In situ cleaning of foulants by gas scouring on the membrane-electrode in an electro-membrane bioreactor.

Low-maintenance membrane cleaning is essential for the stable operation of membrane bioreactors. This work proposes an in-situ electrical-cleaning method using an electro-MBR. When the applied bias was transiently increased, the membrane flux recovered rapidly because of the scouring effect from gas evolution reactions. The exfoliation of the cake layer induced by gas scouring played a major role in mitigating membrane fouling, recovering the transmembrane pressure (TMP) by 88.6 % under optimal conditions. Membrane modules did not require replacement during the operation period due to the efficacy of electrical cleaning, with the TMP varying between 37.5 % and 62.5 % of the ultimate pressure requiring change of the membrane modules. Despite the increase in power consumption of 0.66 Wh·m-3 due to the additional applied bias, there was no need for chemical additives or manual maintenance. Therefore, the electrical cleaning method enhanced the service life and reduced the maintenance costs of the electro-MBR.

A Novel Electromagnetic Driving System for 5-DOF Manipulation in Intraocular Microsurgery.

This work presents a novel electromagnetic driving system that consists of eight optimized electromagnets arranged in an optimal configuration and employs a control framework based on an active disturbance rejection controller (ADRC) and virtual boundary. The optimal system configuration enhances the system's compatibility with other ophthalmic surgical instruments, while also improving its capacity to generate magnetic force in the vertical direction. Besides, the optimal electromagnet parameters provide a superior comprehensive performance on magnetic field generation capacity and thermal power. Hence, the presented design achieves a stronger capacity for sustained work. Furthermore, the ADRC controller effectively monitors and further compensates the total disturbance as well as gravity to enhance the system's robustness. Meanwhile, the implementation of virtual boundaries substantially enhances interactive security via collision avoidance. The magnetic and thermal performance tests have been performed on the electromagnet to verify the design optimization. The proposed electromagnet can generate a superior magnetic field of 2.071 mT at a distance of 65 mm with an applied current of 1 A. Moreover, it demonstrates minimal temperature elevation from room temperature (25 °C) to 46 °C through natural heat dissipation in 3 h, thereby effectively supporting prolonged magnetic manipulation of intraocular microsurgery. Furthermore, trajectory tracking experiments with disturbances have been performed in a liquid environment similar to the practical ophthalmic surgery scenarios, to verify the robustness and security of the presented control framework. The maximum root mean square (RMS) error of performance tests in different operation modes remains 35.8 µm, providing stable support for intraocular microsurgery.

Stress response of Microcystis aeruginosa to chlorine during transportation: The significance of surface-adsorbed organic matter.

The desorption of surface-adsorbed organic matter (S-AOM) without damaging algal cells was reported to be the key to destabilizing Microcystis aeruginosa (M. aeruginosa) cells while avoiding intracellular organic matter (IOM) release in our previous study. However, a temporal effect was found from spontaneous and continuous damage to algal cells even after quenching. This study aims to demonstrate the mechanism of the temporal inactivation effect and the stress response exhibited by chlorine-oxidized algal cells, and finally guide the prechlorination process for algae-laden water at water sources. Chlorine was proved to cause oxidative stress to M. aeruginosa cells, and result in a rapid increase in intracellular reactive oxygen species (ROS) levels. S-AOM appeared to have a protective effect on algal cells against oxidative damage, as evidenced by the maintenance of algal cell integrity and activated antioxidant enzymes. In addition, the activity of Caspase 3, a key protease for the execution of programmed cell death (PCD), was significantly enhanced during prechlorination. Cellular chromatin condensation and DNA fragmentation occurred in the early stages of PCD in algal cells. Therefore, the pre-treatment of algae-laden water at water sources, even with low chlorine doses, can induce a risk of significant algal cell death during the water transfer process due to activation of the PCD process, resulting in a higher health risk for drinking water. These findings indicate that both the dosage of chlorine and the duration of the transportation process should be considered during the prechlorination of algae-laden water, which can provide an important basis for avoiding increasing the risk to drinking water safety.

