Revealing an Extended Adsorption/Insertion-Filling Sodium Storage Mechanism in Petroleum Coke-Derived Amorphous Carbon.

Amorphous carbon holds great promise as anode material for sodium-ion batteries due to its cost-effectiveness and good performance. However, its sodium storage mechanism, particularly the insertion process and origin of plateau capacity, remains controversial. Here, an extended adsorption/insertion-filling sodium storage mechanism is proposed using petroleum coke-derived amorphous carbon as a multi-microcrystalline model. Combining in situ X-ray diffraction, in situ Raman, theoretical calculations, and neutron scattering, the effective storage form and location of sodium ions in amorphous carbon are revealed. The sodium adsorption at defect sites leads to a high-potential sloping capacity. The sodium insertion process occurs in both the pseudo-graphite phase (d002 > 0.370 nm) and graphite-like phase (0.345 ≤ d002 < 0.370 nm) rather than the graphite phase, contributing to low-potential sloping capacity. The sodium filling into accessible closed pores forms quasi-metallic sodium clusters, contributing to plateau capacity. The threshold of the effective interlayer spacing for sodium insertion is extended to 0.345 nm, breaking the consensus of insertion interlayer threshold and enhancing understanding of closed pore filling. The extended adsorption/insertion-filling mechanism explains the sodium storage behavior of amorphous carbon with different microstructures, providing theoretical guidance for the rational design of high-performance amorphous carbon anodes.

Synthesis of Highly Porous Lignin-Sulfonate Sulfur-Doped Carbon for Efficient Adsorption of Sodium Diclofenac and Synthetic Effluents.

Herein, a novel sulfur-doped carbon material has been synthesized via a facile and sustainable single-step pyrolysis method using lignin-sulfonate (LS), a by-product of the sulfite pulping process, as a novel carbon precursor and zinc chloride as a chemical activator. The sulfur doping process had a remarkable impact on the LS-sulfur carbon structure. Moreover, it was found that sulfur doping also had an important impact on sodium diclofenac removal from aqueous solutions due to the introduction of S-functionalities on the carbon material's surface. The doping process effectively increased the carbon specific surface area (SSA), i.e., 1758 m2 g-1 for the sulfur-doped and 753 m2 g-1 for the non-doped carbon. The sulfur-doped carbon exhibited more sulfur states/functionalities than the non-doped, highlighting the successful chemical modification of the material. As a result, the adsorptive performance of the sulfur-doped carbon was remarkably improved. Diclofenac adsorption experiments indicated that the kinetics was better described by the Avrami fractional order model, while the equilibrium studies indicated that the Liu model gave the best fit. The kinetics was much faster for the sulfur-doped carbon, and the maximum adsorption capacity was 301.6 mg g-1 for non-doped and 473.8 mg g-1 for the sulfur-doped carbon. The overall adsorption seems to be a contribution of multiple mechanisms, such as pore filling and electrostatic interaction. When tested to treat lab-made effluents, the samples presented excellent performance.

High-efficient removal of tebuconazole from aqueous solutions using P-doped corn straw biochar: Performance, mechanism and application.

Due to the serious threat posed by tebuconazole to the aquatic ecosystem, it is imperative to develop a highly efficient adsorbent material for the sustainable remediation of tebuconazole-contaminated water. Herein, a phosphorus (P)-doped biochar from corn straw and H3PO4 was fabricated by one-step pyrolysis for tebuconazole adsorption. Results showed that the P-doped biochar produced at 500℃ (PBC500) possesses a large specific surface area (SSA=869.6 m2/g), abundant surface functional groups, and the highest tebuconazole adsorption capacity (429.6 mg/g). The adsorption of tebuconazole on PBC500 followed pseudo-second-order kinetics and Langmuir adsorption isotherm models. Thermodynamic calculations indicated that the adsorption of tebuconazole by PBC500 was a spontaneous, endothermic process with a random increase. Adsorption mechanism mainly involves pore filling, π-π interactions, hydrogen bonding, and hydrophobic interaction. Moreover, PBC500 demonstrated robust anti-interference capabilities in adsorbing tebuconazole from diverse water sources and exhibited excellent reusability, underscoring its potential for a broad array of practical applications.

