Covalent Organic Framework-derived Composite Membranes for Water Treatment.

Water treatment has experienced a surge in the adoption of membrane separation technology. Covalent organic frameworks (COFs), a class of metal-free and open-framework materials, have emerged as potential membrane materials owing to their interconnected periodic porosity, tunability, and chemical stability. However, the challenges associated with processing COF powders into self-standing membranes have spurred the emergence of COF composite membranes. This review article highlights the rationale behind developing COF composite membranes and their categories, including mixed matrix membranes (MMMs) and thin film composite (TFC) membranes. The common fabrication techniques of each category are presented. In addition, the influence of COF additives on the performance of the resultant composite membranes is systematically discussed, with a focus on the recent progress in applying COF composite membranes in the separation of different categories of water pollutants, including organic ions/molecules, toxic solvents, proteins, toxic heavy metals, and radionuclides.

Effects of top electrode material in hafnium-oxide-based memristive systems on highly-doped Si.

This work provides useful insights into the development of HfO2-based memristive systems with a p-type silicon bottom electrode that are compatible with the complementary metal-oxide-semiconductor technology. The results obtained reveal the importance of the top electrode selection to achieve unique device characteristics. The Ag/HfO2/Si devices have exhibited a larger memory window and self-compliance characteristics. On the other hand, the Au/HfO2/Si devices have displayed substantial cycle-to-cycle variation in the ON-state conductance. These device characteristics can be used as an indicator for the design of resistive-switching devices in various scenes such as, memory, security, and sensing. The current-voltage (I-V) characteristics of Ag/HfO2/Si and Au/HfO2/Si devices under positive and negative bias conditions have provided valuable information on the ON and OFF states of the devices and the underlying resistive switching mechanisms. Repeatable, low-power, and forming-free bipolar resistive switching is obtained with both device structures, with the Au/HfO2/Si devices displaying a poorer device-to-device reproducibility. Furthermore, the Au/HfO2/Si devices have exhibited N-type negative differential resistance (NDR), suggesting Joule-heating activated migration of oxygen vacancies to be responsible for the SET process in the unstable unipolar mode.

Bipolar Cu/HfO2/p++ Si Memristors by Sol-Gel Spin Coating Method and Their Application to Environmental Sensing.

In this paper, the memristive switching behavior of Cu/ HfO2/p++ Si devices fabricated by an organic-polymer-assisted sol-gel spin-coating method, coupled with post-annealing and shadow-mask metal sputtering steps, is examined. HfO2 layers of about 190 nm and 80 nm, are established using cost-effective spin-coating method, at deposition speeds of 2000 and 4000 rotations per minute (RPM), respectively. For two types of devices, the memristive characteristics (Von, Ion, and Vreset) and device-to-device electrical repeatability are primarily discussed in correlation with the oxide layer uniformity and thickness. The devices presented in this work exhibit an electroforming free and bipolar memory-resistive switching behavior that is typical of an Electrochemical Metallization (ECM) I-V fingerprint. The sample devices deposited at 4000 RPM generally show less variation in electrical performance parameters compared to those prepared at halved spin-coating speed. Typically, the samples prepared at 4000 RPM (n = 8) display a mean switching voltage Von of 3.0 V (±0.3) and mean reset voltage Vreset of -1.1 V (±0.5) over 50 consecutive sweep cycles. These devices exhibit a large Roff/Ron window (up to 104), and sufficient electrical endurance and retention properties to be further examined for radiation sensing. As they exhibit less statistical uncertainty compared to the samples fabricated at 2000 RPM, the devices prepared at 4000 RPM are tested for the detection of soft gamma rays (emitted from low-activity Cs-137 and Am-241 radioactive sources), by assessing the variation in the on-state resistance value upon exposure. The analysis of the probability distributions of the logarithmic Ron values measured over repeated ON-OFF cycles, before, during and after exposing the devices to radiation, demonstrate a statistical difference. These results pave the way for the fabrication and development of cost-effective soft-gamma ray detectors.

A design of experiment approach to the sol­gel synthesis of titania monoliths for chromatographic applications.

A design of experiement approach is described for the optimization of the microscopic morphology of macro-mesoporous titania monoliths that were elaborated for the chromatographic enrichment of phosphorylated compounds. The monolithic titania gels were formed via an alkoxy-derived sol-gel route in association with a phase separation mechanism. The synthesis was performed at mild temperatures of gelation using starting mixtures of titanium n-propoxide, hydrochloric acid, N-methylformamide, water, and poly (ethylene oxide). The gelation temperature and the chemical compositions of N-methylformamide, water, and poly (ethylene oxide) were chosen as the most relevant experimental factors of the sol­gel process. Using the sizes of the skeletons and macropores as morphological descriptors of the dried porous monoliths, the statistical analyses simultaneously revealed the effects and interactions between the different factors. Crack-free TiO2 monolithic rods of 8 to 10 cm long with well-defined co-continuous macropores and micro-structured skeletons were obtained after selection of the sol-gel parameters and optimization of the drying and heat-treatment steps of the gels. The bimodal texture of the rods exhibited macropores of 1.5 µm and mesopores centered at 5.2 nm with a total surface area of 140 m2 g(-1). The ability of the macro-mesoporous titania rods to selectively bind phosphorylated compounds was demonstrated for O-phosphoamino acids (P-Ser, P-Thr, P-Tyr).

Retention of ß blockers on native titania stationary phase.

In recent years, metal oxides such as titania have been commercially available as chromatographic beds that can potentially be used to achieve novel separations of polar compounds. For example ß blockers, which are more often encountered in environmental sciences, have a wide range of polarity, and their basic character leads to difficult sample treatment and separation on conventional silica-based sorbents. The contribution of titania to the selective analysis of nine ß blockers was evaluated in terms of retention mechanisms observed in hydrophilic interaction LC using acetonitrile/water mobile phases with various additives. The mobile phase additives enabled to control the ß blocker charge as well as the titania surface charge. Depending on their respective ionic state, various retention mechanisms were identified at low water contents (<40%), including mainly adsorption mixed with hydrophilic interaction LC partition, ion exchange and ion exclusion. An unexpected retention was also observed for high water content and high pH, changing the selectivity of the support.

Capillary monolithic titania column for miniaturized liquid chromatography and extraction of organo-phosphorous compounds.

A new sol-gel protocol was designed and optimized to produce titanium-dioxide-based columns within confined geometries such as monolithic capillary columns and porous-layer open-tubular columns. A surface pre-treatment of the capillary enabled an efficient anchorage of the monolith to the silica capillary wall during the synthesis. The monolith was further synthesized from a solution containing titanium n-propoxide, hydrochloric acid, N-methylformamide, water, and poly(ethylene oxide) as pore template. The chromatographic application of capillary titania-based columns was demonstrated with the separation of a set of phosphorylated nucleotides as probe molecules using aqueous normal-phase liquid chromatography conditions. Capillary titania monoliths offered a compromise between the high permeability and the important loading capacity needed to potentially achieve miniaturized sample preparations. The specificity of the miniaturized titania monolithic support is illustrated with the specific enrichment of 5'-adenosine mono-phosphate. The monolithic column offered a ten times higher loading capacity of 5'-adenosine mono-phosphate compared with that of the capillary titania porous-layer open-tubular geometry.