Synchronous in-situ sludge reduction and enhanced denitrification through improving electron transfer during endogenous metabolisms with Fe(â ¡) addition.

The creation of large amounts of excess sludge and residual nitrogen are critical issues in wastewater biotreatment. This study introduced Fe(II) into an oligotrophic anaerobic reactor (OARFe) that was implemented to modify an anoxic-oxic process to motivate in-situ sludge reduction and enhance denitrification under an effective electron shuttle among organic matter, nitrogen, and Fe. The addition of 15 mg L-1 Fe(II) resulted in a sludge reduction efficiency reached 32.0% with a decreased effluent nitrate concentration of 33.3%. This was mostly attributed to the electron transfer from Fe(II) to organic matters and nitrogen species in OARFe. The participation of Fe(II) led to the upregulation of Geothrix and Terrimonas, which caused active organic matter hydrolysis and cell lysis to stimulate the release of extracellular polymeric substances (EPS) and substance transfer between each layer of EPS. The higher utilization of released bioavailable dissolved organic matter improved endogenous denitrification, which can be combined with iron autotrophic denitrification to realize multiple electron donor-based nitrogen removal pathways, resulting in an increased nitrate removal rate of 58.2% in the absence of external carbon sources. These functional bacteria associated with the transformation of nitrogen and carbon and cycling between ferrous and ferric ions were enriched in OARFe, which contributed to efficient electron transport occurred both inside and outside the cell and increased 2,3,5-triphenyltetrazolium chloride electronic transport system activity by 46.9%. This contributed to the potential operational costs of chemical addition and sludge disposal of Fe-AO being 1.9 times lower than those of conventional A2O processes. These results imply that the addition of ferrous ions to an oligotrophic anaerobic zone for wastewater treatment has the potential for low-cost pollution control.

Sulfate Doping Promotes Agglomeration of Calcium Fluoride Crystals.

Calcium salt precipitation is an effective solution to wastewater fluoride pollution. The purity and precipitation efficiency of calcium fluoride is critical for its removal and recovery. This study aimed to reveal the role of coexisting sulfates in the precipitation of calcium fluoride. A low sulfate concentration promoted calcium fluoride precipitation. The size of calcium fluoride-aggregated particle clusters increased from 750 to 2000 nm when the molar ratio of sulfate to fluoride was increased from 0 to 3:100. Sulfate doped in the calcium fluoride crystals neutralized the positive charge of the calcium fluoride. Online atomic force microscopy measurements showed that sulfate reduced the repulsive force between calcium fluoride crystals and increased the adhesion force from 1.62 to 2.46 nN, promoting the agglomeration of calcium fluoride crystals. Sulfate improved the precipitation efficiency of calcium fluoride by promoting agglomeration; however, the purity of calcium fluoride was reduced by doping. Sulfate reduced the induction time of calcium fluoride crystallization and improved the nucleation rate of calcium fluoride. Sulfate should be retained to improve the precipitation of calcium fluoride and to avoid its loss from the effluents. However, it is necessary to separate sulfate from fluoride to obtain high-purity calcium fluoride. Therefore, sulfate concentration regulation in high-fluoride wastewater is key to achieving the efficient removal and recovery of fluoride ions.

Can "Risk-Sharing" Mechanisms Help Clonal Aquatic Plants Mitigate the Stress of Nanoplastics?

