ABSTRACT
The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m-2 h-1 (K+), reaching excellent mono/multivalent selectivity up to 20.1 (K+/Mg2+) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.
ABSTRACT
A tough ion gel membrane containing a CO2-philic ionic liquid, 1-ethyl-3-methylimidazolium tricyanomethanide ([Emim][C(CN)3]), was developed, and its CO2 permeation properties were evaluated under humid conditions at elevated temperatures. Pebax 1657, which is a diblock copolymer composed of a polyamide block and a polyethylene oxide block, was used as the gel network of the ion gel membrane to prepare a tough ion gel with good ionic liquid-holding properties. The polyamide block formed a semicrystalline structure in [Emim][C(CN)3] to toughen the ion gel membrane via an energy dissipation mechanism. The polyethylene oxide block exhibited good compatibility with [Emim][C(CN)3] and contributed to the retention of the ionic liquid in the ion gel. The developed ion gel membrane showed a good CO2 separation performance of 1677 barrer CO2 permeability and 37 CO2/N2 permselectivity under humid conditions of 75% relative humidity at an elevated temperature of 50 °C, which corresponds to an exhaust gas from a coal-fired power plant.
ABSTRACT
Oily wastewater threatens the environment and the human health. Membrane technology offers a simple and efficient alternative to separating oil and water. However, complex membrane modifications are usually employed to optimize the separation performance. In this research, we develop an extremely simple one-step method to in situ calcium carbonate (CaCO3) nanoparticles onto a porous polyketone (PK) membrane via a nonsolvent induced phase separation (NIPS)-mineralization strategy. We utilized the unique chemical property of PK, which allows it to dissolve in a resorcinol aqueous solution. PK was mixed with tannic acid (TA) and calcium chloride (CaCl2) in a resorcinol aqueous solution to fabricate a casting solution. The activated membrane was cast and immersed into a sodium carbonate (Na2CO3) aqueous solution for taking the one-step NIPS-mineralization process. This proposed NIPS-mineralization mechanism comes to two conclusions: (i) the resulting membrane with comprehensive oleophobic properties and enhanced permeation flux for applications of oil/water separation with ultralow fouling and (ii) simplified the procedure to optimize the membrane performance using regular NIPS steps. The current work explores a one-step NIPS-mineralization technique that offers a novel approach to preparing membranes with highly efficient oil/water separation performance.
ABSTRACT
The current study aimed to establish an experimental model in vitro and in vivo of urinary crystal deposition on the surface of ureteral stents, to evaluate the ability to prevent crystal adhesion. Non-treated ureteral stents were placed in artificial urine under various conditions in vitro. In vivo, ethylene glycol and hydroxyproline were administered orally to rats and pigs, and urinary crystals and urinary Ca were investigated by Inductively Coupled Plasma-Optical Emission Spectrometer. in vitro, during the 3- and 4-week immersion periods, more crystals adhered to the ureteral stent in artificial urine model 1 than the other artificial urine models (p < 0.01). Comparing the presence or absence of urea in the composition of the artificial urine, the artificial urine without urea showed less variability in pH change and more crystal adhesion (p < 0.05). Starting the experiment at pH 6.3 resulted in the highest amount of crystal adhesion to the ureteral stent (p < 0.05). In vivo, urinary crystals and urinary Ca increased in rat and pig experimental models. This experimental model in vitro and in vivo can be used to evaluate the ability to prevent crystal adhesion and deposition in the development of new ureteral stents to reduce ureteral stent-related side effects in patients.
Subject(s)
Stents , Animals , Rats , Swine , Male , Hydrogen-Ion Concentration , Calcium/urine , Crystallization , Ureter , Ethylene Glycol/chemistry , Hydroxyproline/urine , Urine/chemistry , Rats, Sprague-DawleyABSTRACT
Chemically converted graphene oxide laminate membranes, which exhibit stable interlayered nanochannels in aqueous environments, are receiving increasing attention owing to their potential for selective water and ion permeation. However, how the molecular properties of conversion agents influence the stabilization of nanochannels and how effectively nanochannels are stabilized have rarely been studied. In this study, mono-, di-, and tri-saccharide molecules of glucose (Glu), maltose (Glu2), and maltotriose (Glu3) are utilized, respectively, to chemically modify graphene oxide (GO). The aim is to create nanochannels with different levels of stability and investigate how these functional conversion agents affect the separation performance. The effects of the property differences between different conversion agents on nanochannel stabilization are demonstrated. An agent with efficient chemical reduction of GO and limited intercalation in the resulting nanochannel ensures satisfactory nanochannel stability during desalination. The stabilized membrane nanochannel exhibits a permeance of 0.69 L m-2 h-1 bar-1 and excellent Na2SO4 rejection of 96.42%. Furthermore, this optimized membrane nanochannel demonstrates enhanced stability under varying external conditions compared to the original GO. This study provides useful information for the design of chemical conversion agents for GO nanochannel stabilization and the development of nanochannel membranes for precise separation.
