Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis.

The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognized as a barrier hampering their practical applications. Here, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100 °C, 24 h) and air (up to 390 °C) is presented. The bifunctional 1-vinylimidazole (VIm) with a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches through a coordination process at room temperature, followed by a radical polymerization. We refer to this material as coordination-supported imidazolate networks (CINs). Interestingly, CINs are composed of rich mesopores from 2-15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. In particular, the stable CINs illustrate a high turnover frequency (TOF) of 779 h-1 in the catalytic oxidation of phenol with H2 O as the green solvent.

Nanoporous ionic organic networks: stabilizing and supporting gold nanoparticles for catalysis.

Nanoporous ionic organic networks (PIONs) with a high ionic density (three cation-anion pairs per unit) have been synthesized by a facile SN2 nucleophilic substitution reaction. Owing to the electrostatic and steric effect, those ionic networks with porous channels can stabilize and support gold (Au) nanoparticles (NPs) in 1-2 nm. The Au@PION hybrid materials used as a heterogeneous catalyst were highly active, selective, and stable in the aerobic oxidation of saturated alcohols.

Charged Porous Polymers using a Solid C-O Cross-Coupling Reaction.

Herein, we report a green, fast, efficient mechanochemical strategy for charged porous polymers (CPPs). A cationic CPP with basic anions and an anionic CPP with Li(+) cations were fabricated by solid grinding under solvent-free conditions. Compared with solution-based synthesis, mechanochemical grinding can shorten the reaction time from dozens of hours to several minutes (60-90 min) to form polymers possessing a high molecular mass and low polydispersity. During the construction of CPPs, a Pd-catalyzed solid polycondensation based on unactivated organic linkers was introduced. In particular, CPPs with basic phenolic or proline anions showed good activity and stability in SO2 capture, and Li(+) -functionalized CPPs can be post-modified to CPPs with other metal ions by ion exchange, highlighting the tailorable feature of ionic-modified CPPs.

Hypercrosslinked phenolic polymers with well-developed mesoporous frameworks.

A soft chemistry synthetic strategy based on a Friedel-Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro-mesoporous architecture with well-preserved organic functional groups, which is effective for carbon capture. Moreover, this soft chemistry synthetic protocol can be further extended to nanotexture other arene-based polymers with robust frameworks.

Thermosensitive aqueous gels with tunable sol-gel transition temperatures from thermo- and pH-responsive hydrophilic ABA triblock copolymer.

This article reports on the synthesis of a well-defined hydrophilic ABA triblock copolymer composed of a poly(ethylene oxide) (PEO) middle block and thermo- and pH-sensitive outer blocks and the study of sol-gel transitions of its aqueous solutions at various pH values. The doubly responsive linear triblock copolymer, poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid)-b-PEO-b-poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid) (P(DEGMMA-co-MAA)-b-PEO-b-P(DEGMMA-co-MAA)), was prepared by atom transfer radical polymerization of a mixture of DEGMMA and tert-butyl methacrylate with a molar ratio of 100: 5 from a difunctional PEO macroinitiator and subsequent removal of tert-butyl groups using trifluoroacetic acid. Dynamic light scattering studies showed that the critical micellization temperature (CMT) of this ABA triblock copolymer in a 0.2 wt % aqueous solution was dependent on the solution pH and can be varied in a large temperature range (>20 degrees C). To study the sol-gel transitions, a 12.0 wt % aqueous solution of the triblock copolymer with a pH of 4.89 was made; its pH value can be readily changed and well controlled by the injection of either a 1.0 M HCl or a 1.0 M KOH solution. From rheological measurements, the sol-gel transition temperature (T(sol-gel)) versus pH curve was found to closely trace the CMT versus pH curve, though there was a shift. By cycling the solution pH between 3.2 and 5.4, we showed that the T(sol-gel) at a specific pH was reproducible. Moreover, multiple sol-gel-sol transitions were realized by judiciously controlling the temperature and pH simultaneously, demonstrating the possibility of achieving on-demand sol-gel transitions by using two external stimuli. In addition, the effect of polymer concentration on T(sol-gel) at pH = 4.0 was investigated. The sol-gel transition temperature increased with the decrease of polymer concentration and the critical gelation concentration was found to be between 4 and 6 wt %.

