Controllable microfluidic strategies for fabricating microparticles using emulsions as templates

Microfluidic techniques provide flexible strategies for fabrication of uniform advanced microparticles with well-tailored sizes, shapes, structures, and functions from controllable emulsion templates. This review highlights recent progress on controllable synthesis of microparticles using versatile microfluidic emulsions as templates, First, highly controllable and scalable microfluidic techniques for the generation of defined emulsions are introduced. Versatile microfluidic strategies for fabricating microparticles from diverse controllable emulsion templates are then summarized, including solid microparticles with spher- ical, non-spherical, and Janus configurations, porous microparticles with flexible pore structures, and compartmental microparticles with controlled internals. Finally, the future development of microfluidic techniques for microparticle fabrication is briefly discussed.

Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template

The morphology regulation of hollow silica microspheres is significant for their properties and applications. In this paper, hollow silica microspheres were formed through the hydrolysis and condensation reaction of tetraethyl orthosilicate(TEOS) at the interface of the emulsion droplet templates composed of liquid paraffin and TEOS, followed by dissolving paraffin with ethanol. The effects of various factors including the emulsifier structure and content, TEOS content, catalyst type, and the ethanol content in the continuous water phase on the particle size, shell thickness and morphology of the prepared hollow silica microspheres were studied in detail. The results show that the diffusion and contact of TEOS and water molecules as well as the hydrolysis condensation reaction of TEOS at the oil-water interface are two critical processes for the synthesis and morphological regulation of hollow silica microspheres. Cationic emulsifier with a hydrophobic chain of appropriate length is the prerequisite for the successful synthesis of hollow silica microspheres. The ethanol content in water phase is the dominant factor to determine the average diameter of hollow microspheres, which can vary from 96 nm to 660 nm with the increase of the volume ratio of alcohol-water from 0 to 0.7. The silica wall thickness varies with the content and the hydrophobic chain length of the emulsifier, TEOS content, and the activity of the catalyst. The component of the soft template will affect the morphology of the silica wall. When the liquid paraffin is replaced by cyclohexane, hollow microspheres with fibrous mesoporous silica wall are fabricated. This work not only enriches the basic theory of interfacial polymerization in the emulsion system, but also provides ideas and methods for expanding the morphology and application of hollow silica microspheres.

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.

Preparation of Porous Poly(3-Hydroxybutyrate)Films by Water-Droplet Templating

Porous resorbable implants are of great interest since they may deliver bioactives or drugs, facilitate the transport of body fluids or degradation products and provide a favorable environment for cell attachment and growth. In this work we report on a method using concentrated emulsions to template interconnected solid foam materials and to produce highly porous poly(3-hydroxybutyrate) (PHB) materials. Porous PHB films were cast made from water-in-oil template emulsions including Span 80 and lithium sulphate. The films were characterized by SEM-EDX and DMA. The water uptake of the films was recorded in order to determine the fraction water available pores. The results show that the addition of lithium sulphate allows a fine tuning of the film morphology with respect to porosity and interconnected porous structure. The film porosity was determined to 51% ± 3%, 52% ± 3% and 45% ± 3% for the films made with 0%, 2.9% and 14.3% lithium sulphate in the template emulsion, respectively. The fraction water available pores was significantly lower, 11% ±3%, 38% ±12% and 48% ± 7% for films with 0%, 2.9% and 14.3% litium sulphate respectively. Differences in fraction water available pores and total porosity for the films reflects the film morphology and differences in pore interconnection.

Novel eco-friendly spherical porous adsorbent fabricated from Pickering middle internal phase emulsions for removal of Pb(Ⅱ) and Cd(Ⅱ)

Spherical porous materials prepared from the emulsion template used in the water treatment have displayed a vast prospect, as the high surface area, abundant porous structure, convenient operation and excellent adsorption performance. But the tedious fabrication process, high consumption of organic solvent and surfactant limited the application widely. Herein, a facile and eco-friendly spherical porous adsorbent(SPA) is fabricated from the green surfactant-free(corn oil)-in-water Pickering medium internal phase emulsions(Pickering MIPEs) via the convenient ion crosslinking procedure. The Pickering MIPEs synergistically stabilized with the semi-coke(SC), which is the natural particle produced from the shale oil distillation, and sodium alginate(SA) has excellent storage and anti-coalescence stability. The as-prepared porous adsorbent possessed the abundant pore structure, which provided favorable conditions for effective mass transfer in adsorption, and could be tuned by varying the SA dosage. The saturation adsorption capacities of Pb(II) and Cd(II) can be achieved with 460.54 and 278.77 mg/g within 45 min at 25 ℃, respectively. Overall, this study supplied a viable and eco-friendly route for fabricating the spherical porous adsorbent with a tunable porous structure for heavy metal ion wastewater.