A simple model for predicting the hydraulic conductivity of MICP-treated sand.

In this research paper, we introduce a novel and sustainable approach for forecasting the hydraulic conductivity of sand layers subjected to microbial-induced carbonate precipitation (MICP) to mitigate the diffusion of toxic pollutants. The proposed model uniquely integrates the impact of varying CaCO3 contents on the void ratio and estimates the average particle size of CaCO3 crystals through scanning electron microscopy (SEM) analysis. By incorporating these parameters into the K-C equation, a simplified predictive model is formulated for assessing the hydraulic conductivity of MICP-treated sand layers. The model's effectiveness is validated through comparison with experimental data and alternative models. The outcomes demonstrate a substantial reduction in hydraulic conductivity, with a decrease ranging between 93 and 97% in the initial assessment and a decrease between 67 and 92% in the follow-up assessment, both at 10% CaCO3 content. Notably, the hydraulic conductivity shows an initial sharp decrease followed by stabilization. These findings provide valuable insights into improving the prediction of hydraulic conductivity in MICP-treated sand layers, promoting a sustainable method for preventing pollution dispersion.

Modified Membranes for Redox Flow Batteries-A Review.

In this review, the state of the art of modified membranes developed and applied for the improved performance of redox flow batteries (RFBs) is presented and critically discussed. The review begins with an introduction to the energy-storing chemical principles and the potential of using RFBs in the energy transition in industrial and transport-related sectors. Commonly used membrane modification techniques are briefly presented and compared next. The recent progress in applying modified membranes in different RFB chemistries is then critically discussed. The relationship between a given membrane modification strategy, corresponding ex situ properties and their impact on battery performance are outlined. It has been demonstrated that further dedicated studies are necessary in order to develop an optimal modification technique, since a modification generally reduces the crossover of redox-active species but, at the same time, leads to an increase in membrane electrical resistance. The feasibility of using alternative advanced modification methods, similar to those employed in water purification applications, needs yet to be evaluated. Additionally, the long-term stability and durability of the modified membranes during cycling in RFBs still must be investigated. The remaining challenges and potential solutions, as well as promising future perspectives, are finally highlighted.

Revisiting Lithium- and Sodium-Ion Storage in Hard Carbon Anodes.

The galvanostatic lithiation/sodiation voltage profiles of hard carbon anodes are simple, with a sloping drop followed by a plateau. However, a precise understanding of the corresponding redox sites and storage mechanisms is still elusive, which hinders further development in commercial applications. Here, a comprehensive comparison of the lithium- and sodium-ion storage behaviors of hard carbon is conducted, yielding the following key findings: 1) the sloping voltage section is presented by the lithium-ion intercalation in the graphitic lattices of hard carbons, whereas it mainly arises from the chemisorption of sodium ions on their inner surfaces constituting closed pores, even if the graphitic lattices are unoccupied; 2) the redox sites for the plateau capacities are the same as those for the closed pores regardless of the alkali ions; 3) the sodiation plateau capacities are mostly determined by the volume of the available closed pore, whereas the lithiation plateau capacities are primarily affected by the intercalation propensity; and 4) the intercalation preference and the plateau capacity have an inverse correlation. These findings from extensive characterizations and theoretical investigations provide a relatively clear elucidation of the electrochemical footprint of hard carbon anodes in relation to the redox mechanisms and storage sites for lithium and sodium ions, thereby providing a more rational design strategy for constructing better hard carbon anodes.

Two-stage preparation of highly mesoporous carbon for super-adsorption of paracetamol and tetracycline in water: Important contribution of pore filling and π-π interaction.

