Jia Min Chin

Tuning the aspect ratio of NH2-MIL-53(Al) microneedles and nanorods via coordination modulation

Micro-needles and nano-rods of NH2-Mil-53(Al) have been synthesized via coordination modulation. PXRD analysis has been utilized to determine the orientation of the micro-needles, showing the preferred growth direction to be [001]. Nanoparticles of NH2-Mil-53(Al) were formed using NaOH as a base.

Photoresponsive Liquid Marbles and Dry Water

Stimuli-responsive liquid marbles for controlled release typically rely on organic moieties that require lengthy syntheses. We report herein a facile, one-step synthesis of hydrophobic and oleophobic TiO2 nanoparticles that display photoresponsive wettability. Water liquid marbles stabilized by these photoresponsive TiO2 particles were found to be stable when shielded from ultraviolet (UV) radiation; however, they quickly collapsed after being irradiated with 302 nm UV light. Oil- and organic-solvent-based liquid marbles could also be fabricated using oleophobic TiO2 nanoparticles and show similar UV-induced collapse. Finally, we demonstrated the formation of the micronized form of water liquid marbles, also known as dry water, by homogenization of the TiO2 nanoparticles with water. The TiO2 dry water displayed a similar photoresponse, whereby the micronized liquid marbles collapsed after irradiation and the dry water turned from a free-flowing powder to a paste. Hence, by exploiting the photoresponsive wettability of TiO2, we fabricated liquid marbles and dry water that display photoresponse and studied the conditions required for their collapse.

CO2 capture by dry alkanolamines and an efficient microwave regeneration process

Removal of acidic gases such as H2S and CO2 is performed during the purification of raw natural gas, most commonly using amine gas treatment. However, this industrially entrenched method is limited by significant shortcomings including low operational capture efficiency, amine pipeline corrosion and a large energy penalty due to the sorbent regeneration process. To address these shortcomings, we have studied the use of perfluorinated silica-stabilized dry alkanolamines (DAf) for CO2 capture. Due to their micronized liquid domains, DAf display high operational CO2 capture efficiency. Further, to minimize energy requirements for sorbent regeneration, microwave-assisted regeneration of the spent DAf sorbent was also studied and shown to decrease the energy requirements by about ten times. In contrast to very recent work, our results show that the use of DAf exhibits extraordinary recyclability, with a negligible decrease in absorption capacity over at least ten absorption–regeneration cycles, indicating the potential of this material for gas treatment applications.

Non-close-packed pore arrays through one-step breath figure self-assembly and reversal

Non-close-packed arrays of micro- and submicron-pores with separation distances many multiples of pore size were fabricated using a dynamic self-assembly method known as breath figure patterning. We report a novel method by which these arrays can be formed via the in situ control of growth and shrinkage of the water droplet arrays during polymer film drying. Transfer of the polymer solution onto a thermally conductive stage midway during the drying process afforded breath figure arrays with feature separation-to-size ratios of up to 12.44. This novel approach introduces the possibility of forming non-close-packed morphologies not typically accessible via traditional self-assembly methods.

Non-Close-Packed Breath Figures via Ion-Partitioning-Mediated Self-Assembly

We report a one-step method of forming non-close-packed (NCP) pore arrays of micro- and sub-micropores using chloroform-based solutions of polystyrene acidified with hydrogen bromide for breath figure (BF) patterning. As BF patterning takes place, water vapor condenses onto the polystyrene solution, forming water droplets on the solution surface. Concurrently, preferential ion partitioning of hydrogen bromide leads to positively charged water droplets, which experience interdroplet electrostatic repulsion. Self-organization of charged water droplets because of surface flow and subsequent evaporation of the droplet templates result in ordered BF arrays with pore separation/diameter (L/D) ratios of up to 16.5. Evidence from surface potential scans show proof for preferential ion partitioning of HBr. Radial distribution functions and Voronoi polygon analysis of pore arrays show that they possess a high degree of conformational order. Past fabrication methods of NCP structures typically require multi-step processes. In contrast, we have established a new route for facile self-assembly of previously inaccessible patterns, which comprises of only a single operational step.

Magnetic control of MOF crystal orientation and alignment

Most metal-organic frameworks (MOFs) possess anisotropic properties, the full exploitation of which necessitates a general strategy for the controllable orientation of such MOF crystals. Current methods largely rely upon layer-by-layer MOF epitaxy or tuning of MOF crystal growth on appropriate substrates, yielding MOFs with fixed crystal orientations. Here, the dynamic magnetic alignment of different MOF crystals (NH2 -MIL-53(Al) and NU-1000) is shown. The MOFs were magnetized by electrostatic adsorption of iron oxide nanoparticles, dispersed in curable polymer resins (Formlabs 1+ clear resin/ Sylgard 184), magnetically oriented, and fixed by resin curing. The importance of crystal orientation on MOF functionality was demonstrated whereby magnetically aligned NU-1000/Sylgard 184 composite was excited with linearly polarized 405 nm light, affording an anisotropic fluorescence response dependent on the polarization angle of the excitation beam relative to NU-1000 crystal orientation.