Template-Free Synthesis of High Dehydration Performance CHA Zeolite Membranes with Increased Si/Al Ratio Using SSZ-13 Seeds.

Pervaporation is an energy-efficient alternative to conventional distillation for water/alcohol separations. In this work, a novel CHA zeolite membrane with an increased Si/Al ratio was synthesized in the absence of organic templates for the first time. Nanosized high-silica zeolite (SSZ-13) seeds were used for the secondary growth of the membrane. The separation performance of membranes in different alcohol-aqueous mixtures was measured. The effects of water content in the feed and the temperature on the separation performance using pervaporation and vapor permeation were also studied. The best membrane showed a water/ethanol separation factor above 100,000 and a total flux of 1.2 kg/(m2 h) at 348 K in a 10 wt.% water-ethanol mixed solution. A membrane with high performance and an increased Si/Al ratio is promising for the application of alcohol dehydration.

Synthesis optimization and separation mechanism of ZSM-5 zeolite membranes for pervaporation dehydration of organic solvents.

Pervaporation (PV), as an energy-efficient mixture separation technology, plays an important role in the chemical industry. In this work, no organic templates were needed to produce high-performance ZSM-5 membranes with an extremely low Si/Al ratio of 3.3 on α-Al2O3 tubular supports using 100 nm nanoseeds. The effects of preparation parameters on the crystalline phase structures, micromorphologies, and PV separation performance of ZSM-5 membranes were comprehensively investigated. The results revealed that the Si/Al ratio of gels significantly affected both the Si/Al ratio and the crystal orientation of the final ZSM-5 membrane. The optimized ZSM-5 membrane with a thickness of 1.8 µm was utilized to dehydrate various organic solvents via PV, and the influence of the operating parameters on PV dehydration performance was evaluated and is described herein. Furthermore, the permeation behaviors of single gases and PV were examined using permeate molecules within a similar size range to reveal the PV mechanism of the ZSM-5 membrane. The results demonstrated that gas permeation followed Knudsen diffusion, while PV permeation was decreased with decreases in the affinity of molecules, revealing an adsorption-diffusion mechanism that dominated PV dehydration through the ZSM-5 membrane. Moreover, the as-synthesized ZSM-5 membrane had good water permselectivity for water/acetone (e.g., total flux = 1.03 kg/(m2 h), α = 307) and for water/isopropanol (e.g., total flux = 1.49 kg/(m2 h), α = 1070) mixtures compared with other membranes reviewed in the literature. The synthesized ZSM-5 membrane also exhibited excellent reproducibility, high stability, and attractive PV separation performance, demonstrating its significant potential application in the PV dehydration of organic solvents.

Differential methylation patterns from clusters associated with glucose metabolism: evidence from a Shanghai twin study.

Aim: To assess the associations between genome-wide DNA methylation (DNAm) and glucose metabolism among a Chinese population, in particular the multisite correlation. Materials & methods: Epigenome-wide associations with fasting plasma glucose (FPG) and hemoglobin A1c (HbA1c) were analyzed among 100 Shanghai monozygotic (MZ) twin pairs using the Infinium HumanMethylationEPIC v2.0 BeadChip. We conducted a Pearson's correlation test, hierarchical cluster and pairwise analysis to examine the differential methylation patterns from clusters. Results: Cg01358804 (TXNIP) was identified as the most significant site associated with FPG and HbA1c. Two clusters with hypermethylated and hypomethylated patterns were observed for both FPG and HbA1c. Conclusion: Differential methylation patterns from clusters may provide new clues for epigenetic changes and biological mechanisms in glucose metabolism.

Conductive nanofiltration membranes via in situ PEDOT-polymerization for electro-assisted membrane fouling mitigation.

Nanofiltration (NF) membranes play a pivotal role in water treatment; however, the persistent challenge of membrane fouling hampers their stable application. This study introduces a novel approach to address this issue through the creation of a poly(3,4-ethylenedioxythiophene) (PEDOT)-based conductive membrane, achieved by synergistically coupling interfacial polymerization (IP) with in situ self-polymerization of EDOT. During the IP reaction, the concurrent generation of HCl triggers the protonation of EDOT, activating its self-polymerization into PEDOT. This interwoven structure integrates with the polyamide network to establish a stable selective layer, yielding a remarkable 90 % increase in permeability to 20.4 L m-2 h-1 bar-1. Leveraging the conductivity conferred by PEDOT doping, an electro-assisted cleaning strategy is devised, rapidly restoring the flux to 98.3 % within 5 min, outperforming the 30-minute pure water cleaning approach. Through simulations in an 8040 spiral-wound module and the utilization of the permeated salt solution for cleaning, the electro-assisted cleaning strategy emerges as an eco-friendly solution, significantly reducing water consumption and incurring only a marginal electricity cost of 0.055 $ per day. This work presents an innovative avenue for constructing conductive membranes and introduces an efficient and cost-effective electro-assisted cleaning strategy to effectively combat membrane fouling.

