Cover illustration
The separation of rare earth elements is particularly difficult due to their similar physicochemical properties. Based on the differences of ionic magnetic moment via quasi-liquid strategy, two typical paramagnetic and diamagnetic rare-earth ions, Er3+ and Y3+, are separated in the external magnetic field. The paramagnetic Er3+ in ionic liquid is rapidly attracted to the permanent magnet and gathered around the magnet finally, while the diamagnetic Y3+ has no response with th[Detail] ...
Poly(ether−ether ketone) (PEEK) is a linear aromatic macromolecule, which can form semi-crystalline aggregative status, allowing PEEK materials to have strong environment tolerance and excellent physicochemical properties. PEEK materials have become a promising alternative to fabricate particular membranes used in extreme conditions. In the past few decades, many researches and evolutions have emerged in membrane fabrication with PEEK materials and its applications for treating organic solvents and their mixtures; however, there are little systematic and comprehensive literature to summarize fabrication approaches, compile applications, and elaborate PEEK property-structure relationship. In this review, the main approaches to fabricate PEEK-based membranes are illustrated concretely, including conventional thermal-induced and non-solvent-induced phase separation, and novel chemical-induced crystallization; the representative applications in ultrafiltration, nanofiltration and membrane contactor containing organic solvents are demonstrated systematically. Meanwhile, the mechanism to tune PEEK solubility in solvents, which can be achieved by altering monomers in synthesis processes or changing membrane preparation routes, is deeply analyzed. Moreover, the existing problems and the future prospects are also discussed. This review provides positive guidance for designing and fabricating membranes using PEEK and its derivative materials for task-specific applications in harsh conditions.
Emulsion systems are widely applied in agriculture, food, cosmetic, pharmaceutical and biomedical industries. Ultrasound has attracted much attention in emulsion preparation, especially for nanoemulsion, due to its advantages of being eco-friendly, cost-effective and energy-efficient. This review provides an overview for readers to the area of ultrasonic emulsification technology. It briefly introduces and summarizes knowledge of ultrasonic emulsification, including emulsion characteristics, acoustic cavitation, emulsification mechanism, ultrasonic devices and applications. The combination of microfluidics and ultrasound is highlighted with huge advantages in controlling cavitation phenomena and emulsification intensification. A novel scale of dμC0.6/μD0.33−EV is proposed to be able to compare the energy efficiency of emulsion preparation in different devices.
The separation of rare earth elements is particularly difficult due to their similar physicochemical properties. Based on the tiny differences of ionic radius, solvent extraction has been developed as the “mass method” in industry with hundreds of stages, extremely intensive chemical consumption and large capital investments. The differences of the ionic magnetic moment among rare earths are greater than that of ionic radius. Herein, a novel method based on the large ionic magnetic moment differences of rare earth elements was proposed to promote the separation efficiency. Rare earths were firstly dissolved in the ionic liquid, then the ordering degree of them was improved with the Z-bond effect, and finally the magnetic moment differences between paramagnetic and diamagnetic rare earths in quasi-liquid system were enhanced. Taking the separation of Er/Y, Ho/Y and Er/Ho as examples, the results showed that Er(III) and Ho(III) containing ionic liquids had obvious magnetic response, while ionic liquids containing Y(III) had no response. The separation factors of Er/Y and Ho/Y were achieved at 9.0 and 28.82, respectively. Magnetic separation via quasi-liquid system strategy provides a possibility of the novel, green, and efficient method for rare earth separation.
The application of iron–carbon (Fe–C) micro-electrolysis to wastewater treatment is limited by the passivation potential of the Fe–C packing. In order to address this problem, high-gravity intensified Fe–C micro-electrolysis was proposed in this study for degradation of dinitrotoluene wastewater in a rotating packed bed (RPB) using commercial Fe–C particles as the packing. The effects of reaction time, high-gravity factor, liquid flow rate and initial solution pH were investigated. The degradation intermediates were determined by gas chromatography-mass spectrometry, and the possible degradation pathways of nitro compounds by Fe–C micro-electrolysis in RPB were also proposed. It is found that under optimal conditions, the removal rate of nitro compounds reaches 68.4% at 100 min. The removal rate is maintained at approximately 68% after 4 cycles in RPB, but it is decreased substantially from 57.9% to 36.8% in a stirred tank reactor. This is because RPB can increase the specific surface area and the renewal of the liquid–solid interface, and as a result the degradation efficiency of Fe–C micro-electrolysis is improved and the active sites on the Fe–C surface can be regenerated for continuous use. In conclusion, high-gravity intensified Fe–C micro-electrolysis can weaken the passivation of Fe–C particles and extend their service life.
