Oxidative Carbonylation of Methanol to Dimethyl Carbonate Over Cu(II)-1,10-Phenanthroline Bromide Complexes☆

In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate (DMC), CuBr2 was selected as the metal source to prepare Cu coordination compo...     

Poly(ethylene oxide)–LiX rubbery electrolytes with X–X disulfonamide anions having two or three ether groups in their structures

This work deals with poly(ethylene oxide), PEO–MX (M=Li, K and Cs) amorphous electrolytes with ⁻X–X⁻, [CF₃SO₂NCH₂(CH₂OCH₂)₂CH₂NSO₂CF₃]²⁻ (EDSA) and [CF₃SO₂NCH₂CH₂(CH₂OCH₂)₃CH₂CH₂NSO₂CF₃]²⁻ (TTSA) disulfonamide anions. These dianions have X⁻ end-groups identical to anions [CF₃SO₂N(CH₂)₂OCH₃]⁻ (MESA) and [CF₃SO₂N(CH₂)₃OCH₃]⁻ (MPSA), one of which (MPSA) was reported to yield chelate-like associated species (presumably LiX₂⁻ triplets) at concentrations above EO/Li=20 in PEO. This feature of LiMPSA, evidenced through glass transition temperature (T_g) measurements, does not apply to Li₂EDSA and Li₂TTSA. Though none of these lithium salts form crystalline intermediate compounds with PEO, the limit of solubility of LiMESA (EO/Li=16) does not allow a clarification of this point for this salt. At lower concentrations, however, a conductivity comparison with the potassium and caesium salts shows that the apparent degree of dissociation (=C_Li+/C_Li) of LiMESA is comparable to that of LiMPSA. As opposed to both these salts and to some extent to Li₂EDSA, a much greater dissociation takes place for Li₂TTSA, the anion of which contains an inner, third ether group in its structure.     

Some evidence refuting the alkenyl mechanism for chain growth in iron-based Fischer–Tropsch synthesis

Recently, Maitlis et al. [J. Catal. 167 (1997) 172] proposed an alternative reaction pathway for chain growth in the Fischer–Tropsch synthesis. In this mechanism, chain growth is assumed to occur by methylene insertion into a metal–vinyl bond, forming an allyl species that will subsequently isomerise to a vinyl species. Organo-metallic allyl complexes, Fe{[η⁵-C₅H₅](CO)₂CH₂CH=CH₂} and Fe{[η⁵-C₅(CH₃)₅](CO)₂CH₂CH=CH₂} were synthesised. Under thermal treatment, the decomposition of these complexes was observed, instead of the isomerisation. In a hydrogen atmosphere, the reduction of the iron–carbon bonds and the hydrogenation yielding iron–alkyl species was observed. This clearly shows that the proposed vinyl–allyl isomerisation is unlikely to occur in mono-nuclear iron complexes. Hence, it might be expected that the reaction mechanism proposed by Maitlis et al. [J. Catal. 167 (1997) 172] is unlikely to be the main route for chain growth in the Fischer–Tropsch synthesis.     

Gold catalysts supported on mesoporous titania for low-temperature water–gas shift reaction

Mesoporous titania with high surface area and uniform pore size distribution was synthesized using surfactant templating method through a neutral [C₁₃(EO)₆–Ti(OC₃H₇)₄] assembly pathway. The different gold content (1–5 wt.%) was supported on the mesoporous titania by deposition–precipitation (DP) method. The catalysts were characterized by X-ray diffraction, TEM, SEM, N₂ adsorption analysis and TPR. The catalytic activity of gold supported mesoporous titania was evaluated for the first time in water–gas shift reaction (WGSR). The influence of gold content and particle size on the catalytic performance was investigated. The catalytic activity was tested at a wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. It is clearly revealed that the mesoporous titania is of much interest as potential support for gold-based catalyst. The gold/mesoporous titania catalytic system is found to be effective catalyst for WGSR.     

Gold catalysts supported on mesoporous zirconia for low-temperature water–gas shift reaction

Mesoporous ZrO₂ with high surface area and uniform pore size distribution, synthesized by surfactant templating through a neutral [C₁₃(EO)₆–Zr(OC₃H₇)₄] assembly pathway, was used as a support of gold catalysts prepared by deposition–precipitation method. The supports and the catalysts were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, N₂ adsorption analysis, temperature programmed reduction and desorption. The catalytic activity of gold supported on mesoporous zirconia was evaluated in water–gas shift (WGS) reaction at wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. The catalytic behaviour and the reasons for а reversible deactivation of Au/mesoporous zirconia catalysts were studied. The influence of gold content and particle size on the catalytic performance was investigated. The WGS activity of the new Au/mesoporous zirconia catalyst was compared to the reference Au/TiO₂ type A (World Gold Council), revealing significantly higher catalytic activity of Au/mesoporous zirconia catalyst. It is found that the mesoporous zirconia is a very efficient support of gold-based catalyst for the WGS reaction.     

