Liquid Metal Nanoparticles as Initiators for Radical Polymerization of Vinyl Monomers
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Nanoporous silica membranes exhibit excellent H 2 /CO 2 separation properties for sustainable H 2 production and CO 2 capture but are prepared via complicated thermal processes above 400 °C, which prevent their scalable production at a low cost. Here, we demonstrate the rapid fabrication (within 2 min) of ultrathin silica-like membranes (~3 nm) via an oxygen plasma treatment of polydimethylsiloxane-based thin-film composite membranes at 20 °C. The resulting organosilica membranes unexpectedly exhibit H2 permeance of 280-930 GPU (1 GPU = 3.347 x 10 -10 mol m -2 s -1 Pa -1 ) and H2/CO2 selectivity of 93-32 at 200 °C, far surpassing state-of-the-art membranes and Robeson’s upper bound for H 2 /CO 2 separation. When challenged with a 3 d simulated syngas test containing water vapor at 200 °C and a 340 d stability test, the membrane shows durable separation performance and excellent hydrothermal stability. The robust H 2 /CO 2 separation properties coupled with excellent scalability demonstrate the great potential of these organosilica membranes for economic H 2 production with minimal carbon emissions.
A lignin-graft-poly(lactic- co -glycolic) acid (PLGA) biopolymer was synthesized with two types of lignin (LGN), alkaline lignin (ALGN) and sodium lignosulfonate (SLGN), at different (A/S)LGN/PLGA ratios (1:2, 1:4, and 1:6 w/w). 1 H NMR and Fourier-transform infrared spectroscopy (FT-IR) confirmed the conjugation of PLGA to LGN. The (A/S)LGN-graft-PLGA biopolymers were used to form nanodelivery systems suitable for entrapment and delivery of drugs for disease treatment. The LGN-graft-PLGA NPs were generally small (100–200 nm), increased in size with the amount of PLGA added, monodisperse, and negatively charged (-48 to -60 mV). Small-angle scattering data showed that particles feature a relatively smooth surface and a compact spherical structure with a distinct core and a shell. The core size and shell thickness varied with the LGN/PLGA ratio, and at a 1:6 ratio, the particles deviated from the core–shell structure to a complex internal structure. The newly developed (A/S)LGN-graft-PLGA NPs are proposed as a potential delivery system for applications in biopharmaceutical, food, and agricultural sectors.
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The hydrophobic polymers polydimethyl siloxane (PDMS) and polypropyleneglycol dimethylether (PPGDME) may provide an alternative to physical solvents based on the hydrophilic polymer polyethyleneglycol dimethylether (PEGDME) for the precombustion capture of CO{sub 2} from the warm, high pressure stream that also contains H{ 2 O and H 2 . PPGDME can be made with a linear repeat unit (PPGDMEl, poly(1,3-propanediol) dimethylether) or a branched repeat unit (PPGDMEb, poly(1,2-propanediol) dimethylether). The solubility of CO 2 and H 2 in each of the four solvents of specified average molecular weight (PEGDME 250, PDMS 550, PPGDMEl 678 and PPGDMEb 430) is determined between 25 and 120 °C at pressures to 10 MPa. CO 2 is much more soluble in each solvent than H{sub 2}; however, the solubility of CO{sub 2} decreases as the solubility of H 2 increases with increasing temperature. PPGDMEl 678 and PPGDMEb 430 are comparable CO 2 solvents. PPGDMEl 678 absorbs less H{sub 2} than all the other solvents, while PPGDMEb 430 absorbs significantly more H 2 }. PDMS 550 is a very good CO 2 solvent, absorbing more CO 2 than all of the other solvents at all temperatures except for PEGDME 250 at 25 °C. PDMS 550 absorbs more H 2 than all of the other solvents.
Post combustion CO{sub 2} capture is most commonly carried out using an amine solution that results in a high parasitic energy cost in the stripper unit due to the need to heat the water which comprises a majority of the amine solution. It is also well known that amine solvents suffer from stability issues due to amine leaching and poisoning by flue gas impurities. Solid sorbents provide an alternative to solvent systems that would potentially reduce the energy penalty of carbon capture. However, the cost of using a particular sorbent is greatly affected by the usable lifetime of the sorbent. This work investigated the stability of a primary amine-functionalized ion exchange resin in the presence of O{sub 2} and SO{sub 2}, both of which are constituents of flue gas that have been shown to cause degradation of various amines in solvent processes. The CO{sub 2} capture capacity was measured over multiple capture cycles under continuous exposure to two simulated flue gas streams, one containing 12 vol% CO{sub 2}, 4% O{sub 2}, 84% N{sub 2}, and the other containing 12.5 vol% CO{sub 2}, 4% O{sub 2}, 431 ppm SO{sub 2}, balance N{sub 2} using a custom-built packed bed reactor. The resin maintained its CO{sub 2} capture capacity of 1.31 mol/kg over 17 capture cycles in the presence of O{sub 2} without SO{sub 2}. However, the CO{sub 2} capture capacity of the resin decreased rapidly under exposure to SO{sub 2} by an amount of 1.3 mol/kg over 9 capture cycles. Elemental analysis revealed the resin adsorbed 1.0 mol/kg of SO{sub 2}. Thermal regeneration was determined to not be possible. The poisoned resin was, however, partially regenerated with exposure to 1.5M NaOH for 3 days resulting in a 43% removal of sulfur, determined through elemental analysis, and a 35% recovery of CO{sub 2} capture capacity. Evidence was also found for amine loss upon prolonged (7 days) continuous exposure to high temperatures (120 C) in air. It is concluded that desulfurization of the flue gas stream prior to CO{sub 2} capture will greatly improve the economic viability of using this solid sorbent in a post-combustion CO{sub 2} capture process.
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A fundamental challenge, shared across many energy storage devices, is the complexity of electrochemistry at the electrode–electrolyte interfaces that impacts the Coulombic efficiency, operational rate capability, and lifetime. Specifically, in energy-dense lithium metal batteries, the charging/discharging process results in structural heterogeneities of the metal anode, leading to battery failure by short-circuit and capacity fade. In this work, we take advantage of organic cations with lower reduction potential than lithium to build an electrically responsive polymer interface that not only adapts to morphological perturbations during electrodeposition and stripping but also modulates the lithium ion migration pathways to eliminate surface roughening. As a result, we find that this concept can enable prolonging the long-term cycling of a high-voltage lithium metal battery by at least twofold compared to bare lithium metal.
The lack of design principle for developing high-performance polymer materials displaying strong fluorescence and high ambipolar charge mobilities limited their performance in organic light-emitting transistors (OLETs), electrically pumped organic laser, and other advanced electronic devices. Here, a series of semiladder polymers by copolymerization of weak acceptors (TPTQ or TPTI) and weak donors (fluorene (F) or carbazole (C)) have been developed for luminescent and charge transporting properties. It was found that enhanced planarity, high crystallinity, and a delicate balance in interchain aggregation obtained in the new copolymer, TPTQ-F, contributed to high ambipolar charge mobilities and photoluminescent quantum yield. TPTQ-F showed excellent performance in solution-processed multilayered OLET devices with an external quantum efficiency (EQE) of 5.3%.
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