Phase Engineering of Zirconium MOFs Enables Efficient Osmotic Energy Conversion: Structural Evolution Unveiled by Direct Imaging.

Creating structural defects in a controlled manner within metal-organic frameworks (MOFs) poses a significant challenge for synthesis, and concurrently, identifying the types and distributions of these defects is also a formidable task for characterization. In this study, we demonstrate that by employing 2-sulfonylterephthalic acid as the ligand for synthesizing Zr (or Hf)-based MOFs, a crystal phase transformation from the common fcu topology to the rare jmt topology can be easily facilitated using a straightforward mixed-solvent strategy. The jmt phase, characterized by an extensively open framework, can be considered a derivative of the fcu phase, generated through the introduction of missing-cluster defects. We have explicitly identified both MOF phases, their intermediate states, and the novel core-shell structures they form using ultralow-dose high-resolution transmission electron microscopy. In addition to facilitating phase engineering, the incorporation of sulfonic groups in MOFs imparts ionic selectivity, making them applicable for osmotic energy harvesting through mixed matrix membrane fabrication. The membrane containing the jmt-phase MOF exhibits an exceptionally high peak power density of 10.08 W m-2 under a 50-fold salinity gradient (NaCl: 0.5 M|0.01 M), which surpasses the threshold of 5 W m-2 for commercial applications and can be attributed to the combination of large pore size, extensive porosity, and abundant sulfonic groups in this novel MOF material.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia 3 ‾ ${\bar{3}}$ d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Space-Confined Synthesis of Monolayer Graphdiyne in MXene Interlayer.

Graphdiyne (GDY) is an artificial carbon allotrope that is conceptually similar to graphene but composed of sp- and sp2 -hybridized carbon atoms. Monolayer GDY (ML-GDY) is predicted to be an ideal 2D semiconductor material with a wide range of applications. However, its synthesis has posed a significant challenge, leading to difficulties in experimentally validating theoretical properties. Here, it is reported that in situ acetylenic homocoupling of hexaethynylbenzene within the sub-nanometer interlayer space of MXene can effectively prevent out-of-plane growth or vertical stacking of the material, resulting in ML-GDY with in-plane periodicity. The subsequent exfoliation process successfully yields free-standing GDY monolayers with micrometer-scale lateral dimensions. The fabrication of field-effect transistor on free-standing ML-GDY makes the first measurement of its electronic properties possible. The measured electrical conductivity (5.1 × 103 S m-1 ) and carrier mobility (231.4 cm2 V-1 s-1 ) at room temperature are remarkably higher than those of the previously reported multilayer GDY materials. The space-confined synthesis using layered crystals as templates provides a new strategy for preparing 2D materials with precisely controlled layer numbers and long-range structural order.

Co-Expression of JcNAC1- and JcZFP8-Improved Agronomic Traits of Tobacco and Enhanced Drought Resistance through NbbHLH1 and NbbHLH2.

Previous studies have identified numerous transcription factors involved in drought response, each of which play different roles in plants. The objective of the present study was to evaluate the effectiveness of two transcription factors on drought response in Jatropha curcas L., JcNAC1 and JcZFP8. The overexpression of these transcription factors in tobacco (Nicotiana benthamiana L.) improved drought resistance, but JcZFP8 delayed germination and JcNAC1 reduced biomass and yield. By constitutively co-expressing these two genes in tobacco, drought resistance was improved, and the negative effects of each of them were overcome. The transgenic plants with double-gene co-expression showed stronger drought tolerance with 1.76-fold greater accumulation of proline and lower H2O2 and malondialdehyde (MDA) content to 43 and 65% of wildtype (WT) levels, respectively. The expression levels of NbbHLH1 and NbbHLH2 genes upregulated linearly with the increased drought tolerance of double genes co-expression plants. In drought conditions, the leaf water contents of bhlh1, bhlh2, and bhlh1bhlh2 deletion mutants obtained by CRISPR-CAS9 knockout technique were maintained at 99%, 97%, and 97% of WT. The bhlh1bhlh2 was found with lower germination rate but with higher reactive oxygen levels (1.64-fold H2O2 and 1.41-fold MDA levels). Thus, the co-expression of two transcription factors with different functions overcame the adverse traits brought by a single gene and enhanced the shared drought-tolerant traits, which can provide guidance on theory and selection of gene combinations for the application of multi-gene co-expression in agriculture in the future.

Artificial intelligence and structural design of inorganic hollow fiber membranes: Materials chemistry.