ABSTRACT
In this work, a novel polydopamine/reduced graphene oxide (PDA/rGO) nanofiltration membrane was prepared to efficiently and stably remove radioactive strontium ions under an alkaline environment. Through the incorporation of PDA and thermal reduction treatment, not only has the interlayer spacing of graphene oxide (GO) nanosheets been appropriately regulated but also an improved antiswelling property has been achieved. The dosage of GO, reaction time with PDA, mass ratio of PDA to GO, and thermal treatment temperature have been optimized to achieve a high-performance PDA/rGO membrane. The resultant PDA/rGO composite membrane has exhibited excellent long-term stability at pH 11 and maintains a steady strontium rejection of over 90%. Moreover, the separation mechanism of the PDA/rGO membrane has been systematically investigated and determined to be a synergistic effect of charge repulsion and size exclusion. Results have indicated that PDA/rGO could be considered as a promising candidate for the separation of Sr2+ ions from nuclear industry wastewater.
ABSTRACT
Metal-organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect-free high-connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined-coordination induced intergrowth strategy to fabricate lattice-defect-free Zr-MOF membrane towards precise molecular separation. The confined-coordination space properties (size and shape) and environment (water or DMF) were regulated to slow down the coordination reaction rate via controlling the counter-diffusion of MOF precursors (metal cluster and ligand), thereby inter-growing MOF crystals into integrated membrane. The resulting Zr-MOF membrane with angstrom-sized lattice apertures exhibits excellent separation performance both for gas separation and water desalination process. It was achieved H2 permeance of ~1200 GPU and H2/CO2 selectivity of ~67; water permeance of ~8â L â m-2 â h-1 â bar-1 and MgCl2 rejection of ~95 %, which are one to two orders of magnitude higher than those of state-of-the-art membranes. The molecular transport mechanism related to size-sieving effect and transition energy barrier differential of molecules and ions was revealed by density functional theory calculations. Our work provides a facile approach and fundamental insights towards developing precise molecular sieving membranes.
ABSTRACT
Over half of the pharmaceutical industry's capital investments are related to the purification of active pharmaceutical ingredients (APIs). Thus, a cost-effective purification process with a highly concentrated solution is urgently required. In addition, the purification process should be nonthermal because most APIs and their intermediates are temperature-sensitive. This study investigated a high-degree concentration organic solvent forward osmosis (OSFO) membrane process. A polyketone-based thin-film composite hollow fiber membrane with a polyamide selective layer on the bore surface was used as the OSFO membrane to achieve a high tolerance for organic solvents and an effective concentration. MeOH, sucrose octaacetate (SoA), and 2M polyethylene glycol 400 (PEG-400)/MeOH solution were used as the solvent, model API, and a draw solution (DS), respectively. OSFO was performed at room temperature (23 ± 3 °C). Consequently, the 11 wt% SoA/MeOH solution was concentrated to 52 wt% without any SoA leakage into the DS. To our knowledge, there are no studies in which up to a 5 wt% concentration by OSFO has been demonstrated. However, the final feed solution contained 17 wt% PEG-400. This study demonstrates the promising potential of OSFO for pharmaceutical pre-concentration and the technical problems that need to be solved for social implementation.
ABSTRACT
Recovery of water, salts, and hazardous dye from complex saline textile wastewater faces obstacles in separating dissolved ionic substances and recovering organic components during desalination. This study realized the simultaneous fractionation, desalination, and dye removal/recovery treatment of textile wastewater by using trehalose (Tre) as an aqueous monomer to prepare polyester loose nanofiltration (LNF) membrane with fine control microstructure via interfacial polymerization. Outperforming the NF270 commercial membrane, the Tre-1.05/TMC optimized membrane achieves zero-discharge textile wastewater treatment, cutting energy consumption by 295% and reducing water consumption by 42.8%. This efficiency surge results from remarkable water permeability (130.83 L m-2 h-1 bar-1) and impressive dye desalination (NaCl/ Direct Red 23 separation factor of 275) of the Tre-1.05/TMC membrane. For a deeper comprehension of filtration performance, the sieving mechanism of polyester LNF membranes was systematically elucidated. This strategic approach offers significant prospects for energy conservation, carbon emission mitigation, and enhanced feasibility of membrane-based wastewater treatment systems.