Formation of Pd nanoparticles in surfactant-mesoporous silica composites and surfactant solutions

Highly dispersed palladium nanoparticles containing mesoporous silicas MCM-41 and MCM-48 were prepared by one-pot synthesis. The method consists of the simultaneous formation of CTA⁺ surfactant templating MCM-41 mesophase and CTA⁺ micelle-capped PdO, which was reduced by hydrogen to Pd metal with particle size ≈ 2 nm and was observed to stay inside the mesochannels of MCM-41 (pore size ≈ 3.8 nm) by TEM, XAS, and PXRD. During hydrothermal synthesis of Pd/MCM-48, Pd nanoparticles of average size ≈ 6–7 nm were deposited on the MCM-48 of pore size = 4 nm. The deposition is probably derived from ethanol reduction of Pd(II) complex generated from PdCl₂ precursor by hydrolysis of TEOS and C₁₂H₂₅(OCH₂CH₂)₄OH surfactant. The formation of Pd(0) from Pd(II) species in solid mesoporous silicas by hydrogen reduction was monitored by in situ XAS, and compared with the formation of Pd(0) from [PdCl₄]²⁻, [PdCl₃(H₂O)], and Pd(OH)₂ by sodium dodecyl sulfate surfactant and alcohol reduction in aqueous solutions.     

Density functional calculations on agostic ethyl-Ti (IV) complexes

First principles, density functional theory embodied in the DMol program has been applied to agostic ethyl-Ti-complexes, including the dmpe complex, [Ti(-CH₂CH₃)C1₃(dmpe)], where DMPE=(Me₂PCH₂)₂ and its model complex, [Ti(−CH₂CH₃)Cl₃(PH₃)₂]. The ethyl moiety of the complexes can adopt two limiting conformations, staggered and eclipsed. In the model complex, [Ti(−CH₂CH₃)C1₃(PH₃)₂], both conformers are found to form agostic structures upon geometry optimization subject to Cs symmetry constraint, with the agostic eclipsed structure being the lower in energy. Full geometry optimization of the dmpe complex, [Ti(−CH₂CH₃)C1₃(dmpe)], yields an agostic structure with geometrical features similar to those measured by single crystal X-ray analysis. It is shown that the HOMO orbital contributes substantially to the agostic bonding.     

The role of vacancies in the hydrogen storage properties of Prussian blue analogues

The porosity and hydrogen storage properties of the dehydrated Prussian blue type solids Ga[Co(CN)₆], Fe₄[Fe(CN)₆]₃, M₂[Fe(CN)₆] (M = Mn, Co, Ni, Cu), and Co₃[Co(CN)₅]₂ are reported and compared to those of M₃[Co(CN)₆]₂ (M = Mn, Fe, Co, Ni, Cu, Zn). Nitrogen sorption measurements suggest partial framework collapse for M₂[Fe(CN)₆] (M = Co, Ni) and Co₃[Co(CN)₅]₂, and complete collapse for Mn₂[Fe(CN)₆]. Hydrogen sorption isotherms measured at 77 K reveal a correlation between uptake capacity and the concentration of framework vacancies, with Langmuir–Freundlich fits predicting saturation values of 1.4 wt.% for Ga[Co(CN)₆], 1.6 wt.% for Fe₄[Fe(CN)₆]₃, 2.1 wt.% for Cu₃[Co(CN)₆]₂, and 2.3 wt.% for Cu₂[Fe(CN)₆]. Enthalpies of H₂ adsorption were calculated from isotherms measured at 77 and 87 K. Importantly, the values obtained for compounds with framework vacancies are not significantly greater than for the fully-occupied framework of Ga[Co(CN)₆] (6.3–6.9 kJ/mol). This suggests that the exposed metal coordination sites in these materials do not dominate the hydrogen binding interaction.     

