Molecularly Mixed Composite Membranes for Advanced Separation Processes.

Porous organic cages (POCs) are individual soluble, porous molecules. When fabricated into mixed-matrix membranes (MMMs), the soluble POC molecules have the potential to exhibit intimate molecular-level mixing with the polymer matrix. POCs have only recently been incorporated into mixed matrix membrane materials, but this process has not yet resulted in significant improvements of membrane performance. Now, vertex-functionalized amorphous scrambled porous organic cages (ASPOCs) have been utilized as membrane performance enhancers and the amorphous ASPOC mixtures are observed to distribute throughout the matrix without any indication of particle formation or agglomeration, creating unique, molecularly mixed composite membranes. Overall, the molecularly mixed composite membrane provide significant increases in both membrane permeability and selectivity, offering new avenues for creation of membranes with unique properties in industrially relevant separations.

Electrostatic-Assisted Liquefaction of Porous Carbons.

Porous liquids are a newly developed porous material that combine unique fluidity with permanent porosity, which exhibit promising functionalities for a variety of applications. However, the apparent incompatibility between fluidity and permanent porosity makes the stabilization of porous nanoparticle with still empty pores in the dense liquid phase a significant challenging. Herein, by exploiting the electrostatic interaction between carbon networks and polymerized ionic liquids, we demonstrate that carbon-based porous nanoarchitectures can be well stabilized in liquids to afford permanent porosity, and thus opens up a new approach to prepare porous carbon liquids. Furthermore, we hope this facile synthesis strategy can be widely applicated to fabricate other types of porous liquids, such as those (e.g., carbon nitride, boron nitride, metal-organic frameworks, covalent organic frameworks etc.) also having the electrostatic interaction with polymerized ionic liquids, evidently advancing the development and understanding of porous liquids.

Multi-scale microstructural construction in ultralight graphene aerogels enables super elasticity and unprecedented durability for impact protection materials.

Ultralight graphene aerogels have gained extensive recognition in the impact protection field. However, attaining both elasticity and durability at low material density is challenging due to their intrinsic conflicts. Inspired by the mantis ootheca, we present a simultaneous improvement in the elasticity, durability, and density restrictions of ultralight graphene aerogels via constructing a multiscale honeycomb microstructure (MHM) within the graphene skeleton. This approach enables resulting graphene aerogel to achieve a strength per unit volume of 284.6 cm3 mg-1, the ability to recover its shape within 10 ms after an impact at 3.569 m/s, and maintain 97.2 % of its sample height after 20,000 cycles at 90 % strain. The operand analyses and calculation results reveal that the MHM structure facilitates this aerogel's dual-stage stress transfer pathway. Initially, the macroscale honeycomb structure (millimeter-scale) of the graphene aerogels bear and transmit stress to the surrounding regions, followed by the microscale honeycomb structure (micron-scale) deformation to convert stress kinetic energy into elastic potential energy. This two-stage stress transition mechanism of the MHM structure can effectively mitigate excessive local stress and suppress strain localization, thus providing remarkable elasticity and durability. Ultimately, the obtained graphene aerogel demonstrates promising applications as a fall height detection device and impact protective material.

Heat- and freeze-tolerant organohydrogel with enhanced ionic conductivity over a wide temperature range for highly mechanoresponsive smart paint.

Binary solvent-based fabrication permits the conductive organohydrogel to function well at low-temperature environments. However, the deep cryogenic and high temperatures are still threatening the performance of conductive organohydrogels in the application of stretchable electronics, biosensors, and intelligent coatings. Here, a radically new method is developed to introduce propylene and carbonate cellulose nanofibrils into freeze tolerance polymer matrix, and fabricate an antifreezing/antiheating organohydrogel integrated a high mechanical strength (1.6 MPa) and high level of ionic conductivity (4.2 S cm-1) over a wide temperature range (-40 to 100 °C). In this designed system, the propylene carbonate with low freezing point and high boiling point was shown to enhance antifreezing (-40 °C) and antiheating (100 °C) performance of organohydrogel. Furthermore, negative charge-rich cellulose nanofibrils (CNFs) were served as an ion transport channel and nanoreinforcements to boost the conductive and mechanical properties of the organohydrogel. In particular, Molecular Dynamics (MD) simulations reveal that propylene carbonate with high dielectric constant is capable of generating ion migration-facilitated effects, enabling the high ionic conductivity of organohydrogel. Tapping into these attributes, potential applications in mechanoresponsive smart coating have been demonstrated utilizing the appealing organohydrogel as a paint, rendering unprecedented protection and monitoring performance.

