Polymer molecular sieve membranes

Sustainable energy supply and environmental protection are the major global scientific challenges in the 21st century, such as greenhouse gas capture, natural gas production, desalination of seawater for clean water production. Membrane separation technology offers attractive energy-efficient and environmental-friendly solutions to these challenges. This PhD thesis is focused on design and fabrication of membranes from novel molecularly defined polymers and understanding their physical properties, particularly the transport properties of gas molecules in polymer membranes. First, we demonstrate a simple approach of fabricating novel polymer nanocomposite membranes using established colloidal science. Crystalline microporous zeolitic imidazolate frameworks (ZIFs) nanocrystals are incorporated into a polyimide polymer matrix via solution mixing. The resulting nanocomposite membranes show excellent dispersion of nanoparticles, good adhesion at the interface, and enhanced gas permeability while the selectivity remain at high level. We then fabricated membranes from novel microporous polymers, polymers of intrinsic microporosity (PIMs). Using the PIM-1 polymer as a prototype, we discovered that ultraviolet irradiation of PIM-1 membranes in the presence of oxygen induces oxidative chain scission at the surface, resulting in local densification and structural transformation of free volume elements. Consequently, the membrane become asymmetric with a more gas-selective layer formed at the surface, while the overall permeability maintains at high level. Finally, we report a simple thermal oxidative crosslinking method to tailor the architecture of channels and free volume elements in PIM-1 polymer membrane by heat treatment in the presence of trace amounts of oxygen molecules. The resulting covalently crosslinked polymer networks offer superior thermal stability, chemical stability, reasonable mechanical strength, and enhanced rigidity. Most important of all, thermally crosslinked PIM-1 polymer membranes show significantly enhanced molecular sieving functions that yield remarkably high selectivity and high gas permeability, which surpass the upper bound that has been limiting the polymer membranes for decades. We also demonstrate that the thermal crosslinking method is effective for crosslinking of nanocomposite membranes with porous or nonporous fillers. These microporous molecular sieve membranes are promising for a wide range of molecular-level separation applications

A cost-effective alkaline polysulfide-air redox flow battery enabled by a dual-membrane cell architecture

With the rapid development of renewable energy harvesting technologies, there is a significant demand for long-duration energy storage technologies that can be deployed at grid scale. In this regard, polysulfide-air redox flow batteries demonstrated great potential. However, the crossover of polysulfide is one significant challenge. Here, we report a stable and cost-effective alkaline-based hybrid polysulfide-air redox flow battery where a dual-membrane-structured flow cell design mitigates the sulfur crossover issue. Moreover, combining manganese/carbon catalysed air electrodes with sulfidised Ni foam polysulfide electrodes, the redox flow battery achieves a maximum power density of 5.8 mW cm−2 at 50% state of charge and 55 °C. An average round-trip energy efficiency of 40% is also achieved over 80 cycles at 1 mA cm−2. Based on the performance reported, techno-economic analyses suggested that energy and power costs of about 2.5 US$/kWh and 1600 US$/kW, respectively, has be achieved for this type of alkaline polysulfide-air redox flow battery, with significant scope for further reduction

Sulfonated microporous polymer membranes with fast and selective ion transport for electrochemical energy conversion and storage

Membranes with fast and selective transport of protons and cations are required for a wide range of electrochemical energy conversion and storage devices, such as proton-exchange membrane (PEM) fuel cells and redox flow batteries. Here we report a new approach to designing solution-processable ion-selective polymer membranes with both intrinsic microporosity and ion-conductive functionality. This was achieved by synthesizing polymers with rigid and contorted backbones, which incorporate hydrophobic fluorinated and hydrophilic sulfonic acid functional groups, to produce membranes with negatively-charged subnanometer-sized confined ionic channels. The facilitated transport of protons and cations through these membranes, as well as high selectivity towards nanometer-sized redox-active molecules, enable efficient and stable operation of an aqueous alkaline quinone redox flow battery and a hydrogen PEM fuel cell. This membrane design strategy paves the way for producing a new-generation of ion-exchange membranes for electrochemical energy conversion and storage applications