Most aquatic plants applied to ecological restoration have demonstrated a clonal growth pattern. The risk-spreading strategy plays a crucial role in facilitating clonal plant growth under external environmental stresses via clonal integration. However, the effects of different concentrations of nanoplastics (NPs) on the growth traits of clonal aquatic plants are not well understood. Therefore, this study aimed to investigate the impact of NPs exposure on seedlings of parent plants and connected offspring ramets. A dose response experiment (0.1, 1, and 10 mg L-1) showed that the growth of Eichhornia crassipes (water hyacinth) was affected by 100 nm polystyrene nanoplastics after 28 days of exposure. Tracer analysis revealed that NPs are accumulated by parent plants and transferred to offspring ramets through stolon. Quantification analysis showed that when the parent plant was exposed to 10 mg L-1 NPs alone for 28 days, the offspring ramets contained approximately 13 ± 2 µg/g NPs. In the case of connected offspring ramets, leaf and root biomass decreased by 24%-51% and 32%-51%, respectively, when exposed to NP concentrations ranging from 0.1 to 10 mg L-1. Excessive enrichment of NPs had a detrimental effect on the photosynthetic system, decreasing the chlorophyll content and nonphotochemical quenching. An imbalance in the antioxidant defense systems, which were unable to cope with the oxidative stress caused by NP concentrations, further damaged various organs. The root system can take up NPs and then transfer them to the offspring through the stolon. Interference effects of NPs were observed in terms of root activity, metabolism, biofilm composition, and the plant's ability to purify water. However, the risk-spreading strategy employed by parent plants (interconnected offspring ramets) offered some relief from NP-induced stress, as it increased their relative growth rate by 1 to 1.38 times compared to individual plants. These findings provide substantial evidence of the high NP enrichment capacity of E. crassipes for ecological remediation. Nevertheless, we must also remain aware of the environmental risk associated with the spread of NPs within the clonal system of E. crassipes, and contaminated cloned individuals need to be precisely removed in a timely manner to maintain normal functions.

Space aquatic chemistry: A roadmap for drinking water treatment in microgravity.

Rapid advancement in aerospace technology has successfully enabled long-term life and economic activities in space, particularly in Low Earth Orbit (LEO), extending up to 2000 km from the mean sea level. However, the sustainance of the LEO Economy and its Environmental Control and Life Support System (ECLSS) still relies on a regular cargo supply of essential commodities (e.g., water, food) from Earth, for which there still is a lack of adequate and sustainable technologies. One key challenge in this context is developing water treatment technologies and standards that can perform effectively under microgravity conditions. Solving this technical challenge will be a milestone in providing a scientific basis and the necessary support mechanisms for establishing permanent bases in outer space and beyond. To identify clues towards solving this challenge, we looked back at relevant scientific research exploring novel technologies and standards for deep space exploration, also considering feedback for enhancing these technologies on land. Synthesizing our findings, we share our outlook for the future of drinking water treatment in microgravity. We also bring up a new concept for space aquatic chemistry, considering the closed environment of engineered systems operating in microgravity.

Enhanced oxidation of organic pollutants by regulating the interior reaction region of reactive electrochemical membranes.

Reactive electrochemical membrane (REM) emerges as an attractive strategy for the elimination of refractory organic pollutants that exist in wastewater. However, the limited reaction sites in traditional REMs greatly hinder its practical application. Herein, a feed-through coating methodology was developed to realize the uniform loading of SnO2-Sb catalysts on the interior surface of a REM. The uniformly coated REM (Unif-REM) exhibited 2.4 times higher reaction kinetics (0.29 min-1) than that of surface coated REM (Surf-REM) for the degradation of 2 mM 4-chlorophenol (4-CP), rendering an energy consumption as low as 0.016 kWh gTOC-1. The fast degradation of various emerging contaminants, e.g., sulfamethoxazole (SMX), ofloxacin (OFLX), and tetracycline (TC), also confirms its superior oxidation capability. Besides, the Unif-REM exhibited good performance in generating hydroxyl radicals (•OH) and a relatively long service lifetime. The simulation of spatial current distribution demonstrates that the interior reaction region in the Unif-REM channels can be drastically extended, thereby maximizing the surface coupling of mass diffusion and electron transfer. This study offers an in-depth look at the spatially confined reactions in REM and provides a reference for the design of electrochemical systems with economically efficient water purification.