This study aimed to develop an extremely highly porous activated carbon derived from soybean curd residues (SCB-AC) through two-step pyrolyzing coupled with KOH activating process and then apply it for removing paracetamol (PRC) and tetracycline (TCH) from water. The optimal conditions for chemical activation were 800 °C and the ratio of KOH to material (4/1; wt./wt.). SCB-AC adsorbents (before and after adsorption) were characterized by Brunauer-Emmet-Teller (BET) analyser, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy, and Raman spectroscopy. Adsorption kinetics, isotherm, and thermodynamics were concluded under batch experiments. The effects of pH (2-10) and NaCl (0-1 M) on adsorption processes were investigated. Reusable properties of laden SCB-AC were evaluated by studying desorption and cycles of adsorption/desorption. Results indicated that SCB-AC exhibited a large specific surface area (3306 m2/g) and high total pore volume (2.307 cm3/g), with mesoporous volume accounting for 86.9%. Its porosity characteristics (average pore width: 2.725 nm) are very appropriate for adsorbing two pharmaceuticals through pore-filling mechanism. Adsorption processes were less affected by the parameters: pH, NaCl, and water matrixes. The kinetics for adsorbing PRC reached a faster equilibrium than that for TCH. The Langmuir maximum adsorption capacity of SCB-AC (pHeq 7.0 and 25 °C) was 1235 mg/g (for adsorbing TCH) and 646 mg/g (PRC). Pore filling (confirmed by BET analyser) and π-π interaction (confirmed by FTIR and Raman spectroscopy) were dominant adsorption mechanisms. Those mechanisms were physisorption (ΔH° = 13.71 and -21.04 kJ/mol for adsorbing TCH and PRC, respectively). SCB-AC can serve as an outstanding material for removing pharmaceuticals from water.

Bipolar Membranes Containing Iron-Based Catalysts for Efficient Water-Splitting Electrodialysis.

Water-splitting electrodialysis (WSED) process using bipolar membranes (BPMs) is attracting attention as an eco-friendly and efficient electro-membrane process that can produce acids and bases from salt solutions. BPMs are a key component of the WSED process and should satisfy the requirements of high water-splitting capability, physicochemical stability, low membrane cost, etc. The water-splitting performance of BPMs can be determined by the catalytic materials introduced at the bipolar junction. Therefore, in this study, several kinds of iron metal compounds (i.e., Fe(OH)3, Fe(OH)3@Fe3O4, Fe(OH)2EDTA, and Fe3O4@ZIF-8) were prepared and the catalytic activities for water-splitting reactions in BPMs were systematically analyzed. In addition, the pore-filling method was applied to fabricate low-cost/high-performance BPMs, and the 50 µm-thick BPMs prepared on the basis of PE porous support showed several times superior toughness compared to Fumatech FBM membrane. Through various electrochemical analyses, it was proven that Fe(OH)2EDTA has the highest catalytic activity for water-splitting reactions and the best physical and electrochemical stabilities among the considered metal compounds. This is the result of stable complex formation between Fe and EDTA ligand, increase in hydrophilicity, and catalytic water-splitting reactions by weak acid and base groups included in EDTA as well as iron hydroxide. It was also confirmed that the hydrophilicity of the catalyst materials introduced to the bipolar junction plays a critical role in the water-splitting reactions of BPM.

Low-Temperature Processed Brookite Interfacial Modification for Perovskite Solar Cells with Improved Performance.

The scaffold layer plays an important role in transporting electrons and preventing carrier recombination in mesoporous perovskite solar cells (PSCs), so the engineering of the interface between the scaffold layer and the light absorption layer has attracted widespread concern. In this work, vertically grown TiO2 nanorods (NRs) as scaffold layers are fabricated and further treated with TiCl4 aqueous solution. It can be found that a thin brookite TiO2 nanoparticle (NP) layer is formed by the chemical bath deposition (CBD) method on the surface of every rutile NR with a low annealing temperature (150 °C), which is beneficial for the infiltration and growth of perovskite. The PSC based on the TiO2 NR/brookite NP structure shows the best power conversion of 15.2%, which is 56.37% higher than that of the PSC based on bare NRs (9.72%). This complex structure presents an improved pore filling fraction and better carrier transport capability with less trap-assisted carrier recombination. In addition, low-annealing-temperature-formed brookite NPs possess a more suitable edge potential for electrons to transport from the perovskite layer to the electron collection layer when compared with high-annealing-temperature-formed anatase NPs. The brookite phase TiO2 fabricated at a low temperature presents great potential for flexible PSCs.