First-principles investigations of hydrogen trapping in Y2O3 and the Y2O3|bcc Fe interface.

Based on first-principles calculations, the binding energy of hydrogen atom to Y2O3 and Y2O3|bcc Fe interface (relative to bcc Fe side) with cube-on-cube orientation is at least 0.45 eV, if hydrogen substitutional is considered, or at least 0.26 eV if only hydrogen interstitial is considered. The calculated binding energies do not have a unique fixed value, because they are dependent on the interface structure, the Fermi level of Y2O3 near the interface and the chemical potential of Y/O. Hydrogen substitutional is more stable than hydrogen interstitial near the interface for Fermi level around calculated Schottky barrier height (SBH) at equilibrium. The Y2O3 particle interior can be an effective trapping site for hydrogen. Hydrogen interstitial, hydrogen substitutional and Y/O vacancy have a much lower energy near the interface than within the Y2O3 particle, presumably due to image charge interaction related to their non-zero charge state. For neutral impurities or defects, the energy near interface and that far away from the interface are similar (⩽0.1 eV difference) for a perfect coherent interface. The Y2O3|bcc Fe interface should provide effective trapping sites for hydrogen atoms in oxide dispersion strengthened (ODS) steels.

Porous liquid zeolites: hydrogen bonding-stabilized H-ZSM-5 in branched ionic liquids.

Porous liquids, as a newly emerging type of porous material, have great potential in gas separation and storage. However, the examples and synthetic strategies reported so far likely represent only the tip of the iceberg due to the great difficulty and challenge in engineering permanent porosity in liquid matrices. Here, by taking advantage of the hydrogen bonding interaction between the alkane chains of branched ionic liquids and the Brønsted sites in H-form zeolites, as well as the mechanical bond of the long alkyl chain of the cation penetrated into the zeolite channel at the interface, the H-form zeolites can be uniformly stabilized in branched ionic liquids to form porous liquid zeolites, which not only significantly improve their gas sorption performance, but also change the gas sorption-desorption behavior because of the preserved permanent porosity. Furthermore, such a facile synthetic strategy can be extended to fabricate other types of H-form zeolite-based porous liquids by taking advantage of the tunability of the counter-anion (e.g., NTf2-, BF4-, EtSO4-, etc.) in branched ionic liquids, thus opening up new opportunities for porous liquids for specific applications in energy and environment.

New Class of Type III Porous Liquids: A Promising Platform for Rational Adjustment of Gas Sorption Behavior.

Porous materials have already manifested their unique properties in a number of fields. Generally, all porous materials are in a solid state other than liquid, in which molecules are closely packed without porosity. "Porous" and "liquid" seem like antonyms. Herein, we report a new class of Type 3 porous liquids based on rational coupling of microporous framework nanoparticles as porous hosts with a bulky ionic liquid as the fluid media. Positron annihilation lifetime spectroscopy (PALS) and CO2 adsorption measurements confirm the successful engineering of permanent porosity into these liquids. Compared to common porous solid materials, as-synthesized porous liquids exhibited pronounced hysteresis loops in the CO2 sorption isotherms even at ambient conditions (298 K, 1 bar). The unique features of these novel porous liquids could bring new opportunities in many fields including gas separation and storage, air separation and regeneration, gas transport, and permanent gas storage at ambient conditions.

Effect of Cross-Link Density on Carbon Dioxide Separation in Polydimethylsiloxane-Norbornene Membranes.

The development of high-performance materials for carbon dioxide separation and capture will significantly contribute to a solution for climate change. Herein, (bicycloheptenyl)ethyl-terminated polydimethylsiloxane (PDMSPNB) membranes with varied cross-link densities were synthesized via ring-opening metathesis polymerization. The developed polymer membranes show higher permeability and better selectivity than those of conventional cross-linked PDMS membrane. The achieved performance (CO2 permeability≈6800 Barrer; CO2 /N2 selectivity≈14) is very promising for practical applications. The key to achieving this high performance is the use of an in situ cross-linking method for difunctional PDMS macromonomers, which provides lightly cross-linked membranes. By combining positron annihilation lifetime spectroscopy, broadband dielectric spectroscopy, and gas solubility measurements, key parameters necessary for achieving excellent performance have been elucidated.