Advanced treatment of coking wastewater: Recent advances and prospects.

Advanced treatment of refractory industrial wastewater is still a challenge. Coking wastewater is one of coal chemical wastewater, which contains various refractory organic pollutants. To meet the more and more rigorous discharge standard and increase the reuse ratio of coking wastewater, advanced treatment process must be set for treating the biologically treated coking wastewater. To date, several advanced oxidation processes (AOPs), including Fenton, ozone, persulfate-based oxidation, and iron-carbon micro-electrolysis, have been applied for the advanced treatment of coking wastewater. However, the performance of different advanced treatment processes changed greatly, depending on the components of coking wastewater and the unique characteristics of advanced treatment processes. In this review article, the state-of-the-art advanced treatment process of coking wastewater was systematically summarized and analyzed. Firstly, the major organic pollutants in the secondary effluents of coking wastewater was briefly introduced, to better understand the characteristics of the biologically treated coking wastewater. Then, the performance of various advanced treatment processes, including physiochemical methods, biological methods, advanced oxidation methods and combined methods were discussed for the advanced treatment of coking wastewater in detail. Finally, the conclusions and remarks were provided. This review will be helpful for the proper selection of advanced treatment processes and promote the development of advanced treatment processes for coking wastewater.

Polydopamine-Modified 2D Iron (II) Immobilized MnPS3 Nanosheets for Multimodal Imaging-Guided Cancer Synergistic Photothermal-Chemodynamic Therapy.

Manganese phosphosulphide (MnPS3 ), a newly emerged and promising member of the 2D metal phosphorus trichalcogenides (MPX3 ) family, has aroused abundant interest due to its unique physicochemical properties and applications in energy storage and conversion. However, its potential in the field of biomedicine, particularly as a nanotherapeutic platform for cancer therapy, has remained largely unexplored. Herein, a 2D "all-in-one" theranostic nanoplatform based on MnPS3 is designed and applied for imaging-guided synergistic photothermal-chemodynamic therapy. (Iron) Fe (II) ions are immobilized on the surface of MnPS3 nanosheets to facilitate effective chemodynamic therapy (CDT). Upon surface modification with polydopamine (PDA) and polyethylene glycol (PEG), the obtained Fe-MnPS3 /PDA-PEG nanosheets exhibit exceptional photothermal conversion efficiency (η = 40.7%) and proficient pH/NIR-responsive Fenton catalytic activity, enabling efficient photothermal therapy (PTT) and CDT. Importantly, such nanoplatform can also serve as an efficient theranostic agent for multimodal imaging, facilitating real-time monitoring and guidance of the therapeutic process. After fulfilling the therapeutic functions, the Fe-MnPS3 /PDA-PEG nanosheets can be efficiently excreted from the body, alleviating the concerns of long-term retention and potential toxicity. This work presents an effective, precise, and safe 2D "all-in-one" theranostic nanoplatform based on MnPS3 for high-efficiency tumor-specific theranostics.

Enzyme-enhanced acidogenic fermentation of waste activated sludge: Insights from sludge structure, interfaces, and functional microflora.