A Composite Membrane with High Stability and Low Cost Specifically for Iron-Chromium Flow Battery.

The iron-chromium flow battery (ICFB), the earliest flow battery, shows promise for large-scale energy storage due to its low cost and inherent safety. However, there is no specific membrane designed that meets the special requirements of ICFBs. To match the harsh operation parameters of ICFBs, we designed and fabricated a composite membrane with high mechanical, chemical, and thermal stability. In the design, a commercial porous polyethylene membrane is selected as the framework material, offering high mechanical stability and reducing the cost. Meanwhile, the Nafion resin is filled in the pores of a porous membrane, which inhibits the transfer of redox-active ions and creates the proton channels via hydrophobic/hydrophilic phase separation. As a result, the composite membrane exhibits high conductivity, selectivity, and stability, especially with almost no swelling at high operating temperatures. Thus, an ICFB with the prepared membrane exhibits a coulombic efficiency of 93.29% at the current density of 80 mA cm-2 and runs stably for over 300 cycles. This work provides an easy method to fabricate high-performance and low-cost membranes specifically for ICFBs and has the potential to promote the development of ICFBs.

Adsorption of soil organic matter by gel-like ferrihydrite and dense ferrihydrite.

Soil is the largest terrestrial carbon pool, and adsorption of soil organic matter (SOM) by ferrihydrite is an essential geochemical process for preservation of organic carbon in soil. Freshly formed gel-like ferrihydrite and seasonally dried dense ferrihydrite are two typical morphologies of ferrihydrite in soil. However, the differences in SOM adsorption by gel-like ferrihydrite and dense ferrihydrite and the underlying mechanisms are unknown. In this study, adsorption of eight SOM or SOM-like compounds by gel-like ferrihydrite and dense ferrihydrite were compared. It was observed that the adsorption capacity of SOM by gel-like ferrihydrite (e.g., 304 mg C/g) was two orders of magnitude higher than that by dense ferrihydrite (e.g., 3.44 mg C/g). SOM adsorbed by the nanosized gel-like ferrihydrite could be mainly attributed to the heteroaggregation, confirmed by not only the TEM images but also the positive linear correlation between adsorption capacity and molecular weight of SOM. However, SOM adsorbed by the microsized dense ferrihydrite should be attributed to the pore-filling adsorption with molecular sieve effects, confirmed by the negative linear correlation between adsorption capacity and molecular weight of SOM. The obtained results could provide a new insight to understand the preservation of organic carbon by ferrihydrite in soil.

Comparative study on characteristics and mechanism of levofloxacin adsorption on swine manure biochar.

This study evaluated the relationship between pyrolysis temperature (300-900 ℃), characteristics of swine manure (SM)-derived biochar (BC), and its adsorption of levofloxacin (LEV). The surface structure and chemistry of SM-derived BCs were characterized using Brunauer-Emmett-Teller analysis, scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. According to the characteristic analysis, the surface area and graphitization degree of SM-derived BC increased as temperature rose. The highest adsorption capacity was achieved by BC-900 (158 mg/g); this level was higher than that achieved in previous studies and comparable to that of commercial activated carbons. Characterization and adsorption experiments indicated that pore-filling, π-π stacking interaction, π-π electron donor-acceptor, H-bonding, and hydrophobic interactions each played a critical role in the adsorption of LEV on SM-derived BC. Collectively, this study confirms the potential utility of SM-derived BC for the removal of antibiotics.

Characterization of Drugs with Good Glass Formers in Loaded-Mesoporous Silica and Its Theoretical Value Relevance with Mesopores Surface and Pore-Filling Capacity.