Oriented Two-Dimensional Porous Organic Cage Crystals

The formation of two-dimensional (2D) oriented porous organic cage crystals (consisting of imine-based tetrahedral molecules) on various substrates (such as silicon wafers and glass) by solution-processing is reported. Insight into the crystallinity, preferred orientation, and cage crystal growth was obtained by experimental and computational techniques. For the first time, structural defects in porous molecular materials were observed directly and the defect concentration could be correlated with crystal growth rate. These oriented crystals suggest potential for future applications, such as solution-processable molecular crystalline 2D membranes for molecular separations

Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage

Membranes with fast and selective ion transport are widely used for water purification and devices for energy conversion and storage including fuel cells, redox flow batteries and electrochemical reactors. However, it remains challenging to design cost-effective, easily processed ion-conductive membranes with well-defined pore architectures. Here, we report a new approach to designing membranes with narrow molecular-sized channels and hydrophilic functionality that enable fast transport of salt ions and high size-exclusion selectivity towards small organic molecules. These membranes, based on polymers of intrinsic microporosity containing Tröger’s base or amidoxime groups, demonstrate that exquisite control over subnanometre pore structure, the introduction of hydrophilic functional groups and thickness control all play important roles in achieving fast ion transport combined with high molecular selectivity. These membranes enable aqueous organic flow batteries with high energy efficiency and high capacity retention, suggesting their utility for a variety of energy-related devices and water purification processes

pH-induced reversal of ionic diode polarity in 300nm thin membranes based on a polymer of intrinsic microporosity

“Ionic diode” (or current rectification) effects are potentially important for a range of applications including water purification. In this preliminary report, we observe novel ionic diode behaviour of thin (300 nm) membranes based on a polymer of intrinsic microporosity (PIM-EA-TB) supported on a poly-ethylene-terephthalate (PET) film with a 20 μm diameter microhole, and immersed in aqueous electrolyte media. Current rectification effects are observed for half-cells with the same electrolyte solution on both sides of the membrane for cases where cation and anion mobility differ (HCl, other acids, NaOH, etc.) but not for cases where cation and anion mobility are more alike (LiCl, NaCl, KCl, etc.). A pH-dependent reversal of the ionic diode effect is observed and discussed in terms of tentatively assigned mechanisms based on both (i) ion mobility within the PIM-EA-TB nano-membrane and (ii) a possible “mechanical valve effect” linked to membrane potential and electrokinetic movement of the membrane as well as hydrostatic pressure effects

Polymer nanofilms with enhanced microporosity by interfacial polymerization

Highly permeable and selective membranes are desirable for energy-efficient gas and liquid separations. Microporous organic polymers have attracted significant attention in this respect owing to their high porosity, permeability, and molecular selectivity. However, it remains challenging to fabricate selective polymer membranes with controlled microporosity which are stable in solvents. Here we report a new approach to designing crosslinked, rigid polymer nanofilms with enhanced microporosity by manipulating the molecular structure. Ultra-thin polyarylate nanofilms with thickness down to 20 nm were formed in-situ by interfacial polymerisation. Enhanced microporosity and higher interconnectivity of intermolecular network voids, as rationalised by molecular simulations, are achieved by utilising contorted monomers for the interfacial polymerisation. Composite membranes comprising polyarylate nanofilms with enhanced microporosity fabricated in-situ on crosslinked polyimide ultrafiltration membranes show outstanding separation performance in organic solvents, with up to two orders of magnitude higher solvent permeance than membranes fabricated with nanofilms made from noncontorted planar monomers

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix.

In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed.D.D. acknowledges the Department of Physics, University of Cambridge and the KACST-Cambridge University Joint Centre of Excellence for financial support. G.L. thanks the Gates Cambridge Trust for support. Q.S. acknowledges the Imperial College Junior Research Fellowship. J.L.M.D. acknowledges ERC Advanced Investigator Grant, Novox, ERC-2009-adG247276. This work was supported by the Engineering and Physical Sciences Research Council, UK.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jz502615e

Ring-opening (co)polymerization of γ-butyrolactone: a review

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