Anaerobic fermentation is widely installed to recovery valuable resources and energy as CH4 from waste activated sludge (WAS), and its implementation in developing countries is largely restricted by the slow hydrolysis, poor efficiency, and complicate inert components therein. In this study, enzyme-enhanced fermentation was conducted to improve sludge solubilization from 283 to 7728 mg COD/L and to enhance volatile fatty acids (VFAs) yield by 58.6 % as compared to the conventional fermentation. The rapid release of organic carbon species, especially for tryptophan- and tyrosine-like compounds, to outer layer of extracellular polymeric substance (EPS) occurred to reduce the structural complexity and improve the sludge biodegradability towards VFAs production. Besides, upon enzymatic pretreatment the simultaneous exposure of hydrophilic and hydrophobic groups on sludge surfaces increased the interfacial hydrophilicity. By quantitative analysis via interfacial thermodynamics and XDLVO theory, it was confirmed that the stronger hydrophilic repulsion and energy barriers in particle interface enhanced interfacial mass transfer and reactions involved in acidogenic fermentation. Meanwhile, these effects stimulate the fermentation functional microflora and predominant microorganism, and the enrichment of the hydrolytic and acid-producing bacteria in metaphase and the proliferation of acetogenic bacteria, e.g., Rubrivivax (+9.4 %), in anaphase also benefits VFAs formation. This study is practically valuable to recovery valuable VFAs as carbon sources and platform chemicals from WAS and agriculture wastes.

Al and Mn speciation changes during the pre-oxidation with potassium permanganate and coagulation removing natural organic matter and its membrane fouling behavior.

In this study, we systematically explore coagulation behavior, ultrafiltration membrane fouling behavior and the mechanism involved in during the process of pre-oxidation of potassium permanganate and coagulation of aluminum chloride at different condition to treat model pollutants (humic acid, HA) and natural water. The KMnO4 pre-oxidation significantly enhances flocs formation, and for HA artificial water the flocs size increases from 82 to 122 µm at pH 5.5, from 63 to 185 µm at pH 7.0 and from 0 to 75 µm at pH 8.5, respectively, as for natural water it increases from 72 to 139 µm. The enhanced coagulation at pH 5.5 is attributed to the increased polymeric Al speciation after pre-oxidation along with the generated Mn2+ damaging the electric double layer structure. And for pH 8.5 it is mainly caused by the in-situ MnO2 as combination nuclei during pre-oxidation. Besides, for pH 7.0, the combined effect of in-situ MnO2 and the increased polymeric Al speciation both contribute to improvement of the coagulation. What's more, the enhanced Al coagulation by pre-oxidation of KMnO4 also helps alleviate the membrane fouling for both HA artificial water and natural water, and a much rougher surface with larger flocs forms after KMnO4-aided Al coagulation filtration. This study provides an alternative perspective on the mechanism of pre-oxidation coagulation process.

Unveiling the spatially confined oxidation processes in reactive electrochemical membranes.

Electrocatalytic oxidation offers opportunities for sustainable environmental remediation, but it is often hampered by the slow mass transfer and short lives of electro-generated radicals. Here, we achieve a four times higher kinetic constant (18.9 min-1) for the oxidation of 4-chlorophenol on the reactive electrochemical membrane by reducing the pore size from 105 to 7 µm, with the predominate mechanism shifting from hydroxyl radical oxidation to direct electron transfer. More interestingly, such an enhancement effect is largely dependent on the molecular structure and its sensitivity to the direct electron transfer process. The spatial distributions of reactant and hydroxyl radicals are visualized via multiphysics simulation, revealing the compressed diffusion layer and restricted hydroxyl radical generation in the microchannels. This study demonstrates that both the reaction kinetics and the electron transfer pathway can be effectively regulated by the spatial confinement effect, which sheds light on the design of cost-effective electrochemical platforms for water purification and chemical synthesis.

Enhanced Hydrosaturation Selectivity and Electron Transfer for Electrocatalytic Chlorophenols Hydrogenation on Ru Sites.