The incorporation of a drug into mesoporous silica (MPS) is a promising strategy to stabilize its amorphous form. However, the drug within MPS has shown incomplete release, despite a supersaturated solution being generated. This indicates the determination of maximum drug loading in MPS below what is experimentally necessary to maximize the drug doses in the system. Therefore, this study aimed to characterize the drugs with good glass former loaded-mesoporous silica, determine the maximum drug loading, and compare its theoretical value relevance to monolayer covering the mesoporous (MCM) surface, as well as pore-filling capacity (PFC). Solvent evaporation and melt methods were used to load each drug into MPS. In addition, the glass transition of ritonavir (RTV) and cyclosporine A (CYP), as well as the melting peak of indomethacin (IDM) and saccharin (SAC) in mesoporous silica, were not discovered in the modulated differential scanning calorimetry (MDSC) curve, demonstrating that each drug was successfully incorporated into the mesopores. The amorphization of RTV-loaded MPS (RTV/MPS), CYP-loaded MPS (CYP/MPS), and IDM-loaded MPS (IDM/MPS) were confirmed as a halo pattern in powder X-ray diffraction measurements and a single glass transition event in the MDSC curve. Additionally, the good glass formers, nanoconfinement effect of MPS and silica surface interaction contributed to the amorphization of RTV, CYP and IDM within MPS. Meanwhile, the crystallization of SAC was observed in SAC-loaded MPS (SAC/MPS) due to its weak silica surface interaction and high recrystallization tendency. The maximum loading amount of RTV/MPS was experimentally close to the theoretical amount of MCM, showing monomolecular adsorption of RTV on the silica surface. On the other hand, the maximum loading amount of CYP/MPS and IDM/MPS was experimentally lower than the theoretical amount of MCM due to the lack of surface interaction. However, neither CYP or IDM occupied the entire silica surface, even though some drugs were adsorbed on the MPS surface. Moreover, the maximum loading amount of SAC/MPS was experimentally close to the theoretical amount of PFC, suggesting the multilayers of SAC within the MPS. Therefore, this study demonstrates that the characterization of drugs within MPS, such as molecular size and interaction of drug-silica surface, affects the loading efficiency of drugs within MPS that influence its relevance with the theoretical value of drugs.

New type of pore-snap-off and displacement correlations in imbibition.

HYPOTHESIS: Imbibition of a fluid into a porous material involves the invasion of a wetting fluid in the pore space through piston-like displacement, film and corner flow, snap-off and pore bypassing. These processes have been studied extensively in two-dimensional (2D) porous systems; however, their relevance to three-dimensional (3D) natural porous media is poorly understood. Here, we investigate these pore-scale processes in a natural rock sample using time-resolved 3D (i.e., four-dimensional or 4D) X-ray imaging. EXPERIMENTS: We performed a capillary-controlled drainage-imbibition experiment on an initially brine-saturated carbonate rock sample. The sample was imaged continuously during imbibition using 4D X-ray imaging to visualize and analyze fluid displacement and snap-off processes at the pore-scale. FINDINGS: We discover a new type of snap-off that occurs in pores, resulting in the entrapment of a small portion of the non-wetting phase in pore corners. This contrasts with previously-observed snap-off in throats which traps the non-wetting phase in pore centers. We relate the new type of pore-snap-off to the pinning of fluid-fluid interfaces at rough surfaces, creating contact angles close to 90°. Subsequently, we provide correlations for displacement events as a function of pore-throat geometry. Our findings indicate that having a small throat does not necessarily favor snap-off: the key criterion is the throat radius in relation to the pore radius involved in a displacement event, captured by the aspect ratio.

Modulating the Graphitic Domains of Hard Carbons Derived from Mixed Pitch and Resin to Achieve High Rate and Stable Sodium Storage.

Resin derived hard carbons (HCs) generally demonstrate remarkable electrochemical performance for both sodium ion batteries (SIBs) and potassium-ion batteries (KIBs), but their practical applications are hindered by their high price and high temperature pyrolysis (≈1500 °C). Herein, low-cost pitch is coated on the resin surface to compromise the cost, and meanwhile manipulate the microstructure at a relatively low pyrolysis temperature (1000 °C). HC-0.2P-1000 has a large number of short graphitic layer structures and a relatively large interlayer spacing of 0.3743 nm, as well as ≈1 nm sized nanopores suitable for sodium storage. Consequently, the as produced material demonstrates a superior reversible capacity (349.9 mAh g-1 for SIBs and 321.9 mAh g-1 for KIBs) and excellent rate performance (145.1 mAh g-1 at 20 A g-1 for SIBs, 48.5 mAh g-1 at 20 A g-1 for KIBs). Furthermore, when coupled with Na3 V2 (PO4 )3 as cathode, the full cell exhibits a high energy density of 251.1 Wh kg-1 and excellent stability with a capacity retention of 73.3% after 450 cycles at 1 A g-1 .

