Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO2 /N2 Selectivity.

Hypercrosslinked polymers (HCPs) are widely used in ion exchange, water purification, and gas separation. However, HCP synthesis typically requires hazardous halogenated solvents e. g., dichloroethane, dichloromethane and chloroform which are toxic to human health and environment. Herein we hypothesize that the use of halogenated solvents in HCP synthesis can be overcome with deep eutectic solvents (DES) comprising metal halides-FeCl3 , ZnCl2 that can act as both the solvent hydrogen bond donor and catalyst for polymer crosslinking via Friedel Crafts alkylation. We validated our hypothesis by synthesizing HCPs in DESs via internal and external crosslinking strategies. [ChCl][ZnCl2 ]2 and [ChCl][FeCl3 ]2 was more suitable for internal and external hypercrosslinking, respectively. The specific surface areas of HCPs synthesized in DES were 20-60 % lower than those from halogenated solvents, but their CO2 /N2 selectivities were up to 453 % higher (CO2 /N2 selectivity of poly-α,α'-dichloro-p-xylene synthesized in [ChCl][ZnCl2 ]2 via internal crosslinking reached a value of 105). This was attributed to the narrower pore size distributions of HCPs synthesized in DESs.

Recent Advances in UV-Cured Encapsulation for Stable and Durable Perovskite Solar Cell Devices.

The stability and durability of perovskite solar cells (PSCs) are two main challenges retarding their industrial commercialization. The encapsulation of PSCs is a critical process that improves the stability of PSC devices for practical applications, and intrinsic stability improvement relies on materials optimization. Among all encapsulation materials, UV-curable resins are promising materials for PSC encapsulation due to their short curing time, low shrinkage, and good adhesion to various substrates. In this review, the requirements for PSC encapsulation materials and the advantages of UV-curable resins are firstly critically assessed based on a discussion of the PSC degradation mechanism. Recent advances in improving the encapsulation performance are reviewed from the perspectives of molecular modification, encapsulation materials, and corresponding architecture design while highlighting excellent representative works. Finally, the concluding remarks summarize promising research directions and remaining challenges for the use of UV-curable resins in encapsulation. Potential solutions to current challenges are proposed to inspire future work devoted to transitioning PSCs from the lab to practical application.

Enhanced plasmonic photocatalytic performance of C doped TiN nanocrystals through ultrathin carbon layers.

Carbon-doped TiN nanoparticles on an ultrathin carbon layer, were successfully used for photocatalytic dye degradation synthesised by a simple calcination process. The resulting catalyst exhibited remarkable plasmonic photocatalytic performance under visible light irradiation. In comparison with benchmark rutile TiO2 and g-C3N4/TiO2 heterostructure catalysts, the first-order reaction rate constant of the developed catalyst improved approximately 34.2 and 6.5 times, respectively. The doping concentration of carbon and the crystal size of TiN nanoparticles, predominantly influenced by the amount of urea and calcination temperature, were identified as crucial factors governing the plasmonic photocatalytic activity. Density functional theory (DFT) calculations indicated that the introduction of carbon-sp bands into the TiN band structure promoted interband excitation of electrons and facilitated the generation of hotter holes, thereby enhancing the degradation of dyes and ultimately contributing to the superior photocatalytic activity observed.

Temperature-Derived Purification of Gold Nano-Bipyramids for Colorimetric Detection of Tannic Acid.

Gold nanostructures have attracted broad attention. Among various nanostructures, gold nanobipyramids have shown great potential in sensing, biomedicine, environmental protection, chemical catalysis, and optics due to their unique physical and optical properties and ease of chemical functionalization. Compared with other plasmonic nanostructures, gold nanobipyramids possess narrow optical resonances, stronger plasmonic local field enhancement, and size- and shape-dependent surface plasmon resonance. However, the synthesis and purification of homogeneous gold nanobipyramids are very challenging. The gold nanobipyramids synthesized via the commonly used seed-mediated growth method have low yields and are often coproduced with spherical nanoparticles. In this study, we reported a temperature-derived purification method for the isolation of gold bipyramids. In the presence of salt, by altering the temperature of the solution, large gold bipyramids can be separated from small spherical nanoparticles. As a result, a yield of as high as 97% gold nanobipyramids can be achieved through a single round of purification, and correspondingly, the ratio between the longitudinal surface plasmon resonance (LSPR) and transverse SPR intensity significantly increases to as high as 6.7. The purified gold nanobipyramids can be used as a colorimetric probe in the detection of tannic acid with a detection limit of 0.86 µM and a linear detection range from 1.25 to 37.5 µM.

Highly-Controlled Soft-Templating Synthesis of Hollow ZIF-8 Nanospheres for Selective CO2 Separation and Storage.

