Polymer‐Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal–Organic Frameworks

A template‐assisted polymer‐derived ceramic route is investigated for preparing a series of silicoboron carbonitride (Si/B/C/N) foams with a hierarchical pore size distribution and tailorable interconnected porosity. A boron‐modified polycarbosilazane was selected to impregnate monolithic silica and carbonaceous templates and form after pyrolysis and template removal Si/B/C/N foams. By changing the hard template nature and controlling the quantity of polymer to be impregnated, controlled micropore/macropore distributions with mesoscopic cell windows are generated. Specific surface areas from 29 to 239 m² g^?1 and porosities from 51 to 77 % are achieved. These foams combine a low density with a thermal insulation and a relatively good thermostructural stability. Their particular structure allowed the in situ growth of metal–organic frameworks (MOFs) directly within the open‐cell structure. MOFs offered a microporosity feature to the resulting Si/B/C/N@MOF composite foams that allowed increasing the specific surface area to provide CO₂ uptake of 2.2 %.     

Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis,Structures, and Quantum Chemical Calculations

Reactions of the tris(3,5‐dimethylpyrazolyl)methanide amido complexes [M′{C(3,5‐Me₂pz)₃}{N(SiMe₃)₂}] (M′=Mg ( 1 a ), Zn ( 1 b ), Cd ( 1 c ); 3,5‐Me₂pz=3,5‐dimethylpyrazolyl) with two equivalents of the acidic Group 6 cyclopentadienyl (Cp) tricarbonyl hydrides [MCp(CO)₃H] (M=Cr ( 2 a ), Mo ( 2 b )) gave different types of heterobimetallic complex. In each case, two reactions took place, namely the conversion of the tris(3,5‐dimethylpyrazolyl)methanide ligand (Tpmd*) into the ‐methane derivative (Tpm*) and the reaction of the acidic hydride M?H bond with the M′?N(SiMe₃)₂ moiety. The latter produces HN(SiMe₃)₂ as a byproduct. The Group 2 representatives [Mg(Tpm*){MCp(CO)₃}₂(thf)] ( 3 a / b ) form isocarbonyl bridges between the magnesium and chromium/molybdenum centres, whereas direct metal–metal bonds are formed in the case of the ions [Zn(Tpm*){MCp(CO)₃}]⁺ ( 4 a / b ; [MCp(CO)₃]^? as the counteranion) and [Cd(Tpm*){MCp(CO)₃}(thf)]⁺ ( 5 a / b ; [Cd{MCp(CO)₃}₃]^? as the counteranion). Complexes 4 a and 5 a / b are the first complexes that contain Zn?Cr, Cd?Cr, and Cd?Mo bonds (bond lengths 251.6, 269.8, and 278.9 pm, respectively). Quantum chemical calculations on 4 a / b* (and also on 5 a / b* ) provide evidence for an interaction between the metal atoms.     

Polyimide polydimethylsiloxane triblock copolymers for thin film composite gas separation membranes

This article demonstrates the successful fabrication of thin‐film‐composite (TFC) membranes containing well‐defined soft‐hard‐soft triblock copolymers. Based on “hard” polyimide (PI) and “soft” polydimethylsiloxane (PDMS), these triblock copolymers (PDMS‐b‐PI‐b‐PDMS), were prepared via condensation polymerization, and end‐group allylic functionalization to prepare the polyimide component and subsequent “click” coupling with the soft azido functionalized PDMS component. The selective layer consisted of pure PDMS‐b‐PI‐b‐PDMS copolymers which were cast onto a precast crosslinked‐PDMS gutter layer which in turn was cast onto a porous polyacrylonitrile coated substrate. The TFC membranes' gas transport properties, primarily for the separation of carbon dioxide (CO₂) from nitrogen (N₂), were determined at 35 °C and at a feed pressure of 2 atm. The TFC membranes showed improvements in gas permselectivity with increasing PDMS weight fraction. These results demonstrate the ability for glassy, hard polymer components to be coated onto otherwise incompatible surfaces of highly permeable soft TFC substrates through covalent coupling. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3372–3382     

A Push Forward Construction and the Comprehensive Factorization for Internal Crossed Modules

In a semi-abelian category, we give a categorical construction of the push forward of an internal pre-crossed module, generalizing the pushout of a short exact sequence in abelian categories. The main properties of the push forward are discussed. A simplified version is given for action accessible categories, providing examples in the categories of rings and Lie algebras. We show that push forwards can be used to obtain the crossed module version of the comprehensive factorization for internal groupoids.     

Hydrocarbon solubility,permeability, and competitive sorption effects in polymer of intrinsic microporosity (PIM‐1) membranes

The sorption and permeation of pentane, hexane, and toluene through highly permeable polymer of intrinsic microporosity (PIM‐1) membranes were investigated. It was established that the hydrocarbons sorbed strongly within the micro‐void regions of the PIM‐1 membrane. The sorption concentration was similar for the paraffins, pentane and hexane, but greater for aromatic toluene at high vapor activities. The magnitude of the hydrocarbon permeability was associated with the critical temperature of the hydrocarbon. The PIM‐1 membrane displayed selectivity for the three hydrocarbons over CO₂. As a consequence, the presence of the three hydrocarbons dramatically reduced the permeability of CO₂ and N₂ under mixed gas–vapor conditions to 68%–95% below the dry gas value. For all three hydrocarbons the N₂ permeability was more strongly impacted than CO₂ permeability, and hence the ideal CO₂/N₂ selectivity of PIM‐1 increased. It was determined that CO₂ and N₂ solubility decreased because of hydrocarbon competitive sorption while CO₂ and N₂ diffusivity also decreased because of anti‐plasticization, which was due to the presence of hydrocarbon clusters within the membrane structure. There was a clear correlation between the magnitude of anti‐plasticization and the critical temperature of the hydrocarbon. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 397–404