Metal-Organic Framework Nanocomposite Thin Films with Interfacial Bindings and Self-Standing Robustness for High Water Flux and Enhanced Ion Selectivity.

Metal-organic framework (MOF)-based materials are promising candidates for a range of separation applications. However, the fabrication of self-standing MOF-based thin films remains challenging. Herein, a facile solution casting strategy is developed for fabricating UiO-66 nanocomposite thin films (UiO66TFs) with thicknesses down to ∼400 nm. Nanosizing UiO-66 and incorporating sulfonated polysulfone additives render high dispersity and interfacial bindings between MOFs and polymer matrices, so UiO66TFs are more mechanically robust and thermally stable than their pure-polymer counterparts. Enhanced microporosity with sub-nanometer pore sizes of the self-standing membranes enables the direct translation of UiO-66-based sorption and ion-sieving properties, thus increasing water flux and separation performance (Na2SO4 rejection of 94-96%) under hydraulic pressure-driven processes and eliminating internal concentration polarization in osmotic pressure-driven processes. Enhanced separation performances are achieved with water/Na2SO4 permselectivity of 13.5 L g-1 and high osmotic water permeability up to 1.41 L m-2 h-1 bar-1, providing 3-fold higher water/Na2SO4 permselectivity and 56-fold-higher water flux than polymer membranes for forward osmosis.

Ion-Responsive Channels of Zwitterion-Carbon Nanotube Membrane for Rapid Water Permeation and Ultrahigh Mono-/Multivalent Ion Selectivity.

The rational combination of polymer matrix and nanostructured building blocks leads to the formation of composite membranes with unexpected capability of selectivity of monovalent electrolytes and water, which affords the feasibility to effeciently remove harmful ions and neutral molecules from the environment of concentrated salines. However, the multivalent ion rejection in salined water of routine nanocomposite membranes was less than 98% when ion strength is high, resulting in a poor ion selectivity far below the acceptable value. In this contribution, the ion-responsive membrane with zwitterion-carbon nanotube (ZCNT) entrances at the surface and nanochannels inside membrane has been proposed to obtain ultrahigh multivalent ion rejection. The mean effective pore diameter of ZCNT membrane was dedicated tuned from 1.24 to 0.54 nm with the rise in Na2SO4 concentration from 0 to 70 mol m(-3) as contrary to the conventional rejection drop in carbon nanotube (CNT) membrane. The ultrahigh selective permeabilities of monovalent anions against divalent anions of 93 and against glucose of 5.5 were obtained on ZCNT membrane, while such selectivities were only 20 and 1.6 for the pristine CNT membrane, respectively. The ZCNT membranes have potential applications in treatment of salined water with general NaCl concentration from 100 to 600 mol m(-3), which are widely applicable in desalination, food, and biological separation processes.

Three-dimensional ordered ZnO/Cu2O nanoheterojunctions for efficient metal-oxide solar cells.

Interface modulation for broad-band light trapping and efficient carrier collection has always been the research focus in solar cells, which provides the most effective way to achieve performance enhancement. In this work, solution-processed 3D ordered ZnO/Cu2O nanoheterojunctions, consisting of patterned n-ZnO nanorod arrays (NRAs) and p-Cu2O films, are elaborately designed and fabricated for the first time. By taking advantage of nanoheterojunctions with square patterned ZnO NRAs, solar cells demonstrate the maximum current density and efficiency of 9.89 mA cm(-2) and 1.52%, which are improved by 201% and 127%, respectively, compared to that of cells without pattern. Experimental analysis and theoretical simulation confirm that this exciting result originates from a more efficient broad-band light trapping and carrier collection of the 3D ordered ZnO/Cu2O nanoheterojunctions. Such 3D ordered nanostructures will have a great potential application for low-cost and all oxide solar energy conversion. Furthermore, the methodology applied in this work can be also generalized to rational design of other efficient nanodevices and nanosystems.

Electronic structure engineering of Cu2O film/ZnO nanorods array all-oxide p-n heterostructure for enhanced photoelectrochemical property and self-powered biosensing application.

We have engineered the electronic structure at the interface between Cu2O and ZnO nanorods (NRs) array, through adjusting the carrier concentration of Cu2O. The electrodeposition of Cu2O at pH 11 acquired the highest carrier concentration, resulting in the largest interfacial electric field between Cu2O and ZnO, which finally led to the highest separation efficiency of photogenerated charge carriers. The optimized Cu2O/ZnO NRs array p-n heterostructures exhibited enhanced PEC performance, such as elevated photocurrent and photoconversion efficiency, as well as excellent sensing performance for the sensitive detection of glutathione (GSH) in PBS buffer even at applied bias of 0 V which made the device self-powered. Besides, the favorable selectivity, high reproducibility and extremely wide detection range, make such heterostructure a promising candidate for PEC biosensing applications, probably for the extended field of PEC water splitting or other solar photovoltaic beacons.

The effect of chain structures on the crystallization behavior and membrane formation of poly(vinylidene fluoride) copolymers.

The crystallization behaviors of two copolymers of PVDF were studied, and the effect of copolymerized chains on the crystallization behavior was investigated. The results indicated that both copolymers had a lowered crystallization temperature and crystallinity. The crystallization rate was improved by the copolymer with symmetrical units in PVDF chains, but hindered by asymmetrical units, compared with the neat PVDF. The symmetrical units in PVDF chains favored the ß-crystals with fiber-like structures. According to the solubility parameter rule, methyl salicylate (MS) can be chosen as a diluent for PVDF copolymers. Both diluted systems had liquid-liquid (L-L) regions in the phase diagrams, which was due to the lowered crystallization temperature.

Design of efficient dye-sensitized solar cells with patterned ZnO-ZnS core-shell nanowire array photoanodes.

The fabrication of photoanodes with a high light-harvesting ability, direct electron pathway and low exciton recombination is a key challenge in dye-sensitized solar cells (DSSCs) today. In this paper, large-scale patterned ZnO-ZnS core-shell nanowire arrays (NWAs) are designed and fabricated as such photoanodes for the fist time. By using the NWA photoanodes with a hexagonal symmetry and FTO-Pt cathodes with an Al reflecting layer, the resulting DSSCs demonstrate a maxiumum efficiency of 2.09%, which is an improvement of 140% compared to the reference cells with line symmetry and no reflecting layer. This improvement is attributed to the enhanced light-harvesting ability of the patterned NWAs, as well as to the remarkable double absorption caused by the Al reflecting layer. Additionally, the ZnO core provides a direct electron pathway and the ZnS shell simultaneously reduces exciton recombination. This study shows an effective method to improve the performance of DSSCs which could be extended to other nanodevices and nanosystems.