Enhancing Demulsification Performance for Oil-Water Separation through Encapsulating Ionic Liquids in the Pore of MIL-100(Fe).

Emulsion poses a greater challenge for the remediation of oily wastewater, which can be effectively resolved by the metal-organic framework of MIL-100(Fe). The formula Fe3O(H2O)2(OH) (BTC)2 pronounces that MIL-100(Fe) suffers from an intrinsic defect of less charged atoms, which limits its demulsification performance for oil-water separation. Herein, cations of the ionic liquid (1-allyl-3-methylimidazolium, Amim+) were encapsulated in the micropore of MIL-100(Fe) in situ to increase the positive charge density of MIL-100(Fe). Zeta potential demonstrated that the encapsulation of Amim+ increased the positive charge amount of MIL-100(Fe). N2 probe isothermal adsorption/desorption and spectral measurements (X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflection spectroscopy, and attenuated total-reflectance infrared spectroscopy) revealed the host-guest interactions of π···Fe complexation and π···cation electrostatic attraction between Amim+ and MIL-100(Fe) for the composite materials. Amim+ encapsulation greatly enhanced the demulsification performance of MIL-100(Fe) for oil-in-water (O/W) emulsion stabilized by sodium dodecyl sulfate. Amim+-encapsulated MIL-100(Fe) with an Amim+/Fe3+ molar ratio of 1:1 [Amim@MIL-100(Fe)-3:3] showed a demulsification efficiency (DE) of 94% within 30 s, compared with MIL-100(Fe) within 30 min. The maximum DE of Amim@MIL-100(Fe)-3:3 was found to be more than 98% within 5 min. The DE lost by MIL-100(Fe) at the third run decreased from 36 to 17% after encapsulating Amim+. The analysis of surface charge and interfacial tension implied a demulsification mechanism of capturing-fusion, which could be promoted by the greater electrostatic attraction. Finally, the role of Amim+ on the outstanding demulsification performance by Amim+-encapsulated MIL-100(Fe) could be explained by the enhanced nonbonded interaction of electrostatic attraction and van der Waals based on the molecular dynamics simulation.

Graphene quantum dots to enhance the photocatalytic hydrogen evolution efficiency of anatase TiO2 with exposed {001} facet.

Hydrogen evolution through photocatalysis is promising with respect to the environmental problems and challenges of energy shortage that we encounter today. In this paper, we have combined graphene quantum dots (GQDs) and {001} faceted anatase TiO2 (with an exposed percentage of 65-75%) together for effective photocatalytic hydrogen evolution. A series of characterizations including X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy and UV-visible absorption spectroscopy have been carried out to study the structure of the as-prepared GQDs/{001}TiO2 composite. It turns out that GQDs could be effectively decorated on {001}TiO2 sheet without changing its intrinsic structure. With an optimum loading amount of GQDs (0.5 wt% to {001}TiO2), GQDs/{001}TiO2 exhibits a hydrogen evolution efficiency 8 times higher than that of bare {001}TiO2, which is a significantly more obvious improvement than many other photocatalytic systems relevant to GQDs and TiO2 hybrids. In addition, GQDs/{001}TiO2 could stand long-term photocatalytic experiments. Photocurrent tests show that such an improvement of the photocatalytic efficiency over GQDs/{001}TiO2 may originate from a higher charge separation efficiency. The present study could offer reference for the construction of photocatalytic hydrogen evolution systems with low cost and long term stability.

Surface-Terminated Hydroxyl Groups for Deciphering the Facet-Dependent Photocatalysis of Anatase TiO2.

Understanding the relation between a crystal facet and photocatalytic performance is of great importance for the development of effective catalysts. In this work, we focus on anatase TiO2 with controllable exposed facets toward photocatalytic hydrogen evolution by water splitting. By combining temperature-programmed desorption (TPD) and diffuse reflectance infrared spectroscopy (DRIFTS), we obtain that the adsorption of hydroxyl groups and the photo-driven breaking of hydroxyl groups depend strongly on the exposed facets. As a result, the higher catalytic hydrogen evolution activity of TiO2 enclosed with (101) facets than that of (001) facets should be ascribed to the more favorable depletion of hydroxyl groups. Moreover, graphene quantum dots (GQDs) with rich surface functional groups are deliberately deposited on the TiO2 surface. The determination of the states and dynamics of surface hydroxyl groups suggests that GQDs facilitate the reaction of hydroxyl groups on (001)TiO2, thus leading to the activity enhancement. By contrast, the already active (101)TiO2 become apparently less efficient after GQD deposition due to the restricted reaction of hydroxyl groups. Overall, our findings not only provide a unique guidance for understanding the crystal-plane-dependent photocatalysis but also present a powerful approach by which to tailor the photocatalytic performance.