Global warming is an ever-rising environmental concern, and carbon dioxide (CO2) is among its major causes. Different technologies, including adsorption, cryogenic separation, and sequestration, have been developed for CO2 separation and storage/utilization. Among these, carbon capture using nano-adsorbents has the advantages of excellent CO2 separation and storage performance as well as superior heat- and mass-transfer characteristics due to their large surface area and pore volume. In this work, an environmentally friendly, facile, bottom-up synthesis of ZIF-8 hollow nanospheres (with reduced chemical consumption) was developed for selective CO2 separation and storage. During this soft-templating synthesis, a combined effect of ultra-sonication and low-temperature hydrothermal synthesis showed better control over an oil-in-water microemulsion formation and the subsequent growth of large-surface-area hollow ZIF-8 nanospheres having excellent particle size distribution. Systematic studies on the synthesis parameters were also performed to achieve fine-tuning of the ZIF-8 crystallinity, hollow structures, and sphere size. The optimized hollow ZIF-8 nanosphere sample having uniform size distribution exhibited remarkable CO2 adsorption capability (∼2.24 mmol g-1 at 0 °C and 1.75 bar), a CO2/N2 separation selectivity of 12.15, a good CO2 storage capacity (1.5-1.75 wt %), and an excellent cyclic adsorption/desorption performance (up to four CO2 adsorption/desorption cycles) at 25 °C. In addition, the samples showed exceptional structural stability with only ∼15% of overall weight loss up to 600 °C under a nitrogen environment. Therefore, the hollow ZIF-8 nanospheres as well as their highly controlled soft-templating synthesis method reported in this work are useful in the course of the development of nanomaterials with optimized properties for future CO2 capture technologies.

Photo-Modulating CO2 Uptake of Hypercross-linked Polymers Upcycled from Polystyrene Waste.

Incorporating photo-switches into skeletal structures of microporous materials or as guest molecules yield photo-responsive materials for low-energy CO2 capture but at the expense of lower CO2 uptake. Here, we overcome this limitation by exploiting trans-cis photoisomerization of azobenzene loaded into the micropores of hypercross-linked polymers (HCPs) derived from waste polystyrene. Azobenzene in HCP pores reduced CO2 uptake by 19 %, reaching 37.7 cm3 g-1 , but this loss in CO2 uptake was not only recovered by trans-cis photoisomerization of azobenzene, but also increased by 22 %, reaching 56.9 cm3 g-1 , when compared to as-prepared HCPs. Computational simulations show that this increase in CO2 uptake is due to photo-controlled increments in 10-20 Šmicropore volume, i. e., adsorption sites and a photo-reversible positive dipole moment. Irradiating these HCPs with visual-range light reverted CO2 uptake to 33 cm3 g-1 . This shows that it is feasible to recycle waste polystyrene into advanced materials for low-energy carbon capture.

Facile fabrication of zeolitic imidazolate framework hollow fibre membranes via a novel scalable continuous fluid circulation process.

A novel continuous fluid circulation system was designed and employed for the impregnation seeding and fabrication of zeolitic imidazolate framework (ZIF) crystals on the internal surface of polymeric hollow fibre membranes. Application of impregnation seeding has been proven effective to decrease crystal size, consequently increasing surface roughness and wettability of the membrane. Evaluation of the as-synthesised membrane demonstrated excellent separation efficiencies (>99%) of surfactant stabilised oil-in-water emulsions. Owing to the simple impregnation strategy assisted by the continuous fluid circulation, the active ZIF layer formed was visibly thinner and denser than typical seeding techniques, hence a high pure water flux of >1150 L m-2 h-1 bar-1 was achieved. The membranes were highly selective and ultra-permeable to water, however, almost impermeable to oils in a water environment, e.g., n-hexane, n-heptane, chloroform and dichloromethane, as well as their emulsion mixtures, with a separation efficiency higher than 99%. Besides, this new continuous fluid circulation method was also found promising for the synthesis of other types of ZIF on hollow fibre membranes.

Cluster formation in symmetric binary SALR mixtures.

The equilibrium cluster fluid state of a symmetric binary mixture of particles interacting through short-ranged attractive and long-ranged repulsive interactions is investigated through Monte Carlo simulations. We find that the clustering behavior of this system is controlled by the cross-interaction between the two types of particles. For a weak cross-attraction, the system displays a behavior that is a composite of the behavior of individual components, i.e., the two components can both form giant clusters independently and the clusters distribute evenly in the system. For a strong cross-attraction, we instead find that the resulting clusters are mixtures of both components. Between these limits, both components can form relatively pure clusters, but unlike clusters can join at their surfaces to form composite clusters. These insights should help to understand the mechanisms for clustering in experimental binary mixture systems and help tailor the properties of novel nanomaterials.

Evolution of Thin-Liquid Films Surrounding Bubbles in Microfluidics and Their Impact on the Pressure Drop and Fluid Movement.