Gold nanoparticles supported on ceria-modified mesoporous titania as highly active catalysts for low-temperature water-gas shift reaction

New gold catalytic system prepared on ceria-modified mesoporous titania (CeMTi) used as water-gas shift (WGS) reaction catalyst is reported. Mesoporous titania (MTi) was synthesized using surfactant templating method through a neutral [C₁₃(EO)₆–Ti(OC₃H₇)₄] assembly pathway. Ceria modifying additive was deposited on MTi by deposition precipitation (DP) method. Gold-based catalysts with different gold content (1–5 wt.%) were synthesized by DP of gold hydroxide on mixed metal oxide support. The supports and the catalysts were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption analysis and temperature-programmed reduction (TPR). The catalytic behavior of the gold-based catalysts was evaluated in WGS reaction in a wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. The influence of gold content and particle size on the catalytic performance was investigated. The WGS activity of the new gold/ceria-modified mesoporous titania catalysts was compared with that of gold catalysts supported on simple oxides CeO₂ and mesoporous TiO₂, as well as gold/ceria-modified titania and reference catalyst Au/TiO₂ type A (World Gold Council). A high degree of synergistic interaction between ceria and mesoporous titania and a positive modification of structural and catalytic properties by ceria has been achieved. It is clearly revealed that the ceria-modified mesoporous titania is of much interest as potential support for gold-based catalyst. The Au/ceria-modified mesoporous titania catalytic system is found to be efficient catalyst for WGSR.     

Photodegradation catalyst screening by combinatorial methodology

In this work, a combinatorial methodology was developed for photodegradation catalyst screening. A fluorescence imaging detection system was designed for high throughput analysis, 1,6-hexamethylenediamine was used as the probe molecule for catalyst testing. The photodegradation activity of catalysts was evaluated by 1,6-hexamethylenediamine consumption during the photodegradation reaction. The methodology could provide reliable results. We found that pure TiO₂, ZrO₂, Nb₂O₅, MoO₃, and WO₃ did not show much activity for 1,6-hexamethylenediamine photodegradation under visible light. TiO₂ catalysts doped with different metal ions were tested. When TiO₂ was doped with Ta₂O₅, Nb₂O₅, V₂O₅, MoO₃, or WO₃, higher activity for photodegradation was observed. The doping of La³⁺, Ba²⁺, and Br⁻ to TiO₂ did not improve the catalytic activities. When doping TiO₂ with Mn²⁺, Cl⁻, Al³⁺, Cu²⁺, Fe³⁺, Na⁺, Mg²⁺, Li⁺, F⁻, Co²⁺, or K⁺, catalytic activity was lower than that of pure TiO₂. After elaborate catalysts screening, we discovered new catalysts, such as 50–70% TiO₂/0–20% WO₃/20–40% VO_2.5 and 20–30% TiO₂/30–50% MoO₃/40–60% VO_2.5 as well as 30% WO₃/20% ZrO₂/50% NbO_2.5 (synthesized from ZrCl₄, NbCl₅, and (NH₄)₅H₅[H₂(WO₄)₆]·H₂O in ethanol solution or suspension) and 60–70% WO₃/Nb₂O₅ (synthesized from WCl₆ and NbCl₅ in ethanol solution). We observed that the catalytic activity is sensitive to preparation methods and catalyst specific surface areas. When P123 (HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H, designated EO₂₀PO₇₀EO₂₀) was used as template to synthesize mesoporous materials, the mesoporous catalysts showed higher activity than regular catalytic materials.     

Zn(Ⅱ)配合物催化C—C键裂解和原位合成2-甲基-4(3H)-喹唑酮

在配合物的水热合成过程中往往可以发现新的化学反应和催化机理。本文通过[Zn(L)₂·(H₂O)₂·(NO₃)₂]（L=4(3H)-喹唑酮）配合物在130℃催化乙腈分子中的CC键断裂,原位合成化合物2-甲基-4(3H)-喹唑酮。利用红外、元素分析和X射线单晶衍射表征分析2-甲基-4(3H)-喹唑酮和[Zn(L)₂·(H₂O)₂·(NO₃)₂]的结构,结果表明[Zn(L)₂·(H₂O)₂·(NO₃)₂]和2-甲基-4(3H)-喹唑酮属于三斜晶系,P-1空间群。三组温度控制实验表明,温度对2-甲基-4(3H)-喹唑啉酮的形成有着重要的影响,并且温度高于130℃有利于该催化反应的进行。采取电喷雾质谱表征2-甲基-4(3H)-喹唑酮的形成机理发现,[Zn(L)₂·(H₂O)₂·(NO₃)₂]催化乙腈分子中的CC键断裂,生成(CN)₂和·CH₃。·CH₃有选择性地引入到4(3H)-喹唑酮中的C原子和N原子之间。本文对原位引入CH₃有着指导作用。     