A key challenge is to produce the uniform morphology and regular pore design of inorganic hollow fiber membranes (HFMs) due to involvement of multiple parameters including, fabrication process and materials chemistry. Inorganic HFMs required technical innovations via novel structural design and artificial intelligence (AI) to produce the uniform structure and regular pore design. Therefore, this review aims at critical analysis on the most recent and relevant approaches to tackle the issues related to tune the morphology and pore design of inorganic HFMs. Structural design and evaluation of routes towards the dope suspension, spinning, and sintering of inorganic HFMs are critically analysed. AI, driving forces and challenges involved for harnessing of materials are revealed in this review. AI programs used for the prediction of pore design and performance of HFMs have also been explained in this review. Overall, this review will provide the understanding to build the equilibrium in spinning and sintering processes to control the design of micro-channels, and structural properties of inorganic HFMs. This review has great significance to control the new design of membranes via AI programs. This review also explain the inorganic membrane efficiency as algal-bioreactor.

Thermodynamics and kinetic analysis of membrane: Challenges and perspectives.

The ultimate structure of the membrane is determined using two important effects: (i) thermodynamic effect and (ii) kinetic effect. Controlling the mechanism of kinetic and thermodynamic processes in phase separation is essential for enhancing membrane performance. However, the relationship between system parameters and the ultimate membrane morphology is still largely empirical. This review focuses on the fundamental ideas behind thermally induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods, including both kinetic and thermodynamic elements. The thermodynamic approach to understanding phase separation and the effect of different interaction parameters on membrane morphology has been discussed in detail. Furthermore, this review explores the capabilities and limitations of different macroscopic transport models used for the last four decades to explore the phase inversion process. The application of molecular simulations and phase field to understand phase separation has also been briefly examined. Finally, it discusses the thermodynamic approach to understanding phase separation and the consequence of different interaction parameters on membrane morphology, as well as possible directions for artificial intelligence to fill the gaps in the literature. This review aims to provide comprehensive knowledge and motivation for future modeling work for membrane fabrication via new techniques such as nonsolvent-TIPS, complex-TIPS, non-solvent assisted TIPS, combined NIPS-TIPS method, and mixed solvent phase separation.

Fluorido-bridged robust metal-organic frameworks for efficient C2H2/CO2 separation under moist conditions.

The modern technology for acetylene production is inevitably accompanied by the contamination of carbon dioxide and moisture impurities. Metal-organic frameworks (MOFs), with rational configurations of fluorine as the hydrogen-bonding acceptor (HBA), exhibit excellent affinities to capture acetylene from the gas mixtures. Currently, most research studies feature anionic fluorine groups as structural pillars (e.g., SiF6 2-, TiF6 2-, NbOF5 2-), whereas in situ insertion of fluorine into metal clusters is rather challenging. Herein, we report a unique fluorine-bridged Fe-MOF, i.e., DNL-9(Fe), which is assembled by mixed-valence FeIIFeIII clusters and renewable organic ligands. The fluorine species in the coordination-saturated structure offer superior C2H2-favored adsorption sites facilitated by hydrogen bonding, with a lower C2H2 adsorption enthalpy than other reported HBA-MOFs, demonstrated by static/dynamic adsorption tests and theoretical calculations. Importantly, DNL-9(Fe) shows exceptional hydrochemical stability under aqueous, acidic, and basic conditions, and its intriguing performance for C2H2/CO2 separation was even maintained at a high relative humidity of 90%.

Correction: Fluorido-bridged robust metal-organic frameworks for efficient C2H2/CO2 separation under moist conditions.

[This corrects the article DOI: 10.1039/D2SC06699H.].

Next-generation ultrafiltration membranes: A review of material design, properties, recent progress, and challenges.

Membrane technology utilizing ultrafiltration (UF) processes has emerged as the most widely used and cost-effective simple process in many industrial applications. The industries like textiles and petroleum refining are promptly required membrane based UF processes to alleviate the potential environmental threat caused by the generation of various wastewater. At the same time, major limitations such as material selection as well as fouling behavior challenge the overall performance of UF membranes, particularly in wastewater treatment. Therefore, a complete discussion on material design with structural property relation and separation performance of UF membranes is always exciting. This state-of-the-art review has exclusively focused on the development of UF membranes, the material design, properties, progress in separation processes, and critical challenges. So far, most of the review articles have examined the UF membrane processes through a selected track of paving typical materials and their limited applications. In contrast, in this review, we have exclusively aimed at comprehensive research from material selection and fabrication methods to all the possible applications of UF membranes, giving more attention and theoretical understanding to the complete development of high-performance UF systems. We have discussed the methodical engineering behind the development of UF membranes regardless of their materials and fabrication mechanisms. Identifying the utility of UF membrane systems in various applications, as well as their mode of separation processes, has been well discussed. Overall, the current review conveys the knowledge of the present-day significance of UF membranes together with their future prospective opportunities whilst overcoming known difficulties in many potential applications.