The increasing applications of seawater desalination technology have led to the wide usage of polyamide reverse osmosis membranes, resulting in a large number of wasted reverse osmosis membranes. In this work, the base nonwoven layer of the wasted reverse osmosis membrane was successfully modified into the hydrophobic membrane via surface deposition strategy including TiO2 and 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS), respectively. Various techniques were applied to characterize the obtained membranes, which were then used to separate the oil–water system. The optimally modified membrane displayed good hydrophobicity with a contact angle of 135.2° ± 0.3°, and its oil–water separation performance was as high as 97.8%. After 20 recycle tests, the oil–water separation performance remained more than 96%, which was attributed to the film adhesion of the anchored TiO2 and PFOTS layer on the surface. This work might provide a new avenue for recycling the wasted reverse osmosis membrane used in oily wastewater purification.
Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties. Here, remarkable acetylene/carbon dioxide separation featuring a high dynamic breakthrough capacity for acetylene (4.3 mmol·g–1) as well as an ultralow acetylene regeneration energy (29.5 kJ·mol–1) was achieved with the novel TiF62–-pillared material ZU-100 (TIFSIX-bpy-Ni). Construction of a pore structure with abundant TiF62– anion sites and pores with appropriate sizes enabled formation of acetylene clusters through hydrogen bonds and intermolecular interactions, which afforded a high acetylene capacity (8.3 mmol·g–1) and high acetylene/carbon dioxide uptake ratio (1.9) at 298 K and 1 bar. Moreover, the NbO52– anion-pillared material ZU-61 investigated for separation of acetylene/carbon dioxide. In addition, breakthrough experiments were also conducted to further confirm the excellent dynamic acetylene/carbon dioxide separation performance of ZU-100.
The number of active components and their dispersion degree are two key factors affecting the performance of adsorbents. Here, we report a simple but efficient strategy for dispersing active components by using a confined space, which is formed by mesoporous silica walls and templates in the as-prepared SBA-15 (AS). Such a confined space does not exist in the conventional support, calcined SBA-15, which does not contain a template. The Cu and Zn precursors were introduced to the confined space in the AS and were converted to CuO and ZnO during calcination, during which the template was also removed. The results show that up to 5 mmol·g–1 of CuO and ZnO can be well dispersed; however, severe aggregation of both oxides takes place in the sample derived from the calcined SBA-15 with the same loading. Confined space in the AS and the strong interactions caused by the abundant hydroxyl groups are responsible for the dispersion of CuO and ZnO. The bimetallic materials were employed for the adsorptive separation of propene and propane. The samples prepared from the as-prepared SBA-15 showed superior performance to their counterparts from the calcined SBA-15 in terms of both adsorption capacity of propene and selectivity for propene/propane.
Although metal–organic frameworks offer a new platform for developing versatile sorption materials, yet coordinating the functionality, structure and component of these materials remains a great challenge. It depends on a comprehensive knowledge of a “real sorption mechanism”. Herein, a ternary mechanism for U(VI) uptake in metal–organic frameworks was reported. Analogous MIL-100s (Al, Fe, Cr) were prepared and studied for their ability to sequestrate U(VI) from aqueous solutions. As a result, MIL-100(Al) performed the best among the tested materials, and MIL-100(Cr) performed the worst. The nuclear magnetic resonance technique combined with energy-dispersive X-ray spectroscopy and zeta potential measurement reveal that U(VI) uptake in the three metal–organic frameworks involves different mechanisms. Specifically, hydrated uranyl ions form outer-sphere complexes in the surface of MIL-100s (Al, Fe) by exchanging with hydrogen ions of terminal hydroxyl groups (Al-OH2, Fe-OH2), and/or, hydrated uranyl ions are bound directly to Al(III) center in MIL-100(Al) through a strong inner-sphere coordination. For MIL-100(Cr), however, the U(VI) uptake is attributed to electrostatic attraction. Besides, the sorption mechanism is also pH and ionic strength dependent. The present study suggests that changing metal center of metal–organic frameworks and sorption conditions alters sorption mechanism, which helps to construct effective metal–organic frameworks-based sorbents for water purification.
Microcapsules are versatile delivery vehicles and widely used in various areas. Generally, microcapsules with solid shells lack selective permeation and only exhibit a simple release mode. Here, we use ultrathin-shell water-in-oil-in-water double emulsions as templates and design porous ultrathin-shell microcapsules for selective permeation and multiple stimuli-triggered release. After preparation of double emulsions by microfluidic devices, negatively charged shellac nanoparticles dispersed in the inner water core electrostatically complex with positively charged telechelic α,ω-diamino functionalized polydimethylsiloxane polymers dissolved in the middle oil shell at the water/oil interface, thus forming a porous shell of shellac nanoparticles cross-linked by telechelic polymers. Subsequently, the double emulsions become porous microcapsules upon evaporation of the middle oil phase. The porous ultrathin-shell microcapsules exhibit excellent properties, including tunable size, selective permeation and stimuli-triggered release. Small molecules or particles can diffuse across the shell, while large molecules or particles are encapsulated in the core, and release of the encapsulated cargos can be triggered by osmotic shock or a pH change. Due to their unique performance, porous ultrathin-shell microcapsules present promising platforms for various applications, such as drug delivery.