ABSTRACT
This study aimed to establish a high-level phenol bioproduction system from glycerol through metabolic engineering of the yeast Pichia pastoris (Komagataella phaffii). Introducing tyrosine phenol-lyase to P. pastoris led to a production of 59 mg/L of phenol in flask culture. By employing a strain of P. pastoris that overproduces tyrosine-a precursor to phenol-we achieved a phenol production of 1052 mg/L in glycerol fed-batch fermentation. However, phenol concentrations exceeding 1000 mg/L inhibited P. pastoris growth. A phenol pertraction system utilizing a hollow fiber membrane contactor and tributyrin as the organic solvent was developed to reduce phenol concentration in the culture medium. Integrating this system with glycerol fed-batch fermentation resulted in a 214 % increase in phenol titer (3304 mg/L) compared to glycerol fed-batch fermentation alone. These approaches offer a significant framework for the microbial production of chemicals and materials that are highly toxic to microorganisms.
Subject(s)
Glycerol , Phenol , Saccharomycetales , Fermentation , Glycerol/metabolism , Phenol/metabolism , Pichia/metabolism , Recombinant Proteins/metabolism , Methanol/metabolismABSTRACT
Ammoniacal nitrogen (NH4N) is a ubiquitous nitrogen pollutant found in wastewater, which could cause eutrophication and severe environmental stress. It is therefore necessary to manage NH4N by enrichment and recovery for potential reuse, as well as to regulate the amount of environmental discharge. Hybridization of membrane-based processes is an attractive option for further enhancing water and nutrient reclamation from waste streams; thus, in this present work, a hybrid osmotically assisted reverse osmosis (OARO) and reverse osmosis (RO) process was demonstrated for subsequent ammoniacal nitrogen enrichment and wastewater discharge management. Using a commercially-available cellulose triacetate membrane module, model and real wastewater containing approximately 4,000ppm NH4N were effectively dewatered and enriched to a final NH4N content of 40,300ppm. This corresponds to enrichment of around 10 times and approximately 90% pure water recovery. The effective combination of both processes resulted in high efficiency, as well as economical and energy-saving benefits, as shown by the process performance and our preliminary techno-economic analysis. The specific energy consumption of the hybrid process projected to operate at a capacity of 2,000 m3h-1 was determined to be 8.8kWh m-3, or 0.56kWh kg-1 NH4Cl removed/recovered for an initial feed solution containing around 15,300ppm NH4Cl. Hybrid OARO and RO operation was able to achieve satisfactory enrichment by the OARO process and obtaining clean water by the RO process. The hybrid OARO-RO process has shown great potential as a suitable end-stage membrane-based process for wastewater dewatering and NH4N enrichment and recovery toward a circular economy and environmental management, as well as clean water recovery.
Subject(s)
Wastewater , Water Purification , Nitrogen , Water Purification/methods , Osmosis , Membranes, Artificial , Water , Waste Disposal, Fluid/methodsABSTRACT
Membrane distillation (MD) has prominent advantages such as treating high-salinity wastewater with a low-grade thermal energy, high salt rejection, and zero discharge. However, organic fouling and mineral scaling are two major challenges for hydrophobic MD membranes when used for practical applications. Commonly, improving organic fouling- and mineral scaling-resistance require oppositely enhanced wetting properties of membrane, thus is difficult to simultaneously realize dual resistance with one membrane. Here, we proposed to use underwater thermodynamically stable high-surface-energy coating to modify the hydrophobic membrane with Janus structures comprising different surface energy. The underlayered structure meets the hydrophobicity requirements of the MD membrane, while the coating layer realizes dual resistance to organic and inorganic foulants. Theoretical analysis and experimental proof reveal that the membrane with the high-surface-energy coating layer outperforms the pristine one with approximately 10 times of longevity. This strategy provides a new way for the use of high-surface-energy materials in versatilely fouling-resistant MD process.
