Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins

Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.     

Supported titanium‐magnesium catalysts for ethylene polymerization: A comparative study of catalysts containing isolated and clustered titanium ions in different oxidation states

Supported titanium–magnesium catalysts (TMC) comprising isolated and clustered titanium ions in different oxidation states, which are obtained using titanium compounds of different composition (TiCl₄, TiCl₃?nDBE (DBE – dibutyl ether), [η⁶–BenzeneTiAl₂Cl₈]), were synthesized and tested in ethylene polymerization. The state of titanium ions was studied by the ESR method both for the procatalysts and after their interaction with triisobutilaluminum. For identification of ESR‐silent Ti³⁺ ions and Ti²⁺ ions, special procedures of additional catalyst treatment with pyridine, water, and chloropentafluorobenzene were used to obtain Ti³⁺ ions that are observable in ESR spectra. In distinction to numerous earlier works performed with the TiCl₄/MgCl₂ catalyst comprising after the interaction with AlR₃ the Ti³⁺ surface compounds both as isolated ions and clusters (ESR‐silent), this work considers the [η⁶–BenzeneTiAl₂Cl₈]/MgCl₂ catalyst (TMC‐3) comprising mainly the isolated Ti²⁺ ions and a new catalyst TMC‐4 obtained by treating the TMC‐3 with chloropentafluorobenzene. This catalyst comprises only the isolated Ti³⁺ ions both before and after the interaction with triisobutylaluminum. It was shown that in spite of sharp distinctions between the catalysts under consideration concerning titanium oxidation state and the ratio of isolated Ti³⁺ ions to clustered ones, all these catalysts produce polyethylenes with similar molecular weights and molecular‐weight distributions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6362–6372, 2009     

On the reactivity of supported zirconium organic catalysts in the polymerization of ethylene

The ethylene polymerization with tetrabenzyl zirconium displays a higher concentration of active centres on catalysts obtained by supporting of the organometallic compound on alumina or silica-alumina carriers than by activation without supporting. The active centres of the supported catalysts possess different polymerization reactivity. At the beginning of the polymerization in the presence of monomer, these active centres are formed from a small amount of the stable surface compounds originated in the carrier impregnation. The maximum polymerization rate depends on the pretreatment, the loading and the porosity of the carrier. The more active these centres, the quicker they lose their activity. A relation was found between a chemical deactivation reaction and the concentration of the hydroxyl groups remaining on the catalyst after impregnation. Addition of hydrogen or butyllithium can change the polymerization in a different manner. The addition of butyllithium causes an increase in the number and the reactivity of the active centres and a suppression of the chemical deactivation.     

Multi-scan cyclic voltammetry of a solution containing mixed valence states

Journal of Solid State Electrochemistry - When both members of a redox pair are present in a voltammetric cell, the applied signal must start at the null potential if pure cyclic voltammetry is to...     

Studies of the composition and catalytic properties of supported catalysts prepared through halide-substituted titanium and zirconium benzyl complexes

Composition and catalytic properties in ethylene polymerization of supported systems prepared via the interaction of Ti(CH₂C₆H₅)₃X (X=F, Cl, Br) and Zr(CH₂C₆H₅)₂Cl₂ complexes with silica and alumina have been studied. Halide addition to benzyl complexes decreases the polymer molecular mass.

---

, Ti(CH₂C₆H₅)₃X (X=F, Cl, Br) Zr(CH₂C₆H₅)₂Cl₂ SiO₂ Al₂O₃. , .

     

Estimation of electronegativity values of elements in different valence states

The electronegativities of 82 elements in different valence states and with the most common coordination numbers have been quantitatively calculated on the basis of an effective ionic potential defined by the ionization energy and ionic radius. It is found that for a given cation, the electronegativity increases with increasing oxidation state and decreases with increasing coordination number. For the transition-metal cations, the electronegativity of the low-spin state is higher than that of the high-spin state. The ligand field stabilization, the first filling of p orbitals, the transition-metal contraction, and especially the lanthanide contraction are well-reflected by the relative values of our proposed electronegativity. This new scale is useful for us to estimate some quantities (e.g., the Lewis acid strength for the main group elements and the hydration free energy for the first transition series) and predict the structure and property of materials.     