Synthesis of ordered small pore mesoporous silicates with tailorable pore structures and sizes by polyoxyethylene alkyl amine surfactant

Ordered mesoporous silicates with tailorable pore structures and small pore sizes have been synthesized by using polyoxyethylene alkyl amine surfactant PN-430 [CH₃(CH₂)₁₇N(EO)_x(EO)_y, x + y = 5] as a structure-directing agent under acidic condition. Two-dimensional (2-D) hexagonal (p6mm) mesoporous silicates have been prepared via an evaporation-induced self-assembly (EISA) process. The N₂ sorption isotherms show that the product has a small uniform pore size distribution of 1.8 nm by BJH model, a BET surface area of 730 m²/g and a pore volume of 0.36 cm³/g. 3-D cubic (Pm-3n) mesoporous silicate with small uniform pore size (1.76 nm) can also be prepared at high concentration of PN-430 by EISA method in tetrahydrofuran solvent. The solvothermal post-treatment by n-hexane at 70 °C for 3 d to the above material results in the phase transition of the mesostructure from Pm-3n to P6₃/mmc based on XRD and TEM analyses. In comparison, by using nonionic oligometric alkyl-ethylene oxide surfactant such as Brij 78 (C₁₈H₃₇EO₂₀) or Triton X-100 (CH₃C(CH₃)₂CH₂C(CH₃)₂C₆H₄ EO₁₀) as co-templates, high-quality hexagonal (p6mm) small pore mesoporous silicates have also been prepared in ethanol media. Our results show that the blend templates composed of PN-430 and a small amount of nonionic surfactant can increase the efficiency of organic and inorganic hybrid species assembly, improve the quality of the structural regularity, and decrease the pore size to about 1.65 nm.     

Three metal-organic frameworks prepared from mixed solvents of DMF and HAc

Three metal-organic framework compounds [HZn₃(OH)(BTC)₂(2H₂O) (DMF)] · H₂O (MOF-CJ3), [Co₆(BTC)₂(HCOO)₆(DMF)₆] (MOF-CJ4), and [Co₁₈(HCOO)₃₆] · 3H₂O (MOF-CJ5) have been solvothermally synthesized in mixed solvents of DMF and HAc, respectively. These MOFs are characterized by single-crystal X-ray diffraction, X-ray powder diffraction, ICP, TG analyses, IR, and photoluminescence spectroscopy analyses. MOF-CJ3 crystallizes in tetragonal, space group I4cm (No. 108) with a = 20.588(3) Å, b = 20.588(3) Å, c = 17.832(4) Å. Its framework can be described as a 3D decorated (3, 6)-connected net based on the assembly of trigonal prismatic SBUs and triangular links. MOF-CJ4 crystallizes in hexagonal, space group P-3 (No. 147) with a = 13.975(2) Å, b = 13.975(2) Å, c = 8.1650(16) Å. The 2D network of MOF-CJ4 is constructed from [Co₆(R(CO₂)₃)₂(HCO₂)₆(DMF)₆] (R = C₉H₃–) clusters and 1,3,5-benzene-tricarboxylates linkers. MOF-CJ5 crystallizes in triclinic, space group (No. 2) with a = 15.205(3) Å, b = 18.005(4) Å, c = 21.500(4) Å,  = 71.21(3)°, β = 84.47(3)°, γ = 67.15(3)°. MOF-CJ5 has a diamond framework with Co-centered CoCo₄ tetrahedra as nodes. It is noteworthy that the formic ligands in MOF-CJ4 and MOF-CJ5 are generated by the decomposition of DMF under acid conditions and incorporated into these two compounds.     

Structural studies of reaction products between paramolybdate anion and some cationic [metal(II) and (III)-(ethylenediamine)n] complexes utilized as new photocatalysts under UV–VIS light illumination