Electrocatalytic hydrogenation is acknowledged as a promising strategy for chlorophenol dechlorination. However, the widely used Pd catalysts exhibit drawbacks, such as high costs and low selectivity for phenol hydrosaturation. Herein, we demonstrate the potential and mechanism of Ru in serving as a Pd substitute using 2,4,6-trichlorophenol (TCP) as a model pollutant. Up to 99.8% TCP removal efficiency and 99% selectivity to cyclohexanol, a value-added compound with an extremely low toxicity, were achieved on the Ru electrode. In contrast, only 66% of TCP was removed on the Pd electrode, with almost no hydrosaturation selectivity. The superiority of Ru over Pd was especially noteworthy in alkaline conditions or the presence of interfering species such as S2-. The theoretical simulation demonstrates that Ru possesses a hydrodechlorination energy barrier of 0.72 eV, which is comparable to that on Pd. Meanwhile, hydrosaturation requires an activation energy of 0.69 eV on Ru, which is much lower than that on Pd (0.92 eV). The main reaction mechanism on Ru is direct electron transfer, which is distinct from that on Pd (indirect pathway via atomic hydrogen, H*). This work thereby provides new insights into designing cost-effective electrocatalysts for halogenated phenol detoxification and resource recovery.

Stimuli-Responsive Functional Micro-/Nanorobots: A Review.

Stimuli-responsive functional micro-/nanorobots (srFM/Ns) are a class of intelligent, efficient, and promising microrobots that can react to external stimuli (such as temperature, light, ultrasound, pH, ion, and magnetic field) and perform designated tasks. Through adaptive transformation into the corresponding functional forms, they can perfectly match the demands depending on different applications, which manifest extremely important roles in targeted therapy, biological detection, tissue engineering, and other fields. Promising as srFM/Ns can be, few reviews have focused on them. It is therefore necessary to provide an overview of the current development of these intelligent srFM/Ns to provide clear inspiration for further development of this field. Hence, this review summarizes the current advances of stimuli-responsive functional microrobots regarding their response mechanism, the achieved functions, and their applications to highlight the pros and cons of different stimuli. Finally, we emphasize the existing challenges of srFM/Ns and propose possible strategies to help accelerate the study of this field and promote srFM/Ns toward actual applications.

In situ regulation of selectivity and permeability by electrically tuning pore size in trans-membrane ion process.

Regulating ion transport behavior through pore size variation is greatly attractive for membrane to meet the need for precise separation, but fabricating nanofiltration (NF) membranes with tunable pore size remains a huge challenge. Herein, a NF membrane with electrically tunable pores was fabricated by intercalating polypyrrole into reduced graphene oxide interlayers. As the potential switches from reduction to oxidation, the membrane pore size shrinks by 11%, resulting in a 16.2% increase in salt rejection. The membrane pore size expands/contracts at redox potentials due to the polypyrrole volume swelling/shrinking caused by the insertion/desertion of cations, respectively. In terms of the inserted cation, Na+ and K+ induce larger pore-size stretching range for the membrane than Ca2+ due to greater binding energy and larger doping amount. Such an electrical response characteristic remained stable after multiple cycles and enabled application in ion selective separation; e.g., the Na+/Mg2+ separation factor in the reduced state is increased by 41% compared to that in the oxide state. This work provides electrically tunable nanochannels for high-precision separation applications such as valuable substance purification and resource recovery from wastewater.

Dehydration-enhanced ion-pore interactions dominate anion transport and selectivity in nanochannels.

State-of-the-art ion-selective membranes with ultrahigh precision are of significance for water desalination and energy conservation, but their development is limited by the lack of understanding of the mechanisms of ion transport at the subnanometer scale. Herein, we investigate transport of three typical anions (F-, Cl-, and Br-) under confinement using in situ liquid time-of-flight secondary ion mass spectrometry in combination with transition-state theory. The operando analysis reveals that dehydration and related ion-pore interactions govern anion-selective transport. For strongly hydrated ions [(H2O)nF- and (H2O)nCl-], dehydration enhances ion effective charge and thus the electrostatic interactions with membrane, observed as an increase in decomposed energy from electrostatics, leading to more hindered transport. Contrarily, weakly hydrated ions [(H2O)nBr-] have greater permeability as they allow an intact hydration structure during transport due to their smaller size and the most right-skewed hydration distribution. Our work demonstrates that precisely regulating ion dehydration to maximize the difference in ion-pore interactions could enable the development of ideal ion-selective membranes.