Energies of electronic states of promoter ions in hydrodesulfurization catalysts

Poly-vinylpyrrolidone-anchored (PVP) supported platinum catalyst (PVP-Pt) and rare earth metals (Sm³⁺, Pr³⁺, Ce³⁺, Nd³⁺and La³⁺) promoted PVP-Pt catalysts were prepared and used in the hydrogenation of o- and m-chloronitrobenzene (CNB) in ethanol at 303 K and atmospheric pressure. It was found that rare earth metals improved the selectivity of chloronitrobenzene to chloroaniline (CAN), while the hydrogenation rate of CNB decreased. In the presence of NaOH, PVP-Pr-Pt and PVP-La-Pt catalysts exhibit the highest selectivity in the hydrogenation of CNB. At the same time different support materials of Pt catalyst (such as polyethylene glycol (PEG), ethyl cellulose (EC)) possessed great influence on catalytic activity and selectivity of p-CAN.This revised version was published online in December 2005 with corrections to the Cover Date.     

Nanoparticle supported bis (cyclopentadienyl) zirconium dichloride catalysts for styrene polymerization

Heterogeneous nanoparticle NA-MgO-MAO/NA-TiO₂ (anatase)-MAO supported bis (cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂) are synthesized and used for the polymerization of styrene monomer. The supporting process is confirmed via X-ray photoelectron spectroscopy (XPS) and FTIR. Characterization of the obtained polymer is done by gel permeation chromatography (GPC), ¹³C NMR spectroscopy and differential scanning calorimetry (DSC).     

Palladium catalysts supported on activated carbon with different textural and surface chemical properties

A commercial activated carbon was used as catalyst support in Pd/AC catalysts. The effects of the different surface oxygen groups and textural properties of the carbon supports on the metal dispersion of the supported catalysts were analyzed.     

Chromium oxide catalysts with low valence state ions for heterocyclic ring formation

Conclusions In aluminum-chromium catalysts promoted by potassium and rare-earth oxides, used in the synthesis of 2-methylthiophene by heterocyclization of n-pentane with hydrogen sulfide, there are present low-valence cations of chromium and the rare-earth that enter into the active centers of the catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 782–784, April, 1986.     

Specific properties of dehydrogenation centers in supported platinum catalysts

Cyclohexane dehydrogenation was used as a model reaction to study the dehydrogenation function of Pt/Al₂O₃ catalysts. Fresh and coked catalysts were tested in two ranges of reaction conditions: model conditions (T=280–340°C, P=1 atm) and the conditions used in the naphtha reforming process (T=420–460°C, P=15 atm). Intrinsic properties of the dehydrogenation active centers were found to be identical throughout the experimental conditions. The coke deposits only block a part of the active centers without their qualitative modification.     

Ordering of Cu(II) ions in supported copper-titanium oxide catalysts

Two types of ESR spectrum (A and B) of exchange-coupled Cu²⁺ ions have been found for Cu-Ti-O catalysts at 77 K and 300 K. In associates A and B, the Cu²⁺ ions form a system with orbital ordering. The difference between the spectra is due to the difference between the ground states of adjacent Cu²⁺ ions in the associates: the ground states are $d_{x^2 } $ and $d_{y^2 } $ for A type associates and $d_{x^2 - y^2 } $ and $d_{z^2 - x^2 } $ for B type associates. The copper associates lie on the surface of the TiO₂ (anatase) support microparticles.     

Hydrogenation of 4-tert-butylphenol over supported catalysts in different solvents

It has been established that in hydrogenation of 4-tert-butylphenol over Rh/-Al₂O₃ in isopropanol the addition of CH₃COOH increases the yield of 4-tert-butylcyclohexanol.

---

, CH₃COOH -4- 4- Rh/-Al₂O₃ .