Five cationic transition metal (ethylenediamine) complexes (M=Cr(III), Co(III), Ni(II), and Cu(II)):paramolybdate anion (Mo₇O₂₄⁶⁻) have been synthesis and characterized via their elemental analysis, magnetic susceptibility (μ_eff), thermal analysis (TG and DTA), FTIR spectra, and X-ray diffraction (XRD). The FTIR study suggests that the compounds prepared be of the ion-pair type ([M(en)_n]_m·Mo₇O₂₄). Thermal study showed that molybdenum in the Cr(III), and Co(III) compounds is reduced from oxidation state (VI) to (V) at high temperature. The stoichiometries of the resulting mixed oxides at elevated temperatures (500–750°C) are: Cr₂O₃·7MoO_2.5, Co₂O₃·7MoO_2.5, 6CoOCl·7MoO_2.5, 3NiO·7MoO₃ and 3CuO·7MoO₃. Above 750°C the molybdenum oxide in the ion-pair compounds start the sublimation process. X-ray diffraction of [Cr(en)₃]·Mo₇O₂₄, [Co(en)₃]·Mo₇O₂₄, and [Cu(en)₂(H₂O)₂]₃·Mo₇O₂₄ shows that these complexes are crystalline solids with a similar structure, while the [Ni(en)(H₂O)₄]₃·Mo₇O₂₄, and [Co(en)(H₂O)₂Cl₂]₆·Mo₇O₂₄ ion-pair compounds display a different structure.

A novel technique based on photocatalysis to eliminate Cr(VI) ions, a toxic pollutant in the environment, was applied. The photoreduction of Cr(VI) to Cr(III) ion in aqueous suspensions using new-mixed oxides as photocatalysts (Cr₂O₃·MoO_2.5, Co₂O₃·MoO_2.5, NiO·MoO₃, and CuO·MoO₃) under air-equilibration and irradiation by a medium pressure mercury lamp (UV–VIS) was investigated.     

Transition metal catalysis in fluorous media: application of a new immobilization principle to rhodium-catalyzed hydrogenation of alkenes

Biphase systems were generated by combining toluene solutions of alkenes (2-cyclohexen-1-one, 1-dodecene, cyclododecene, 4-bromostyrene) and CF₃C₆F₁₁ solutions of the pre-catalyst ClRh[P(CH₂CH₂(CF₂)₅CF₃)₃]₃ ((1); 1.1–0.8 mol%) and placed under 1 atm of H₂. The perfluoroalkyl segments in (1) confer high affinities for fluorocarbons. After 8–26 h at 45°C, the CF₃C₆F₁₁ phases were separated, and extracted with an equal volume of toluene. GLC analyses of the toluene solutions showed 98–87% yields of the hydrogenation products cyclohexanone, dodecane, cyclododecane, and 4-bromoethylbenzene (turnover numbers 120–87). The CF₃C₆F₁₁ phases were charged with new toluene solutions of 2-cyclohexen-1-one or 1-dodecene, and similarly treated with H₂. There was no significant loss of catalyst activity over three cycles. A preparative reaction gave cyclohexanone in 89% yield. Some C=C isomerization could be detected during the course of 1-dodecene hydrogenation, and (1) gave a dihydride complex in the absence of alkene.     

Hydrodenitrogenation of pyridine over alumina-supported iridium catalysts

The catalytic properties of alumina-supported Ir catalysts (≈1 wt% Ir) were studied in the hydrodenitrogenation (HDN) of pyridine at 320°C and 20 bar of pressure in the absence as well as presence of parallel hydrodesulfurization (HDS) of thiophene. The effects of Ir precursor (Ir(AcAc)₃, Ir₄(CO)₁₂, H₂IrCl₆, (NH₄)₂IrCl₆), metal dispersion and sulfur addition were investigated. Ir₄(CO)₁₂ gave the most active catalyst which was ascribed to a lower amount of contaminants originated from the starting Ir compounds rather than to a better Ir dispersion. The decrease of Ir dispersion by sintering in air led to much higher decrease of the rate of C–N bond hydrogenolysis than that of pyridine hydrogenation. The Ir dispersion determined partly the HDN selectivity; a better dispersed Ir phase gave a lower amount of intermediate piperidine. Presulfidation of the reduced catalyst led to 20% decline of the rates of both consecutive HDN steps. An additional and much larger activity decline was caused by the simultaneous execution of HDS. The competitive adsorption of thiophene (or H₂S) was selectively affecting C–N bond hydrogenolysis more than pyridine hydrogenation. The alumina-supported Ir catalysts possessed much higher HDN activity and HDN/HDS selectivity than a conventional NiMo system.     