Visible Light-Driven Micromotors in Fuel-Free Environment with Promoted Ion Tolerance.

Light-driven electrophoretic micromotors have gained significant attention recently for applications in drug delivery, targeted therapy, biosensing, and environmental remediation. Micromotors that possess good biocompatibility and the ability to adapt to complex external environments are particularly attractive. In this study, we have fabricated visible light-driven micromotors that could swim in an environment with relatively high salinity. To achieve this, we first tuned the energy bandgap of rutile TiO2 that was hydrothermally synthesized, enabling it to generate photogenerated electron-hole pairs under visible light rather than solely under UV. Next, platinum nanoparticles and polyaniline were decorated onto the surface of TiO2 microspheres to facilitate the micromotors swimming in ion-rich environments. Our micromotors exhibited electrophoretic swimming in NaCl solutions with concentrations as high as 0.1 M, achieving a velocity of 0.47 µm/s without the need for additional chemical fuels. The micromotors' propulsion was generated solely by splitting water under visible light illumination, therefore offering several advantages over traditional micromotors, such as biocompatibility and the ability to operate in environments with high ionic strength. These results demonstrated high biocompatibility of photophoretic micromotors and high potential for practical applications in various fields.

Influence of water quality factors on cake layer 3D structures and water channels during ultrafiltration process.

The three-dimensional (3D) structure of the cake layer, which could be influenced by water quality factors, plays a significant role in the ultrafiltration (UF) efficiency of water purification. However, it remains challenging to precisely reveal the variation of cake layer 3D structures and water channel characteristics. Herein, we systematically report the variation in the cake layer 3D structure at the nanoscale induced by key water quality factors and reveal its influence on water transport, in particular the abundance of water channels within the cake layer. In comparison with pH and Na+, Ca2+ played more significant role in determining cake layer structures. The sandwich-like cake layer, which was induced by the asynchronous deposition of humic acids and sodium alginate (SA), shifted to an isotropic structure when Ca2+ was present due to the Ca2+ bridging. In comparison with the sandwich-like structure, the isotropic cake layer has higher fractions of free volume (voids) and more water channels, leading to a 147% improvement in the water transport coefficient, 60% reduction in the cake layer resistance, and 21% increase in the final membrane specific flux. Our work elucidates a structure-property relationship where improving the isotropy of the cake layer 3D structure is conducive to the optimization of water channels and water transport within cake layers. This could inspire tailored regulation strategies for cake layers to enhance the UF efficiency of water purification.

Steric Hindrance-Induced Dehydration Promotes Cation Selectivity in Trans-Subnanochannel Transport.

Dehydration is a basic phenomenon in ion transport through confined nanochannels, but how it affects ion trans-membrane selectivity has not been understood due to a lack of characterization techniques and suitable pore structures. Herein, hydration number distributions of typical alkali metal ions were characterized by combining uniform subnanochannels of ZIF-8-based membranes with the in situ liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS) technique, revealing that steric hindrance induced ion dehydration through neutral confined ZIF-8 windows. The reduction in size due to partial dehydration increased the intrapore velocity for monovalent cations. The highest entropy value with maximum size changes resulting from dehydration drove fast and efficient selective transport of Li+ over other alkaline metal ions, leading to a Li+/Rb+ selectivity of 5.2. The dehydration at the entrance of membrane pores was shown to account for the majority of overall barriers, being a dominant element for ion transport. High hydration energy (>1500 kJ/mol) hindered the dehydration and transport of typical alkaline earth metal ions, achieving ultrahigh monovalent/bivalent cation selectivity (∼104). These findings uncover the crucial role of dehydration energy barriers and size-based entropy barriers in ion selectivity of trans-subnanochannel transport, providing guidelines for designing selective membranes with specific pore sizes to promote the dehydration of desired solutes.