Chromium-Salophen as a Soluble or Silica-Supported Co-Catalyst for the Fixation of CO2 Onto Styrene Oxide at Low Temperatures

Addition of a soluble or a supported CrIII-salophen complex as a co-catalyst greatly enhances the catalytic activity of Bu4NBr for the formation of styrene carbonate from styrene epoxide and CO2. Their combination with a very low co-catalyst:Bu4NBr:styrene oxide molar ratio = 1:2:112 (corresponding to 0.9 mol% of CrIII co-catalyst) led to an almost complete conversion of styrene oxide after 7 h at 80°C under an initial pressure of CO2 of 11 bar and to a selectivity in styrene carbonate of 100%. The covalent heterogenization of the complex was achieved through the formation of an amide bond with a functionalized {NH2}-SBA-15 silica support. In both conditions, the use of these CrIII catalysts allowed excellent conversion of styrene already at 50°C (69 and 47% after 24 h, respectively, in homogeneous and heterogeneous conditions). Comparison with our previous work using other metal cations from the transition metals particularly highlights the preponderant effect of the nature of the metal cation as a co-catalyst in this reaction, that may be linked to its calculated binding energy to the epoxides. Both co-catalysts were successfully reused four times without any appreciable loss of performance.

Mesoporous Silica-Supported Ionic Liquids as Catalysts for Styrene Carbonate Synthesis from CO2

Various types of mesoporous silica were used as carriers to synthesize a series of immobilized imidazolium-based ionic liquids. Their activity was tested in the synthesis of styrene carbonate from CO2 and styrene. This is one-pot process, whereby two stages are carried out in one reactor and there is no need to isolate the intermediate product, epoxide. A systematic study on the influence of parameters such as temperature, the reaction time, CO2 pressure, as well as the amount and type of catalyst used was carried out. A strong synergistic catalytic effect of ionic liquid and Lewis acid was observed in promoting this reaction. The addition sequence of regents and amount of immobilized catalyst were considered crucial for the synthesis of styrene carbonate from CO2 and styrene. The tested silica-supported ionic liquids gave an easily-recyclable system which under the most favorable conditions ([mtespim]Cl/@SiO2; ZnBr2, 0.1 mol%; 110 °C, 4 h, 1 MPa) can be reused without a significant loss of catalytic activity nor selectivity.

A kinetic study of Zn halide/TBAB-catalysed fixation of CO2 with styrene oxide in propylene carbonate

Synthesis of styrene carbonate (SC) via the fixation of CO2 with styrene oxide (SO) has been investigated using a combination of zinc bromide (ZnBr2) and tetrabutylammonium halides (TBAX) as acid-base binary homogeneous catalysts. The combination of ZnBr2 and TBAB had a synergistic effect, which led to about 6-fold enhancement in the rate of SC formation as compared to using TBAB alone as a catalyst. Propylene carbonate (PC) was chosen as a green solvent for a comprehensive study of reaction kinetics. The reaction followed a first-order kinetics with respect to SO, CO2, and TBAB, whereas a fractional order was observed for the ZnBr2 when used in combination with the TBAB. Arrhenius and Eyring’s expressions were applied to determine the kinetic and thermodynamic activation parameters, where activation energy (Ea) of 23.3 kJ mol−1 was obtained for the SC formation over the temperature range of 90-120°C. The thermodynamic analysis showed that positive values for enthalpy (ΔH‡ = 18.53 kJ mol−1), Gibbs free energy (ΔG‡ = 79.74 kJ mol−1), whereas a negative entropy (ΔS‡ = –162.88 J mol−1 K−1) was obtained. These thermodynamic parameters suggest that endergonic and kinetically controlled reactions were involved in the formation of SC from SO and CO2.

Laminaria digitata and Palmaria palmata Seaweeds as Natural Source of Catalysts for the Cycloaddition of CO2 to Epoxides

Seaweed powder has been found to act as an effective catalyst for the fixation of CO2 into epoxides to generate cyclic carbonates under solvent free conditions. Model background reactions were performed using metal halides and amino acids typically found in common seaweeds which showed potassium iodide (KI) to be the most active. The efficacy of the seaweed catalysts kelp (Laminaria digitata) and dulse (Palmaria palmata) was probed based on particle size, showing that kelp possessed greater catalytic ability, achieving a maximum conversion and selectivity of 63.7% to styrene carbonate using a kelp loading of 80% by weight with respect to epoxide, 40 bar of CO2, 120 °C for 3 h. Maximizing selectivity was difficult due to the generation of diol side product from residual H2O found in kelp, along with a chlorinated by-product thought to form due to a high quantity of chloride salts in the seaweeds. Data showed there was loss of organic matter upon use of the kelp catalyst, likely due to the breakdown of organic compounds and their subsequent removal during product extraction. This was highlighted as the likely cause of loss of catalytic activity upon reuse of the Kelp catalyst.

A Series of Metal-Organic Frameworks for Selective CO2 Capture and Catalytic Oxidative Carboxylation of Olefins

<p>Three novel lanthanide metal˗organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 were constructed from a naphthalene diimide tetracarboxylic acid. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO₂ (low pressure, at room temperature) and moderate CO₂ selectivity over N₂ and CH₄. Accordingly, breakthrough measurements were performed on a representative MOF-592, in which the separation of CO₂ from binary mixture containing N₂ and CO₂ was demonstrated without any loss in performance over three consecutive cycles. Moreover, MOF-590, MOF-591, and MOF-592 exhibited catalytic activity in the one-pot synthesis of styrene carbonate from styrene and CO₂ under mild conditions (1 atm CO₂, 80 °C, and solvent-free). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%). </p><br>

A Series of Metal-Organic Frameworks for Selective CO2 Capture and Catalytic Oxidative Carboxylation of Olefins

<p>Three novel lanthanide metal˗organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 were constructed from a naphthalene diimide tetracarboxylic acid. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO₂ (low pressure, at room temperature) and moderate CO₂ selectivity over N₂ and CH₄. Accordingly, breakthrough measurements were performed on a representative MOF-592, in which the separation of CO₂ from binary mixture containing N₂ and CO₂ was demonstrated without any loss in performance over three consecutive cycles. Moreover, MOF-590, MOF-591, and MOF-592 exhibited catalytic activity in the one-pot synthesis of styrene carbonate from styrene and CO₂ under mild conditions (1 atm CO₂, 80 °C, and solvent-free). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%). </p><br>