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Author ORCID ID is 0000000339254174
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  1. The family of diamine-appended metal–organic frameworks exemplified by compounds of the type mmen–M 2(dobpdc) (mmen = N,N'-dimethylethylenediamine; M = Mg, Mn, Fe, Co, Zn; dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are adsorbents with significant potential for carbon capture, due to their high working capacities and strong selectivity for CO 2 that stem from a cooperative adsorption mechanism. Herein, we use first-principles density functional theory (DFT) calculations to quantitatively investigate the role of mmen ligands in dictating the framework properties. Our van der Waals-corrected DFT calculations indicate that electrostatic interactions between ammonium carbamate units significantly enhance the CO 2 binding strength relative tomore » the unfunctionalized frameworks. Additionally, our computed energetics show that mmen–M 2(dobpdc) materials can selectively adsorb CO 2 under humid conditions, in agreement with experimental observations. The calculations further predict an increase of 112% and 124% in the orientationally-averaged Young's modulus E and shear modulus G, respectively, for mmen–Zn 2(dobpdc) compared to Zn 2(dobpdc), revealing a dramatic enhancement of mechanical properties associated with diamine functionalization. Taken together, our calculations demonstrate how functionalization with mmen ligands can enhance framework gas adsorption and mechanical properties.« less
  2. Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation whilemore » maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. Finally, these studies provide a template for the future design of other redox-active oligomers for this application.« less
  3. Many forward-looking clean-energy technologies hinge on the development of scalable and efficient membrane-based separations. Ongoing investment in the basic research of microporous materials is beginning to pay dividends in membrane technology maturation. Specifically, improvements in membrane selectivity, permeability, and durability are being leveraged for more efficient carbon capture, desalination, and energy storage, and the market adoption of membranes in those areas appears to be on the horizon. Herein, an overview of the microporous materials chemistry driving advanced membrane development, the clean-energy separations employing them, and the theoretical underpinnings tying membrane performance to membrane structure across multiple length scales is provided.more » The interplay of pore architecture and chemistry for a given set of analytes emerges as a critical design consideration dictating mass transport outcomes. Also discussed are opportunities and outstanding challenges in the field, including high-flux 2D molecular-sieving membranes, phase-change adsorbents as performance-enhancing components in composite membranes, and the need for quantitative metrologies for understanding mass transport in heterophasic materials and in micropores with unusual chemical interactions with analytes of interest.« less
    Cited by 2
  4. We predict that the orientationally-averaged Young's modulus of mmen–Zn 2 (dobpdc) increases by 112% compared to Zn 2 (dobpdc), a remarkable increase.
  5. Polymer binders in battery electrodes may be either active or passive. This distinction depends on whether the polymer influences charge or mass transport in the electrode. Though it is desirable to understand how to tailor the macromolecular design of a polymer to play a passive or active role, design rules are still lacking, as is a framework to assess the divergence in such behaviors. We reveal the molecular-level underpinnings that distinguish an active polyelectrolyte binder designed for lithium-sulfur batteries from a passive alternative. The binder, a cationic polyelectrolyte, is shown to both facilitate lithium-ion transport through its reconfigurable network ofmore » mobile anions and restrict polysulfide diffusion from mesoporous carbon hosts by anion metathesis, which we show is selective for higher oligomers. These attributes then allow cells to be operated for > 100 cycles with excellent rate capability using cathodes with areal sulfur loadings up to 8.1 mg cm -2 .« less
  6. Despite the availability of chemistries to tailor the pore architectures of microporous polymer membranes for chemical separations, trade-offs in permeability and selectivity with functional group manipulations nevertheless persist, which ultimately places an upper bound on membrane performance. We introduce a new design strategy to uncouple these attributes of the membrane. Key to our success is the incorporation of phase-change metal-organic frameworks (MOFs) into the polymer matrix, which can be used to increase the solubility of a specific gas in the membrane, and thereby its permeability. We further show that it is necessary to scale the size of the phase-change MOFmore » to nanoscopic dimensions, in order to take advantage of this effect in a gas separation. Our observation of an increase in solubility and permeability of only one of the gases during steady-state permeability measurements suggests fast exchange between free and chemisorbed gas molecules within the MOF pores. While the kinetics of this exchange in phase-change MOFs are not yet fully understood, their role in enhancing the efficacy and efficiency of the separation is clearly a compelling new direction for membrane technology.« less
  7. Bicontinuous jammed emulsions (or bijels) are tortuous, interconnected structures of two immiscible liquids, kinetically trapped by colloidal particles that are irreversibly bound to the oil–water interface. A wealth of applications has been proposed for bijels in catalysis, energy storage and molecular encapsulation, but large domain sizes (on the order of 5 µm or larger) and difficulty in fabrication pose major barriers to their use. In this paper, we show that bijels with sub-micrometre domains can be formed via homogenization, rather than spinodal decomposition. We achieve this by using nanoparticle surfactants: polymers and nanoparticles of complementary functionality (for example, ion-pairing) thatmore » bind to one another at the oil–water interface. This allows the stabilization of the bijel far from the demixing point of the liquids, with interfacial tensions on the order of 20 mN m -1. Finally, furthermore, our strategy is extremely versatile, as solvent, nanoparticle and ligand can all be varied.« less
    Cited by 1
  8. Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

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