coordinated M(II) ion is placed. Four Zn(II) ions are located at the corners of the coordination units. Each Zn center is bound to a monodentate Cl(-) anion and three N-donor atoms stemming from different benzotriazolate ligands. The fact that open-shell redox-active M(II) ions can be introduced selectively into the central octahedral coordination sites is unambiguously proven by a combination of magnetic measurements, UV-vis spectroscopy, and energy-dispersive X-ray and inductively coupled plasma atomic emission spectrometry analysis. The phase purity of all compounds was checked by powder X-ray diffractometry, IR spectroscopy, and elemental analysis. The electronic spectra and magnetic properties of the compounds are in complete agreement with their structures determined from single-crystal data. Thermogravimetric analysis shows that all compounds possess a high thermal stability up to 673 K. The pentanuclear compounds retain their structural integrity in solution, as evidenced by time-of-flight mass spectrometry analysis and comparative solution and solid-state diffuse-reflectance spectroscopy. High stability paired with the presence of redox-active metal ions and Lewis-acidic Zn centers renders Kuratowski-type compounds structural and functional models for future MFU-4-type bi- and multifunctional heterogeneous catalysts.

RESUMEN

The self-assembly of copper(II) ions and 5-(2-hydroxyethoxy)benzene-1,3-dicarboxylate (1) leads to Nanoballs in which twelve dinuclear copper(II) paddle-wheel units are interconnected via 24 ligands. The structure of the spherical coordination compound decorated with 24 hydroxy groups has been determined by single crystal X-ray structure analysis. As a model for the integration of Nanoballs into bulk polyurethane polymers and coatings, its reaction with phenylisocyanate is investigated. The stability of Nanoballs against hydrolytic decomposition is studied under acidic conditions and compared to simple copper(II) complexes. Release of copper(II) ions from Nanoballs is much slower than from discrete copper(II) paddle-wheel complexes, suggesting the use of Nanoballs as monomers for polyurethane-based antifouling coatings.