Surface Charge Regulation of MIL-100(Fe) by Anion Exchange for Demulsifying the Cationic Surfactant-Stabilized O/W Emulsion.

Demulsifying ionic surfactant-stabilized emulsions remains an emerging issue due to the stringent electrostatic barriers. In this work, a phosphate-mediated anion exchange strategy was proposed to fabricate a metal-organic framework, MIL-100(Fe), with adjustable surface charge for effective demulsification toward a cationic surfactant-stabilized emulsion. By adjusting the pH of the phosphate precursor solution, the surface charge of MIL-100(Fe) can be fine-tuned. At pH 3.0, the phosphate-exchanged MIL-100(Fe) with the zeta potential decreasing from 21.4 to 6.1 mV exhibited a significant enhancement of the demulsification efficiency (DE) from 35 to 91%. Further elevating the pH to 9.0 results in the zeta potential of the phosphate-exchanged MIL-100(Fe) to be reversed to -2.0 mV, and the DE can be optimized to 96% within 5 min. The demulsification mechanism was systematically explored based on the zeta potential, distribution of the surfactant, viscoelastic modulus evaluation, and morphological characterization of the emulsion in combination with monitoring of the dynamics process of demulsification. It was found that the phosphate-exchanged MIL-100(Fe) captured by the emulsion can lead to the release of the surfactant and heterogenization of the interfacial film, causing the elasticity of the emulsion to decrease and the irreversible deformation of emulsion droplets. Consequently, the destabilized emulsion could be subjected to the effective demulsification either by the fusion pathway mediated by the phosphate-exchanged MIL-100(Fe) or direct rupture. This work emphasized a facile and promising approach to deal with the cationic surfactant-emulsified oily wastewater and disclosed the fundamental demulsification process.

Zinc ions modified InP quantum dots for enhanced photocatalytic hydrogen evolution from hydrogen sulfide.

Through direct addition of inorganic zinc ions into the solution of indium phosphide quantum dots (InP QDs) at ambient environment, we here present a facile but effective method to modify InP QDs for photocatalytic hydrogen evolution from hydrogen sulfide (H2S). X-ray diffraction patterns and transmission electron microscopic images demonstrate that zinc ions have no significant influence on the crystal structure and morphology of InP QDs, while X-ray photoemission spectra and UV-Vis diffuse and reflectance spectra indicate that zinc ions mainly adsorbed on the surface of InP QDs. Photocatalytic results show the average hydrogen evolution rate has been enhanced to 2.9 times after modification and H2S has indeed involves in the hydrogen evolution process. Steady-state and transient photoluminescence spectra prove that zinc ions could effectively eliminate the surface traps on InP QDs, which is crucial to suppress the recombination of charge carriers. In addition, the electrostatic interaction between zinc ions and the surface sulfide from InP QDs could mitigate the repulsion between QDs and sulfide/hydrosulfide, which may promote the surface oxidative reaction during photocatalysis. This work avoids the traditional harsh and complicated operations required for surface passivation of QDs, which offers a convenient way for optimization of QDs in photocatalysis.

CdSe Quantum Dots/g-C3N4 Heterostructure for Efficient H2 Production under Visible Light Irradiation.

Novel photocatalysts -CdSe quantum dots (QDs)/g-C3N4- were successfully constructed. The structure, chemical composition, and optical properties of the prepared samples were investigated via a series of characterization techniques. The results indicated that CdSe QDs/g-C3N4 photocatalysts exhibited remarkably enhanced photocatalytic activity for visible-light-induced H2 evolution compared to pristine g-C3N4 and CdSe QDs and addition of 13.6 wt % CdSe QDs into the composite photocatalyst generated the highest H2 production rate. The enhanced photocatalytic performance of CdSe QDs/g-C3N4 can be attributed to the synergistic effects of excellent visible absorption and high charge separation efficiency from the heterostructure. This work could not only provide a facile method to fabricate semiconductor QDs-modified g-C3N4 photocatalysts but also contribute to the design for heterostructures.

Photostability and Photodegradation Processes in Colloidal CsPbI3 Perovskite Quantum Dots.

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.