Subject(s)
Biofouling , Water Purification , Distillation , Biofouling/prevention & control , Membranes, Artificial , Seawater , MineralsABSTRACT
Subnanometer interlayer space in graphene oxide (GO) laminates is desirable for use as permselective membrane nanochannels. Although the facile modification of the local structure of GO enables various nanochannel functionalizations, precisely controlling nanochannel space is still a challenge, and the roles of confined nanochannel chemistry in selective water/ion separation have not been clearly defined. In this study, macrocyclic molecules with consistent basal plane but varying side groups were used to conjunct with GO for modified nanochannels in laminates. We demonstrated the side-group dependence of both the angstrom-precision tunability for channel free space and the energy barrier setting for ion transport, which challenges the permeability-selectivity trade-off with a slightly decreased permeance from 1.1 to 0.9 L m-2 h-1 bar-1 but an increased salt rejection from 85% to 95%. This study provides insights into the functional-group-dependent intercalation modifications of GO laminates for understanding laminate structural control and nanochannel design.
ABSTRACT
Interfacial polymerization (IP) and self-assembly are two thermodynamically different processes involving an interface in their systems. When the two systems are incorporated, the interface will exhibit extraordinary characteristics and generate structural and morphological transformation. In this work, an ultrapermeable polyamide (PA) reverse osmosis (RO) membrane with crumpled surface morphology and enlarged free volume was fabricated via IP reaction with the introduction of self-assembled surfactant micellar system. The mechanisms of the formation of crumpled nanostructures were elucidated via multiscale simulations. The electrostatic interactions among m-phenylenediamine (MPD) molecules, surfactant monolayer and micelles, lead to disruption of the monolayer at the interface, which in turn shapes the initial pattern formation of the PA layer. The interfacial instability brought about by these molecular interactions promotes the formation of crumpled PA layer with larger effective surface area, facilitating the enhanced water transport. This work provides valuable insights into the mechanisms of the IP process and is fundamental for exploring high-performance desalination membranes.
ABSTRACT
Laminar membranes comprising graphene oxide (GO) and metal-organic framework (MOF) nanosheets benefit from the regular in-plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two-step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4-carboxyphenyl)porphyrin (H2 TCPP) to realize in situ transformation of ZnO into Zn-TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn-TCPP/rGO laminar membrane exhibits preferential orientation of Zn-TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m-2 h-1 bar-1 and high anionic dye rejection (>99% for methyl blue).
ABSTRACT
Encrustation, caused by deposition of calcium and magnesium salts present in urine, is a common problem of indwelling urinary devices, such as ureteral stent. Encrustation was also found to be related to urinary tract infections; thus, it is necessary to prepare ureteral stents with antibacterial and antifouling surfaces to mitigate the occurrence of encrustation. In this study, commercial ureteral stent was coated with polydopamine (PDA), formed from self-polymerization of dopamine. The PDA coating was optimized in terms of dopamine concentration, pH, and coating time using response surface methodology. The chosen response parameters for optimization were calcium oxalate (CaC2 O4 ) encrustation and protein adsorption. Optimized PDA coating conditions were determined to be the following: pH 9.0, 2 mg/mL DA, and 3 days coating. The optimized PDA-coated ureteral stent exhibited outstanding resistance against CaC2 O4 encrustation, protein fouling, and bacterial adhesion due to its hydrophilic and functional coating layer. In comparison with the pristine ureteral stent, PDA coating was able to suppress approximately 97% and 87% of CaC2 O4 and protein adsorption, respectively. The PDA-coated ureteral stent was compared against those of commercially available ureteral stents and found to have superior encrustation and protein fouling mitigation performance. Finally, PDA coating was found to be highly stable for a storage period of 90 days, whether stored in wet or dry conditions.
Subject(s)
Ureter , Urinary Tract Infections , Humans , Calcium , Dopamine , Stents , Urinary Tract Infections/microbiologyABSTRACT
Nanochannels in laminated graphene oxide nanosheets featuring confined mass transport have attracted interest in multiple research fields. The use of nanochannels for reverse osmosis is a prospect for developing next-generation synthetic water-treatment membranes. The robustness of nanochannels under high-pressure conditions is vital for effectively separating water and ions with sub-nanometer precision. Although several strategies have been developed to address this issue, the inconsistent response of nanochannels to external conditions used in membrane processes has rarely been investigated. In this study, we develop a robust interlayer channel by balancing the associated chemistry and confinement stability to exclude salt solutes. We build a series of membrane nanochannels with similar physical dimensions but different channel functionalities and reveal their divergent deformation behaviors under different conditions. The deformation constraint effectively endows the nanochannel with rapid deformation recovery and excellent ion exclusion performance under variable pressure conditions. This study can help understand the deformation behavior of two-dimensional nanochannels in pressure-driven membrane processes and develop strategies for the corresponding deformation constraints regarding the pore wall and interior.