In situ FTIR study on reaction pathways in Ni(CO)4/CH3OK catalytic system for low-temperature methanol synthesis in a liquid medium

An in situ infrared spectroscopic study was conducted to elucidate the reaction pathways for low-temperature methanol synthesis in a catalytic system composed of Ni(CO)₄ and CH₃OK (denoted as Ni(CO)₄/CH₃OK). The reaction was conducted in a liquid medium at 313–333 K with an initial pressure of 3.0 MPa. When CH₃OK was added to Ni(CO)₄ solution at 293 K, different carbonylnickelates, [Ni₅(CO)₁₂]²⁻, [Ni₆(CO)₁₂]²⁻ and [Ni(CO)₃(COOCH₃)]⁻, were immediately formed from Ni(CO)₄. The species and the composition of the carbonylnickel complexes varied with temperature. The variations in concentrations of methanol (MeOH) and methyl formate (MF) during the run, which were determined from their IR absorptions, indicated a pattern characteristic of consecutive reactions with MF as an intermediate. Thus, it was shown that methanol was produced through the carbonylation of MeOH to MF and the subsequent hydrogenation of MF to MeOH. Stable hydridocarbonylnickel anions, [HNi(CO)₃]⁻ and/or [HNi₂(CO)₆]⁻, were observed together with a small amount of Ni(CO)₄ throughout the methanol synthesis. Since Ni(CO)₄ alone showed no activity for the hydrogenation of MF, the hydridocarbonylnickel anions generated in the presence of CH₃OK must be responsible for the reaction. The dual role of CH₃OK in the catalytic system was stated.     

Hydrodesulfurization of model diesel using Pt/Al2O3 catalysts prepared by supercritical deposition

Pt/Al₂O₃ catalysts with Pt loadings ranging from 0.5 to 11 wt.% were synthesized by supercritical carbon dioxide (scCO₂) deposition method. Transmission electron microscopy (TEM) images showed that the synthesized catalysts contained small Pt nanoparticles (1–4 nm in diameter) with a narrow size distribution, no observable agglomeration, and uniformly dispersed on the alumina support. The catalysts were found to be active for hydrodesulfurization of dibenzothiophene (DBT) dissolved in n-hexadecane (n-HD) without sulfiding the metal phase. The reaction proceeded only via the direct hydrogenolysis route in the temperature range 310–400 °C and at atmospheric pressure. The activity increased with increasing the metal loading. Increasing [H₂]₀/[DBT]₀ by either increasing [H₂]₀ or decreasing [DBT]₀, increased the DBT conversion. At a fixed weight hourly space velocity and feed concentration, conversion did not increase with increasing temperature beyond 330 °C. The presence of toluene inhibited the catalyst activity presumably due to competitive adsorption between DBT and toluene. Under the operating conditions, the reaction was far from equilibrium.     

Incorporation of a tungsten Fischer-type metal carbene covalently bound to functionalized SBA-15

A metal Fischer carbene [(CO)₅WC(φ)OCH₂CH₃] was covalently linked for the first time to the silanol groups of the mesoporous channels of SBA15 by following two different synthetic anchoring routes. The first one goes through the reaction of the SBA15 mesoporous silica walls functionalized by aminopropyltriethoxysilane (APTES) with a tungsten carbene Wφ, while in the second approach a precursor synthesized by reacting APTES with the carbene Wφ is then anchored via a direct bond to the silanol groups in the interior pore channels of SBA-15.

This tethering is helpful to prevent the decomposition of the metallic complex. XRD, N₂ adsorption–desorption, and TEM analysis provide strong evidence that the mesoporous support structure retains its long-range ordering after the grafting process, despite a significant reduction of its specific surface area, pore-volume and pore-size. The chemical bonding of the tungsten carbene to the silanol groups of SBA-15 materials was studied with solid-state NMR spectroscopy. Both ¹³C MAS NMR and ²⁹Si CP MAS NMR spectra confirm the covalent linking of the carbene to the silica-pore system.     

Study of the impedance of a platinum electrode in the system Br2/Br (HClO4, aq.)—II. Mechanism of the electrode reaction

The Randles circuit well represents impedance measurements carried out with activated Pt electrodes. This enables us to study the variation of j_o for redox reactions with concentration of the reactants, at constant potential, and also the variation of j_o with potential, keeping constant the concentration of one of the reactants. The results thus obtained indicate that the step Br₂ + e Br₂⁻ is rate-determining; it is followed or preceded by the rapid equilibria Br₂⁻ Br⁻ + Br 2Br Br₂. The mechanisms proposed hitherto for the electrochemical behaviour of the halogen/halide systems at inert electrodes are discussed, and it is reasoned that the ‘reversibility’ of these systems increases in the order Cl₂/Cl⁻ < Br₂/Br⁻ < I₂/I.