Zeolitic Pickering Emulsifier with Intrinsic Amphiphilicity.

The formation of oil-in-water Pickering emulsions stabilized by lamellar zeolite MWW (International Zeolite Association, three-letters code) emulsifier without surface grafting is investigated. The crucial emulsification factors are the oligolayer morphology and amphiphilicity developed upon acidic treatment (NH4+ exchange/calcination, HNO3 treatment). In contrast with the readily available/abundant hydrophilic ≡Si-OH group in layer MWW, the lipophilicity generated by strong acid sites is another key to the success of emulsification. Hydrocarbon-strong acid site interaction is long known in petrochemistry and superacid research. However, to the best of our knowledge, this interaction was first introduced to gain lipophilicity in emulsion formation. Finally, the Pd-loaded acidic form of the MWW zeolite successfully stabilized the toluene/H2O emulsion system. The biphasic interfacial nitroarene hydrogenation demonstrated excellent catalytic performance. Overall, this work provided not only a new kind of intrinsic solid to emulsify the organic-aqueous biphase system but also a new mechanism to generate lipophilicity. Both are important for the applications and designs of Pickering emulsion materials.

Amphiphilic polymers facilitated solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for direct extraction and analysis of zearalenone and zearalanone in corn juice samples.

In this work, amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions are demonstrated to be capable of direct extracting zearalenone and zearalanone in samples consisting of an oil-water emulsion system. Under optimal conditions, the maximum adsorption capacities for zearalenone and zearalanone are 17.27 and 13.26 mg/g. The adsorption is mainly attributed to π-π interaction, hydrophobic interaction, and hydrogen-bonding interaction for zearalenone and zearalanone. The adsorption isotherms reveal that the adsorption of zearalenone and zearalanone on amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions follows Freundlich model with multilayer and heterogeneous adsorption due to the presence of multiple kinds of adsorption sites. The relative recoveries of the spiked zearalenone and zearalanone in corn juice samples range from 85% to 93% with relative standard deviations lower than 3.52%. The results manifest the high efficiency of amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions for the adsorption and separation of analytes in the oil-water emulsion system. This study provides a new perspective on adsorbent engineering for the adsorption application in heterogeneous media.

Wettability tunable metal organic framework functionalized high internal phase emulsion porous monoliths for fast solid-phase extraction and sensitive analysis of hydrophilic heterocyclic amines.

Surface wettability greatly influences the adsorptive, catalytic, and diffuse performances of a porous material. To realize the improved adsorption performance to hydrophilic heterocyclic amines (HAs), polymeric high internal phase emulsions (polyHIPEs) that can be tuned from hydrophobic to hydrophilic is synthesized by facilely regulating the amount of metal organic frameworks (MOFs). The water contact angle of the MOFs and polyHIPEs hybrids (MOFs@polyHIPEs) decreases from 133° to 0° as the amount of amide-modified MOFs increases from 0% to 10%. The hydrophilization of divinybenzene (DVB) based polyHIPEs by MOFs hybridization significantly enhances their adsorption performance and enables them to be suitable for the solid phase extraction (SPE) of hydrophilic HAs. Under the optimized conditions, the MOFs@polyHIPEs achieve adsorption capacities ranging from 42.89 to 86.71 µg/g for HAs through the π-π interaction and hydrogen bonding. The adsorption follows the pseudo-second-order kinetic model, and the nitrogen atoms in/on the imidazole ring are identified as the active adsorption sites for hydrogen bonding. This SPE method, along with HPLC-MS detection, provides detection limits of HAs as low as 0.00020-0.00040 ng/mL. This work offers a feasible strategy in tuning the surface wettability of polyHIPEs without post-modification to achieve high-efficiency enrichment and analysis of HAs.

Preparation of porous polymers based on high internal phase emulsion for enrichment of estrogens in urine.