     

Diffusion coefficients of ions through ion excange membrane in Donnan dialysis using ions of different valence

Donnan dialysis with an ion exchange membrane was investigated for ions of different valence. The effective diffusion coefficients (D_e) of various kinds of ions in the membrane were obtained by fitting of the equation derived from the Nernst–Planck equation to three or more sets of experimental data for Donnan dialysis. It became apparent that the value of D_e/D_s of monovalent ions (e.g., K⁺ or Na⁺ ions) at z_A=1 and z_B=2 (feed ions are monovalent ones and driving ions are bivalent ones) remained constant at ca. 1/210 and that of bivalent ions (e.g., Ca²⁺, Cu²⁺, or Mg²⁺ ions) remained constant at ca. 1/526 where D_s denotes the diffusion coefficient of ions at infinite dilution in water calculated from the Nernst–Einstein equation, and z_A and z_B represent the valences of the feed and driving ions, respectively. D_e/D_s of monovalent ions (e.g., H⁺, K⁺, or Na⁺ ions) at z_A=2 and z_B=1 (feed ions are bivalent ones and driving ions are monovalent ones) was constant at ca. 1/23.3 and that of bivalent ions remained constant at ca. 1/58.4. It was proved that D_e/D using D_e at z_A=1 and z_B=2 was constant at 1/3.0 and that at z_A=2 and z_B=1 remained constant at 3.0 where D represents the diffusion coefficient of ions in the membrane at z_A=z_B (the valences of both feed and driving ions are equal). Therefore, it was found that a large flux of ions could be obtained using the monovalent driving ions in Donnan dialysis. On the other hand, the small flux can be obtained using bi- or higher-valent driving ions.     

Interaction of ethylene with Ti(III) ions in supported organotitanium catalysts

The interaction of ethylene with Ti(III) ions in ethylene polymerization catalysts prepared by the interaction of Ti(CH₂C₆H₅)₄ with silica has been studied by the ESR method. It has been found that at low temperatures (120 K) ethylene is reversibly adsorbed on titanium ions with further ethylene insertion into the Ti–C bond upon increasing temperatures.

---

Ti(III) , Ti(CH₂C₆H₅)₄ . , (120°K) Ti–C.

     

Adsorption properties of Ni-Pd catalysts supported on aluminum oxide

The surface composition of Ni-Pd/Al₂O₃ catalysts has been studied using XPES and adsorption methods. The bimetallic catalysts differ from the single-metal Ni and Pd catalysts in the dispersivity of the metal phase which depends on the method of preparation and the presence of K⁺ promoter. A catalyst produced by the immersion method is strongly enriched in Pd compared with impregnated catalysts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1746–1751, August, 1991.     

The properties of supported rhenium catalysts in the dehydrogenation of cyclohexane

The 2 % Re/sibunite catalyst is more active than 2 % Re/-Al₂O₃ and 2 % Re/-Al₂O₃ catalysts in the dehydrogenation of cyclohexane into benzene (T = 350 °C,w = 0.5 h–1). The substitution of NH₄ReO₄ by HReO₄ in the preparation of the catalyst enhances its activity by a factor of 1.3. Treatment with HNO₃ or oxalic acid increases the selectivity by a factor of 1.2 and 1.35, respectively, the overall conversion of cyclohexane being 32–40 %.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2119–2121, August, 1996.     

Anion-exchange properties of composite ceramic membranes containing hydrated zirconium dioxide

Composite membranes consisting of an inert ceramic matrix based on aluminum and zirconium oxides and of an ion-exchange component, hydrated zirconium dioxide, were prepared. The selectivity of these membranes to Cl^? ions was studied.     

γ-Radiation produced supported metal complex catalysts : II. Cobalt carbonyl hydroformylation catalysts supported on polypropylene containing pyridine side chains

The optimum conditions necessary to prepare novel polymer supports for use in catalysis by the γ-radiation grafting of 4-vinylpyridine on to polypropylene are shown to be a total dose of 2 Mrad at a dose rate of 300 Krad h^?1 using a monomer to polymer ratio of 40 per cent mol/mol. Addition of 0.1 per cent w/v of p-tert-butylcatechol increases the grafting yield almost two fold. Comparison of the hydroformylation of 1-hexene in the presence of cobalt carbonyl supported on 4-vinylpyridine grafted on to polypropylene shows an increase in specificity, as determined by the ratio of normal/branched heptanal formed, by a factor of about 2.5 over the corresponding homogeneous catalyst. The supported system is of similar activity to the homogeneous system. The greater specificity of the supported catalyst is ascribed to the total environment surrounding the catalytically active site in which both the pyridine sidechain and the polypropylene backbone are believed to play an important role.