ABSTRACT
Domestic wastewater (DWW) contains a reservoir of nutrients, such as nitrogen, potassium, and phosphorus; however, emerging micropollutants (EMPs) hinder its applications in resource recovery. In this study, a novel class of nanofiltration (NF) membranes was developed; it enabled the efficient removal of harmful EMP constituents while preserving valuable nutrients in the permeate. Neutral (IM-N) and positively charged (IM-P) imidazole derivative compounds have been used to chemically functionalize pristine polyamide (PA) membranes to synchronously inhibit the hydrolysis of residual acyl chloride and promote their amination. Owing to their distinct properties, these IM modifiers can custom-build the membrane physicochemical properties and structures to benefit the NF process in DWW treatment. The electroneutral NF membrane exhibited ultrahigh solute-solute selectivity by minimizing the Donnan effects on ion penetration (K, N, and P ions rejection < 25%) while imposing remarkable size-sieving obstruction against EMPs (rejection ratio > 91%). Moreover, the hydrophilic IM-modifier synergistically led to enhanced water permeance of 9.2 L m-2 h-1 bar-1, reaching a 2-fold higher magnitude than that of the pristine PA membrane, along with excellent antifouling/antibacterial fouling properties. This study may provide a paradigm shift in membrane technology to convert wastewater streams into valuable water and nutrient resources.
Subject(s)
Membranes, Artificial , Wastewater , Chlorides , Nylons , Water , ImidazolesABSTRACT
For the first time, we have successfully fabricated microfiltration (MF) hollow fiber membranes by the thermally induced phase separation (TIPS) and non-solvent induced phase separation (NIPS) methods using cellulose acetate benzoate (CBzOH), which is a cellulose derivative with considerable chemical resistance. To obtain an appropriate CBzOH TIPS membrane, a comprehensive solvent screening was performed to choose the appropriate solvent to obtain a membrane with a porous structure. In parallel, the CBzOH membrane was prepared by the NIPS method to compare and evaluate the effect of membrane structure using the same polymer material. Prepared CBzOH membrane by TIPS method showed high porosity, pore size around 100 nm or larger and high pure water permeability (PWP) with slightly low rection performance compared to that by NIPS. On the contrary, CBzOH membranes prepared with the NIPS method showed three times lower PWP with higher rejection. The chemical resistance of the prepared CBzOH membranes was compared with that of cellulose triacetate (CTA) hollow fiber membrane, which is a typical cellulose derivative as a control membrane, using a 2000 ppm sodium hypochlorite (NaClO) solution. CBzOH membranes prepared with TIPS and NIPS methods showed considerable resistance against the NaClO solution regardless of the membrane structure, porosity and pore size. On the other hand, when the CTA membrane, as the control membrane, was subjected to the NaClO solution, membrane mechanical strength sharply decreased over the exposure time to NaClO. It is interesting that although the CBzOH TIPS membrane showed three times higher pure water permeability than other membranes with slightly lower rejection and considerably higher NaClO resistance, the mechanical strength of this membrane is more than two times higher than other membranes. While CBzOH samples showed no change in chemical structure and contact angle, CTA showed considerable change in chemical structure and a sharp decrease in contact angle after treatment with NaClO. Thus, CBzOH TIPS hollow fiber membrane is noticeably interesting considering membrane performance in terms of filtration performance, mechanical strength and chemical resistance on the cost of slightly losing rejection performance.
ABSTRACT
In recent years, a well-known membrane-based process called pervaporation (PV), has attracted remarkable attention due to its advantages for selective separation of a wide variety of liquid mixtures. However, some restrictions of polymeric membranes have led to research studies on developing membranes for efficient separation in the PV process. Recent studies have focused on preparation of nanocomposite membranes as an effective method to improve both selectivity and permeability of polymeric membranes. The present study provides a review of PV nanocomposite membranes for various applications. In this review, recent developments in the field of nanocomposite membranes, including the fabrication methods, characterization, and PV performance, are summarized.