In this work, graphene oxide-hybridized high internal emulsion polymers with crosslinking and open-cell structure was prepared and applied for separation and enrichment of estrogens. The prepared graphene oxide-hybridized high internal emulsion polymer monoliths had hydrophobicity, porosity and stability, which were just obtained by one step in-situ emulsion polymerization of 2-ethylhexyl acrylate, glycidyl methacrylate, and divinylbenzene after doping with graphene oxide. Benefit from the advantages of its unique character, the graphene oxide-hybridized high internal emulsion polymers monolith with low background pressure (85 kPa) and high mechanical strength could be applied for efficient separation for trace estrogens in urine. Under the optimized condition, trace estrogens, including estrone, estradiol, and diethylstilbestrol in urine, were detected by high-performance liquid chromatography, all the sample preparation process were carried out in 15 min, the recovery rate was ranged from 85.0 to 106.0% and the relative standard deviation was less than 4.

Assembly and application advancement of organic-functionalized graphene-based materials: A review.

Owing to the remarkable physicochemical properties such as hydrophobicity, conductivity, elasticity, and light weight, graphene-based materials have emerged as one of the most appealing carbon allotropes in materials science and chemical engineering. Unfortunately, pristine graphene materials lack functional groups for further modification, severely hindering their practical applications. To render graphene materials with special characters for different applications, graphene oxide or reduced graphene oxide has been functionalized with different organic agents and assembled together, via covalent binding and various noncovalent forces such as π-π interaction, electrostatic interaction, and hydrogen bonding. In this review, we briefly discuss the state-of-the-art synthetic strategies and properties of organic-functionalized graphene-based materials, and then, present the prospective applications of organic-functionalized graphene-based materials in sample preparation.

A porous carbon absorbent based on high internal phase emulsion for separation and enrichment of trifluralin from soil.

A porous carbon absorbent was obtained by using high internal phase emulsions (HIPEs) polymerization followed by high temperature carbonization under nitrogen protection. Graphene oxide (GO) and silica nanoparticles were doped into the HIPEs to enhance the adsorption ability and reusability. Fourier infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were used for characterization and several parameters of separation and enrichment of trifluralin. The results showed that a hyper-crosslink framework material was obtained with abundant porous (pore size of about 30 µm) and a good adsorption and separation efficiency. The adsorption rate was up to 100% and trifluralin was completely eluted from the absorbent by 2.0 mL of an acetic acid-acetonitrile mixture. Graphical abstractSchematic representation of synthesis of porous carbon absorbent by GO and SiO2 doped HIPEs.POLYHIPES-GO&SiO2: Polymerized High Internal Phase Emulsions doped with Silica and Graphene oxide.

Novel porous carbon composites derived from a graphene-modified high-internal- phase emulsion for highly efficient separation and enrichment of triazine herbicides.

In this study, novel porous carbon composites were successfully prepared with graphene-modified high-internal-phase emulsions (HIPEs) via a simple process of polymerization followed by carbonization. The morphology of the macroporous composites was observed and the verification of structural and functional groups were verified by scanning electron microscopy (SEM), and other characterizations techniques including Fourier transform infrared (FI-IR), X-ray photoelectron spectroscopy (XPS) spectra and Raman spectroscopy. The prepared porous carbon composites were applied to farmland water for the simultaneous adsorption of triazine herbicides and the conditions of extraction and desorption were optimized. Due to the π-π interaction and hydrophobic interaction between triazine herbicides and carbon composites, the maximum adsorption capacity of simazine, prometon and prometryn were 33.4, 34.5 and 33.8 µg g-1, respectively. Adsorption and desorption of triazine herbicides can be achieved in 10 min, and high-speed mass transfer was observed. The calibration curves of three triazine herbicides were linear (R2 ≥0.9996) in the range from 25.0 to 500.0 ng mL-1. The LOD of three triazine herbicides by using the proposed SPE-HPLC-DAD method were 2.5-5.6 ng mL-1. All the results suggest that these materials may be useful for more efficient hazardous residue separations.