Two-dimensional nanosheets are highly effective tougheners for vinyl ester resins. The toughening effect is related to the high specific surface area and unique two-dimensional planar structure of the nanosheets. In this study, a coupling agent γ-(2,3-epoxypropoxy) propytrimethoxysilane (Kh-560) was used to modify MXene nanosheets (M-MXene) for use in toughening vinyl ester resin. The mechanical properties, including the tensile strength, flexural strength, Young’s modulus and elongation, of neat vinyl ester resin and vinyl ester resin modified with MXene and M-MXene were investigated. The results showed that modification significantly improved the mechanical properties of the vinyl ester resin. The tensile and flexural strengths of the MXene-nanosheet-modified vinyl ester resin were 27.20% and 25.32% higher, respectively, than those of the neat vinyl ester resin. The coupling agent improved the interfacial compatibility between the MXene nanosheets and vinyl ester resin, which resulted in the tensile and flexural strengths of the M-MXene-nanosheet-modified vinyl ester resin being 52.57% and 54.60% higher, respectively, than those of the neat vinyl ester resin for a loading quantity of nanosheets of only 0.04 wt %, which is economically viable. The main mechanisms by which the nanosheets toughen the resin are crack deflection and crack pinning.
For decades, distiller waste and CO2 were not the first choice for production of high valued products. Here, CaCO3 hollow microspheres, a high-value product was synthesized from such a reaction system. The synthetic methods, the formation mechanism and operational cost were discussed. When 2.5 L·min–1·L–1 CO2 was flowed into distiller waste (pH = 11.4), spheres with 4–13 μm diameters and about 2 μm shell thickness were obtained. It is found that there is a transformation of CaCO3 particles from solid-cubic nuclei to hollow spheres. Firstly, the Ca(OH)2 in the distiller waste stimulated the nucleation of calcite with a non-template effect and further maintained the calcite form and prevented the formation of vaterite. Therefore, in absence of auxiliaries, the formation of hollow structures mainly depended on the growth and aging of CaCO3. Studies on the crystal morphology and its changes during the growth process point to the inside–out Ostwald effect in the formation of hollow spheres. Change in chemical properties of the bulk solution caused changes in interfacial tension and interfacial energy, which promoted the morphological transformation of CaCO3 particles from cubic calcite to spherical clusters. Finally, the flow process for absorption of CO2 by distiller waste was designed and found profitable.
Droplet impacting on the stainless steel wire mesh is very common in chemical devices, like a rotating packed bed. Surface wettability of wire mesh significantly affects the liquid flow pattern and liquid dispersion performance. However, the effect of surface wettability on the impaction phenomena at microscale such as liquid film is still unknown. In this work, the dynamic behavior of liquid film on the surface of wire mesh was analyzed by computational fluid dynamics simulation. The dynamic behavior of liquid film on the surface of wire mesh can be divided into the following three steps: (1) spreading step; (2) shrinkage process; (3) stabilizing or disappearing step. Effects of surface wettability, as well as operating conditions, on wetting area and liquid film thickness were studied. Compared to the hydrophilic wire mesh, the final wetting area of hydrophobic wire mesh is zero in most cases. The average liquid film thickness on the surface of hydrophilic wire mesh is 30.02–77.29 μm, and that of hydrophobic wire mesh is 41.76–237.37 μm. This work provided a basic understanding of liquid film flow at microscale on the surface with various surface wettabilities, which can be guiding the packing optimization and design.
Bubbles and foams are ubiquitous in daily life and industrial processes. Studying their dynamic behaviors is of key importance for foam manufacturing processes in food packaging, cosmetics and pharmaceuticals. Bare bubbles are inherently fragile and transient; enhancing their robustness and shelf lives is an ongoing challenge. Their rupture can be attributed to liquid evaporation, thin film drainage and the nuclei of environmental dust. Inspired by particle-stabilized interfaces in Pickering emulsions, armored bubbles and liquid marble, bubbles are protected by an enclosed particle-entrapping liquid thin film, and the resultant soft object is termed gas marble. The gas marble exhibits mechanical strength orders of magnitude higher than that of soap bubbles when subjected to overpressure and underpressure, owing to the compact particle monolayer straddling the surface liquid film. By using a water-absorbent glycerol solution, the resulting gas marble can persist for 465 d in normal atmospheric settings. This particle-stabilizing approach not only has practical implications for foam manufacturing processes but also can inspire the new design and fabrication of functional biomaterials and biomedicines.