High-Performance FAU Zeolite Membranes Derived from Nano-Seeds for Gas Separation.

In this study, high-performance FAU (NaY type) zeolite membranes were successfully synthesized using small-sized seeds of 50 nm, and their gas separation performance was systematically evaluated. Employing nano-sized NaY seeds and an ultra-dilute reaction solution with a molar composition of 80 Na2O: 1Al2O3: 19 SiO2: 5000H2O, the effects of synthesis temperature, crystallization time, and porous support (α-Al2O3 or mullite) on the formation of FAU membranes were investigated. The results illustrated that further extending the crystallization time or increasing the synthesis temperature led to the formation of a NaP impurity phase on the FAU membrane layer. The most promising FAU membrane with a thickness of 2.7 µm was synthesized on an α-Al2O3 support at 368 K for 8 h and had good reproducibility. The H2 permeance of the membrane was as high as 5.34 × 10-7 mol/(m2 s Pa), and the H2/C3H8 and H2/i-C4H10 selectivities were 183 and 315, respectively. The C3H6/C3H8 selectivity of the membrane was as high as 46, with a remarkably high C3H6 permeance of 1.35 × 10-7 mol/(m2 s Pa). The excellent separation performance of the membrane is mainly attributed to the thin, defect-free membrane layer and the relatively wide pore size (0.74 nm).

Secular trends of low birth weight, preterm birth, and small for gestational age in Shanghai from 2004 to 2020: an age-period-cohort analysis.

BACKGROUND: Although highly heterogeneous among countries, the incidence rates of low birth weight (LBW), preterm birth (PTB), and small for gestational age (SGA) have been increasing globally over the past two decades. To better understand the cause of these secular trends, this study aimed to investigate the effects of age, period, and birth cohort on LBW, PTB, and SGA rates in Shanghai. METHODS: Data from 2,958,695 singleton live births at 24-41 gestational weeks between 2004 and 2020 were obtained for this study. Age-period-cohort models based on Poisson regression were used to evaluate the independent effects of maternal age, delivery period, and maternal birth cohort on the trends in LBW, PTB, and SGA. RESULTS: The overall prevalence rates of LBW, PTB, and SGA were 2.9%, 4.7%, and 9.3%, respectively, and significant changes were observed (average annual change: + 10.7‰, + 9.1‰, -11.9‰) from 2004 to 2020. Cohort effect increased steadily, from 1960 (risk ratio [RR] = 0.71, 95% confidence interval [CI]: 0.65-0.78) to 1993 (RR = 0.97, 95% CI: 0.94-1.01) for LBW and from 1960 (RR = 0.69, 95% CI: 0.64-0.75) to 2004 (RR = 1.02, 95% CI: 0.94-1.12) for PTB. A strong cohort effect was found with the highest risk of SGA (RR = 1.82, 95% CI: 1.72-1.93) in 1960 and the lowest risk (RR = 0.57, 95% CI: 0.54-0.61) in 2004, compared with the reference cohort of 1985. There was a "U-shaped" maternal age effect on LBW and PTB and a weak period effect on the three birth outcomes. CONCLUSIONS: Our findings suggested a significant independent effect of age, period, and birth cohort on the three birth outcomes. The increasing rates of LBW and PTB motivated us to focus on young and advanced pregnant women. Meanwhile, the prevalence of SGA decreased steadily, illustrating the need for further research on the mechanisms underlying these trends.

In Situ Synthesis of Cation-Free Zirconia-Supported Zeolite CHA Membranes for Efficient CO2/CH4 Separation.

Cation-free zirconosilicate zeolite CHA and thin zirconia-supported membranes were in situ synthesized in a fluoride-free gel for the first time. The usage of the ZrO2/Al2O3 composite support inhibited the transportation of aluminum from the support into zeolite membranes. No fluorite source was used for the synthesis of cation-free zeolite CHA membranes, indicating the green property of the synthesis. The thickness of the membrane was only 1.0 µm. The best cation-free zeolite CHA membrane prepared by the green in situ synthesis displayed a high CO2 permeance of 1.1 × 10-6 mol/(m2 s Pa) and CO2/CH4 selectivity of 79 at 298 K and 0.2 MPa pressure drop for an equimolar CO2/CH4 mixture.

Recent Progress in Silicon Carbide-Based Membranes for Gas Separation.