A quantitative analysis of cell bridging kinetics on a scaffold using computer vision algorithms.

Tissue engineering involves the seeding of cells into a structural scaffolding to regenerate the architecture of damaged or diseased tissue. To effectively design a scaffold, an understanding of how cells collectively sense and react to the geometry of their local environment is needed. Advances in the development of melt electro-writing have allowed micron and submicron polymeric fibres to be accurately printed into porous, complex and three-dimensional structures. By using melt electrowriting, we created a geometrically relevant in vitro scaffold model to study cellular spatial-temporal kinetics. These scaffolds were paired with custom computer vision algorithms to investigate cell nuclei, cell membrane actin and scaffold fibres over different pore sizes (200-600 µm) and time points (28 days). We find that cells proliferated much faster in the smaller (200 µm) pores which halved the time until confluence versus larger (500 and 600 µm) pores. Our analysis of stained actin fibres revealed that cells were highly aligned to the fibres and the leading edge of the pore filling front, and we found that cells behind the leading edge were not aligned in any particular direction. This study provides a systematic understanding of cellular spatial temporal kinetics within a 3D in vitro model to inform the design of more effective synthetic tissue engineering scaffolds for tissue regeneration. STATEMENT OF SIGNIFICANCE: Advances in the development of melt electro-writing have allowed micron and submicron polymeric fibres to be accurately printed into porous, complex and three-dimensional structures. By using melt electrowriting, we created a geometrically relevant in vitro model to study cellular spatial-temporal kinetics to provide a systematic understanding of cellular spatial temporal kinetics within a 3D in vitro model. The insights presented in this work help to inform the design of more effective synthetic tissue engineering scaffolds by reducing cell culture time; which is valuable information for the implant or lab-grown-meat industries.

Correlations between Properties of Pore-Filling Ion Exchange Membranes and Performance of a Reverse Electrodialysis Stack for High Power Density.

The reverse electrodialysis (RED) stack-harnessing salinity gradient power mainly consists of ion exchange membranes (IEMs). Among the various types of IEMs used in RED stacks, pore-filling ion exchange membranes (PIEMs) have been considered promising IEMs to improve the power density of RED stacks. The compositions of PIEMs affect the electrical resistance and permselectivity of PIEMs; however, their effect on the performance of large RED stacks have not yet been considered. In this study, PIEMs of various compositions with respect to the RED stack were adopted to evaluate the performance of the RED stack according to stack size (electrode area: 5 × 5 cm2 vs. 15 × 15 cm2). By increasing the stack size, the gross power per membrane area decreased despite the increase in gross power on a single RED stack. The electrical resistance of the PIEMs was the most important factor for enhancing the power production of the RED stack. Moreover, power production was less sensitive to permselectivities over 90%. By increasing the RED stack size, the contributions of non-ohmic resistances were significantly increased. Thus, we determined that reducing the salinity gradients across PIEMs by ion transport increased the non-ohmic resistance of large RED stacks. These results will aid in designing pilot-scale RED stacks.

Sorption of organic compounds by pyrolyzed humic acids.