Behavior and control of chlorine in dyestuff residue incineration.

Dyestuff residue, a type of hazardous waste, is incinerated in the tubular furnace, and thermodynamic equilibrium model is used to calculate and analyze the chlorine behavior. The HCl emission and its effects on the behaviors of heavy metals are studied. Meanwhile, the effects of three dechlorine reagents are predicted at a high temperature. Results show that HCl emission is dependent on incineration temperature. The HCl evaporated mainly derives from the organic chlorine. Under the working condition of 500-900 degrees C, the main products of Hg, Pb, Cu, Ni, Zn, and Mn in reaction with HCl are HgCl2 (g), PbCl4(g), PbCl2 (g), (CuCl)3 (g), NiCl2 (s), NiCl2 (g), ZnCl2 (s), ZnCl2 (g), Zn (g), MnCl2 (s), and MnCl2 (g), respectively. Among the three dechlorine reagents, CaCO3 is optimal to remove chlorine at high temperature, little of HCl is released below 800 degrees C, whereas Fe3O4 is unstable at high temperature.

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries.

A polymer gel electrolyte using AlCl3 complexed acrylamide as a functional monomer and acidic ionic liquid based on a mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl3 (EMImCl-AlCl3, 1-1.5, in molar ratio) as a plasticizer has been successfully prepared for the first time via free radical polymerization. Aluminum deposition is successfully achieved using a polymer gel electrolyte containing 80 wt% ionic liquid. The polymer gel electrolytes are also good candidates for rechargeable aluminum ion batteries.

New ionic liquids based on the complexation of dipropyl sulfide and AlCl3 for electrodeposition of aluminum.

A new kind of ionic liquid based on the complexation of dipropyl sulfide (DPS) and AlCl3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 × 10(-4) S cm(-1). This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

A stable fluorinated and alkylated lithium malonatoborate salt for lithium ion battery application.

A new fluorinated and alkylated lithium malonatoborate salt, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), has been synthesized for lithium ion battery application. A 0.8 M LiBMFMB solution is obtained in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1 : 2 by wt). The new LiBMFMB based electrolyte exhibits good cycling stability and rate capability in LiNi0.5Mn1.5O4 and graphite based half-cells.

Polymerized Ionic Networks with High Charge Density: Quasi-Solid Electrolytes in Lithium-Metal Batteries.

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10(-3) S cm(-1) at 22°C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Memory of surface patterns in mixed polymer brushes: simulation and experiment.

The correlation between the morphology of mixed polymer brushes and fluctuations of the grafting points is investigated by single-chain-in-mean-field simulations and experiments. The local topography of two types of mixed polystyrene-polymethylmethacrylate (PS-PMMA) brushes that differ in their modes of attachment has been studied during repeated microphase separation into laterally structured and homogeneous morphologies upon changing solvents. In the first type of brush (conventional), each of the surface-attached initiator groups starts the growth of either a PS or a PMMA chain in a random fashion. In the second case (Y-shaped mixed brushes), two chains of different types are attached to the same anchor group on the substrate. Whereas in the first case statistical fluctuations of the chemical composition occur on a local scale, such composition fluctuations are strongly suppressed in the latter case. The microphase-separated morphology is similar in both cases, but Y-shaped brushes exhibit a significantly weaker domain memory than do conventional PS-PMMA mixed brushes. The results of the experiment are compared with simulations, and a simple phenomenological argument and qualitative agreement are found. The observations demonstrate that small fluctuations in the grafting points are amplified by the microphase separation and nucleate the location of the domains in the mixed brush.