The scale of research for developing and applying silicon carbide (SiC) membranes for gas separation has rapidly expanded over the last few decades. Given its importance, this review summarizes the progress on SiC membranes for gas separation by focusing on SiC membrane preparation approaches and their application. The precursor-derived ceramic approaches for preparing SiC membranes include chemical vapor deposition (CVD)/chemical vapor infiltration (CVI) deposition and pyrolysis of polymeric precursor. Generally, SiC membranes formed using the CVD/CVI deposition route have dense structures, making such membranes suitable for small-molecule gas separation. On the contrary, pyrolysis of a polymeric precursor is the most common and promising route for preparing SiC membranes, which includes the steps of precursor selection, coating/shaping, curing for cross-linking, and pyrolysis. Among these steps, the precursor, curing method, and pyrolysis temperature significantly impact the final microstructures and separation performance of membranes. Based on our discussion of these influencing factors, there is now a good understanding of the evolution of membrane microstructures and how to control membrane microstructures according to the application purpose. In addition, the thermal stability, oxidation resistance, hydrothermal stability, and chemical resistance of the SiC membranes are described. Due to their robust advantages and high separation performance, SiC membranes are the most promising candidates for high-temperature gas separation. Overall, this review will provide meaningful insight and guidance for developing SiC membranes and achieving excellent gas separation performance.

One-Step Scalable Fabrication of Highly Selective Monolithic Zeolite MFI Membranes for Efficient Butane Isomer Separation.

The reproducible fabrication of large-area zeolite membranes for gas separation is still a great challenge. We report the scalable fabrication of high-performance zeolite MFI membranes by single-step secondary growth on the 19-channel alumina monoliths for the first time. The packing density and mechanical strength of the monolithic membranes are much higher for these than for tubular ones. Separation performance of the monolithic membranes toward the butane isomer mixture was comparably evaluated using the vacuum and Wicke-Kallenbach modes. The n-butane permeances and n-butane/i-butane separation factors for the three membranes with an effective area of ∼84 cm2 were >1.0 × 10-7 mol (m2 s Pa)-1 and >50 at 343 K for an equimolar n-butane/i-butane mixture, respectively. We succeeded in scaling up the membrane synthesis with the largest area of 270 cm2 to date which has 1.3 times the area of an industrial 1 m long tubular membrane. Monolith supported zeolite MFI membranes show great potential for industrial n-butane/i-butane separation.

Highly Ordered Nanochannels in a Nanosheet-Directed Thin Zeolite Nanofilm for Precise and Fast CO2 Separation.

Precise molecular and ion separations depend largely on the size and uniformity of the nanochannels in a defect-free microporous nanofilm. Ordered and perpendicular nanochannels with uniform pore size are assembled into a continuous and defect-free film by a "gel nuclei-less" route. The ultrathin (<50 nm) zeolite nanosheets seeding layer induces the formation of defect-free zeolite nanofilms (500-800 nm) with preferential [100] orientation well-aligned to the transport pathway. The large-area and thin silicoaluminophosphate-34 (SAPO-34) nanofilm consisting of uniform and straight nanochannels shows a milestone CO2 permeance of ≈1.0 × 10-5 mol (m2 s Pa)-1 and high CO2 /CH4 and CO2 /N2 selectivities of 135 and 41 in equimolar binary mixtures at room temperature and 0.2 MPa feed pressure, respectively. These results suggest that highly oriented and thin SAPO-34 nanofilms prepared from nanosheets might have great potential for CO2 capture from natural gas, biogas, and flue gas.

Insights into hydrogen bond dynamics at the interface of the charged monolayer-protected Au nanoparticle from molecular dynamics simulation.

The structure and dynamics properties of water molecules at the interface of the charged monolayer-protected Au nanoparticle (MPAN) have been investigated in detail by using classical molecular dynamics simulation. The simulation results demonstrated clearly that a well-defined hydration layer is formed at the interface of MPAN and a stable "ion wall" consisting of terminal NH3 (+) groups and Cl(-) counterions exists at the outmost region of self-assembled monolayer (SAM) where the translational and rotational motions of water molecules slow considerably down compared to those in the bulk owing to the presence of SAM and ion wall. Furthermore, we found that the translational motions of interfacial water molecules display a subdiffusive behavior while their rotational motions exhibit a nonexponential feature. The unique behavior of interfacial water molecules around the MPAN can be attributed to the interfacial hydrogen bond (HB) dynamics. By comparison, the lifetime of NH3 (+)-Cl(-) HBs was found to be the longest, favoring the stability of ion wall. Meanwhile, the lifetime of H2O-H2O HBs shows an obvious increase when the water molecules approach the Au core, suggesting the enhanced H2O-H2O HBs around the charged MPAN, which is contrary to the weaken H2O-H2O HBs around the neutral MPAN. Moreover, the HB lifetimes between water molecules and the ion wall (i.e., the Cl(-)-H2O and NH3 (+)-H2O HBs) are much longer than that of interfacial H2O-H2O HBs, which leads to the increasing rotational relaxation time and residence time of water molecules surrounding the ion wall. In addition, the corresponding binding energies for different HB types obtained from the precise density functional theory are in excellent accordance with above simulation results. The detailed HB dynamics studied in this work provides insights into the unique behavior of water molecules at the interface of charged self-assemblies of nanoparticles as well as proteins.