Humic acids (HAs) are frequently subjected to pyrolysis and carbonization by wildfires, which could significantly change the sorption of organic contaminants and their environmental risks in natural system. In previous studies, sorption of organic compounds was investigated for HAs pyrolyzed at temperature below 330 °C, but not for HAs pyrolyzed at higher temperature. Therefore, in this study, sorption of 22 typical organic compounds by HAs pyrolyzed at a series of temperatures from 300 to 700 °C was investigated. Sorption of organic compounds was dominated by nonlinear partition for HAs pyrolyzed at low temperature (e.g., 300 and 400 °C) due to the aliphatic and nonporous structures of pyrolyzed humic acids (PyHAs), while it was dominated by pore-filling adsorption for HAs pyrolyzed at high temperature (e.g., 700 °C) due to the aromatic and porous structures of PyHAs. For HAs pyrolyzed at moderate temperature (e.g., 450, 500 and 600 °C), both nonlinear partition and pore-filling adsorption were responsible for the sorption of organic compounds. Meanwhile, the contribution of pore-filling adsorption to overall sorption increased but the contribution of nonlinear partition decreased with the increasing pyrolytic temperature of PyHAs, attributed to the structure change of PyHAs from aliphatic and nonporous to the aromatic and porous. Moreover, with the increasing pyrolytic temperature of PyHAs, sorption affinity of organic compounds increased, while the change of sorption capacity could be explained by the decrease of nonlinear partition and the increase of pore-filling adsorption. The obtained results could help to evaluate the transport, bioavailability and health risks of organic contaminants in the environment.

Crosslinked Pore-Filling Anion Exchange Membrane Using the Cylindrical Centrifugal Force for Anion Exchange Membrane Fuel Cell System.

In this study, novel crosslinked pore-filling membranes were fabricated by using a centrifugal force from the cylindrical centrifugal machine. For preparing these crosslinked pore-filling membranes, the poly(phenylene oxide) containing long side chains to improve the water management (hydrophilic), porous polyethylene support (hydrophobic) and crosslinker based on the diamine were used. The resulting membranes showed a uniform thickness, flexible and transparent because it is well filled. Among them, PF-XAc-PPO70_25 showed good mechanical properties (56.1 MPa of tensile strength and 781.0 MPa of Young's modulus) and dimensional stability due to the support. In addition, it has a high hydroxide conductivity (87.1 mS/cm at 80 °C) and low area specific resistance (0.040 Ω·cm2), at the same time showing stable alkaline stability. These data outperformed the commercial FAA-3-50 membrane sold by Fumatech in Germany. Based on the optimized properties, membrane electrode assembly using XAc-PPO70_25 revealed excellent cell performance (maximum power density: 239 mW/cm2 at 0.49 V) than those of commercial FAA-3-50 Fumatech anion exchange membrane (maximum power density: 212 mW/cm2 at 0.54 V) under the operating condition of 60 °C and 100% RH as well. It was expected that PF-XAc-PPO70_25 could be an excellent candidate based on the results superior to those of commercial membranes in these essential characteristics of fuel cells.

Sorption and desorption of seven steroidal synthetic progestins in five agricultural soil-water systems.

Manure fertilization and wastewater irrigation can introduce the biologically potent synthetic progestins into agricultural soils, causing endocrine disruption in organisms of nearby surface waters. Therefore, this study investigated the sorption and desorption potential of etonogestrel, medroxyprogesterone, gestodene, norgestrel, cyproterone acetate, levonorgestrel, and dienogest in five agricultural soil-water systems. Sorption data were well-described by the linear sorption model. In most batch systems, cyproterone acetate exhibited the highest affinities for soils, followed by etonogestrel, medroxyprogesterone, levonorgestrel, gestodene, norgestrel, and dienogest. The sorption magnitudes (logKoc or logKd) were significantly correlated with the progestin hydrophobicities (R2 = 0.72-0.86, p < 0.05). The Kd values of the progestins were also significantly correlated with organic carbon content and pore volumes of the soils (R2 = 0.68-0.98, p < 0.05). In addition, 0.5 M urea resulted in 3-19% decreases in Kd values of the progestins. Taken together, these data indicated that hydrophobic partitioning interaction, hydrogen bonding interaction, and pore filling were the sorption mechanisms for the progestins in soil-water systems. No significant desorption hysteresis was observed for the progestins, indicating that they can be readily desorbed under rainfall or irrigation events. Based on the sorption and desorption data, we estimated the dynamic transport of the progestins in conventional agricultural management systems, and predicted the concentrations of the progestins as a function of soil-sorbed concentration, water-soil ratio, and dilution factor of receiving waters. This study will improve the understanding of the risks posed by the progestins under field-scale hydrological conditions.