The evolution of thin-liquid films in a microchannel is one of the most critical and intricate phenomena to understand two-phase movement, evaporation, micromixing, heat transfer, chemical synthesis, biological processes, and efficient energy devices. In this paper, we demonstrate experimentally the effect of a liquid film on the removal of an initially dry and lodged bubble in laser-etched poly(methyl methacrylate) microfluidic networks and discuss the evolution of the liquid film in accordance with the bubble superficial velocity and the effect of liquid properties and branch angle on the evolution of the liquid film and the pressure drop. During the removal of a dry bubble, four stages have been observed in the bubble velocity profile and they directly relate to the evolution of the liquid film. The correlation of maximum bubble velocity has been derived as a function of bubble length, fluid viscosity, surface tension, geometry of the cross-sectional area, and dimensions of the microchannel and agrees with the experimental results. The bubble moving distance required for the full deposition of a continuous and stable thin-liquid film is affected by the liquid viscosity and network branch angle. The liquid with a higher viscosity will increase the pressure drop for removing dry bubbles from microfluidic networks, while this effect will be hampered by increasing the microfluidic network complexity. The deposition of the thin-liquid film surrounding bubbles significantly decreases the pressure drop required to remove bubbles from microfluidics. Compared with deionized water, the glycerol solution is prone to acting as the lubricating liquid due to its strong H-bond interaction with the channel wall and the reduction in interfacial energy of the gas-water interface.

Effect of Ag Co-catalyst on TiO2-Cu2O nanocomposites structure and apparent visible photocatalytic activity.

Although Cu2O is a commonly used narrow band gap semiconductor to fabricate visible response photocatalysts, up to date there are only a few reports on Ag co-catalysed TiO2-Cu2O nanocomposites. Herein we report a facile wet chemical synthesis approach to prepare TiO2-Ag-Cu2O ternary hybrid nanomaterials. Uniquely, both the effect of Ag content and the synthesis sequence of Ag deposition step was investigated on the visible decoloration rate. The crystal structure, morphology, optical and dark adsorption properties of the nanostructures were characterized by XRD, SEM, TEM and diffuse reflectance, respectively. Due to the mixed indirect and direct nature of the nanocomposites, the band gap estimation was performed by using both Tauc plot and differential reflectance model. The dark adsorption properties of catalysts could be typically well-approximated by pseudo-second order kinetics, while TiO2-Ag(5%)-Cu2O catalyst cannot be described by standard models due to a delayed adsorption behaviour observed in the first 50 min. The apparent visible activities followed pseudo-zero order kinetics. It was found that TiO2-Ag(3%)-Cu2O catalyst exhibited the highest rate constant which was ca. two times as high as that of the binary TiO2-Cu2O catalyst. The synthesis sequence of the Ag deposition step significantly altered the material properties which resulted in different dark adsorption and apparent visible activities.

Adsorption of CO2 on amine-functionalized green metal-organic framework: an interaction between amine and CO2 molecules.

The efficient capture of CO2 is a critical problem for porous adsorbents. The inadequacy of conventional adsorbents has low adsorption capacity towards CO2 removal. Metal organic frame work has been considered as very effective for CO2 adsorption as it shows higher rate of CO2 adsorption at room temperature. In conventional amine processes, a comparatively high energy penalty is required, whereas a novel class of metal-organic framework by the combination of amine solvent have improve the potential of adsorption process and also the efficiency of separation. Amine-functionalized MOFs become more fascinated due to strong interaction between carbon dioxide and amine-functionalized MOF. A renewable green γCD-MOF was synthesized by using vapor diffusion method. Post-synthetic modification of γCD-MOF was done with piperazine and analyzed to expose its crystalline structure, morphology, and porous structure. The main aim of this paper is to enhance the CO2 adsorption by functionalization of inexpensive, green, nanoporous γCD-MOF and also to highlight the effects of amine-based functionalization towards potential application. Gravimetric CO2 adsorption isotherms for γCD-MOF, pip-γCD-MOF are reported up to 60 °C and found to follow a pseudo-second-order reaction. The pip-γCD-MOF confirms comparatively increased rapid adsorption rate of CO2 than that of γCD-MOF and desorption of CO2, and need less energy for regeneration. These results are the complete evidence of piperazine as an efficient amine group for increasing the CO2 adsorption uptake capacity.

Bubble Dislodgment in a Capillary Network with Microscopic Multichannels and Multibifurcation Features.

Bubble lodgment in a complex capillary network is a common issue in many industrial and biological processes. Research work reported in the literature only investigated bubble dislodgment in single channels and did not consider the effect of network complexity on the dislodgment. This paper focuses on the pressure required to dislodge single bubbles from a microscopic capillary network and investigates the factors affecting the dislodging pressure to facilitate the precise control of bubble flows in porous media. A capillary network with multibifurcation and a smoothly changed diameter is designed to closely mimic the structure of the physiological vascular networks. Over 600 bubble dislodgment experiments have been conducted to understand the effect of the network structure, channel dimensions, and bubble length on the dislodging pressure. The results indicate that the network structure is a dominant factor affecting the dislodging pressure that increases with the increase in network complexity. The effect of bubble length on the dislodging pressure depends on the bubble length. When the bubble length is less than a certain value, which is around 2 mm in this study, the dislodging pressure increases significantly with the decrease of bubble length. When the bubble length is larger than 2 mm, the dislodging pressure is independent of the bubble length. A model has been proposed to explain the bubble dislodgment in complex capillary networks. The impact of the network structure on the bubble dislodging pressure is characterized by a parameter c j. The model indicates that the dislodging pressure is the function of bubble length, channel dimension, and network structure. The analysis of model parameters NB j and MA j shows that parameter c j, rather than the channel size, dominates the dislodging pressure for bubbles with a length greater than 2 mm, and the increase rate of the dislodging pressure is significantly affected by both channel size and parameter c j.

[Isolation of filamentous fungi capable of enhancing sludge dewaterability and study of mechanisms responsible for the sludge dewaterability enhancement].

To study the influence of filamentous fungi on the sludge dewaterability is very significant for the development of biological treatment methods for enhancing sludge dewaterability. In this study, filamentous fungi capable of enhancing sludge dewaterability were isolated from sewage sludge and the related mechanisms responsible for the sludge dewaterability enhancement were investigated. A filamentous fungus Mucor circinelloides ZG-3 was successfully isolated from sludge, and sludge dewaterability could be drastically improved by this fungus. Further study revealed that the enhancement of sludge dewaterability was influenced by inoculation method, inoculum size and solid content of sludge. The optimal inoculation method was mycelia inoculation, the optimal inoculum size was 10%, and the optimal solid content of sludge was about 4%. Under the optimized conditions, the specific resistance to filtration (SRF) of sludge could be decreased by 75.1% after being treated by M. circinelloides ZG-3. After the treatment, the COD value of sludge supernatant was only 310 mg x L(-1), and the treated sludge still exhibited good settleability. During the treatment of sewage sludge by M. circinelloides ZG-3, the mechanisms responsible for the sludge dewaterability enhancement included the degradation of sludge extracellular polymeric substances (EPS) and the decrease of sludge pH. Therefore, the treatment of sewage sludge using M. circinelloides ZG-3 is a useful and novel method for sludge conditioning.

Modification of ilmenite surface chemistry for enhancing surfactants adsorption and bubble attachment.

In this study, microwave irradiation is used to modify ilmenite surface chemistry to enhance the adsorption of surfactants and the air bubble attachment. The results indicate that microwave irradiation can increase ilmenite flotation recovery by 20%. A positron emission particle tracking technique is used to study the dynamic behaviour of ilmenite particles in a Denver cell. The data shows that the poor flotation recovery of ilmenite is not only due to the reduce probability of ilmenite being captured by air bubbles, but also the short residence time of the particles remaining in the froth phase. The ilmenite particles can be frequently captured by air bubbles, but dropped to the bulk liquid from the froth phase, normally over 15 s. Microwave irradiation changes the ilmenite flow pattern in the Denver cell. The average time of ilmenite remaining in froth phase is increased from 11.5 to 29.1 s.

A simple and selective method for the separation of Cu radioisotopes from nickel.

Separation of copper radioisotopes from a nickel target is normally performed using solvent extraction or anion exchange rather than using cationic exchange. A commonly held opinion is that cationic exchangers have very similar thermodynamic complexation constants for metallic ions with identical charges, therefore making the separation very difficult or impossible. The results presented in this article indicate that the selectivity of Chelex-100 (a cationic ion exchanger) for Cu radioisotope and Ni ions not only depends on the thermodynamic complexation constant in the resin but also markedly varies with the concentration of mobile H+. In our developed method, separation of copper radioisotopes from a nickel target was fulfilled in a column filled with Chelex-100 via controlling the HNO3 concentration of the eluent, and the separation is much more effective, simple and economical in comparison with the common method of anion exchange. For an irradiated nickel target with 650 mg Ni, after separation, the loss of Cu radioisotopes in the nickel portion was reduced from 30% to 0.33% of the total initial radioactivity and the nickel mixed into the radioactive products was reduced from 9.5 to 0.5 mg. This significant improvement will make subsequent labeling much easier and reduce consumption of chelating agents and other chemicals during labeling. If the labeled agent is used in human medical applications, the developed method will significantly decrease the uptake of Ni and chelating agents by patients, therefore reducing both the stress on human body associated with clearing the chemicals from blood and tissue and the risk of various types of acute and chronic disorder due to exposure to Ni.