Highly Efficient Production of Nanoporous Block Copolymers with Arbitrary Structural Characteristics for Advanced Membranes.

The great significance of boosting the design of percolating nanopore structures in block copolymers (BCPs) for various cases has been widely demonstrated in the past several decades. However, it still remains challenging to prepare the desired porous structures in a rapid, facile, and universal manner. Here we have developed an unconventional and benchtop strategy to rapidly generate the nanoporous polystyrene-based BCPs with arbitrary structural characteristics regardless of the BCP bulk morphology. This universal pore-forming strategy enables the sustainable CO2 -based BCPs to form advanced membranes after 1 s soaking for efficiently rejecting 94.2 % brilliant blue R (826 g mol-1 ). Meanwhile, the water permeance retains around 1020 L (m2 h bar)-1 , which is 1-3 orders of magnitude higher than that of other membranes. This strategy may offer an excellent opportunity to introduce percolating pore structures in those newly developed BCPs with which the previously reported pore-forming methods may not deal.

Tuning of Microenvironment in Covalent Organic Framework via Fluorination Strategy promotes Selective CO2 Capture.

Herein, we have designed and synthesized two heteroatom (N, O) rich covalent organic frameworks (COF), PD-COF and TF-COF, respectively, to demonstrate their relative effect on CO2 adsorption capacity and also CO2 /N2 selectivity. Compared to the non-fluorinated PD-COF (BET surface area 805 m2 g-1 , total pore volume 0.3647 ccg-1 ), a decrease in BET surface area and also pore volume have been observed for fluorinated TF-COF due to the incorporation of fluorine to the porous framework (BET surface area 451 m2 g-1 , total pore volume 0.2978 ccg-1 ). This fact leads to an enormous decrease in the CO2 adsorption capacity and CO2 /N2 selectivity of TF-COF, though it shows stronger affinity towards CO2 with a Qst of 37.76 KJ/mol. The more CO2 adsorption capacity by PD-COF can be attributed to the large specific surface area with considerable amount of micropore volume compared to the TF-COF. Further, PD-COF exhibited CO2 /N2 selectivity of 16.8, higher than that of TF-COF (CO2 /N2 selectivity 13.4).

Switchable Na+ and K+ selectivity in an amino acid functionalized 2D covalent organic framework membrane.

Biological cell membranes can efficiently switch Na+/K+ selectivity in response to external stimuli, but achieving analogous functions in a single artificial membrane is challenging. Here, we report highly crystalline covalent organic framework (COF) membranes with well-defined nanochannels and coordinative sites (i. e., amino acid) that act as ion-selective switches to manipulate Na+ and K+ transport. The ion selectivity of the COF membrane is dynamic and can be switched between K+-selective and Na+-selective in a single membrane by applying a pH stimulus. The experimental results combined with molecular dynamics simulations reveal that the switchable Na+/K+ selectivity originates from the differentiated coordination interactions between ions and amino acids. Benefiting from the switchable Na+/K+ selectivity, we further demonstrate the membrane potential switches by varying electrolyte pH, miming the membrane polarity reversal during neural signal transduction in vivo, suggesting the great potential of these membranes for in vitro biomimetic applications.

LRP1-Mediated Endocytosis May Be the Main Reason for the Difference in Cytotoxicity of Curcin and Curcin C on U2OS Osteosarcoma Cells.

Curcin and Curcin C, both of the ribosome-inactivating proteins of Jatropha curcas, have apparent inhibitory effects on the proliferation of osteosarcoma cell line U20S. However, the inhibitory effect of the latter is 13-fold higher than that of Curcin. The mechanism responsible for the difference has not been studied. This work aimed to understand and verify whether there are differences in entry efficiency and pathway between them using specific endocytosis inhibitors, gene silencing, and labeling techniques such as fluorescein isothiocyanate (FITC) labeling. The study found that the internalization efficiency of Curcin C was twice that of Curcin for U2OS cells. More than one entering pathway was adopted by both of them. Curcin C can enter U2OS cells through clathrin-dependent endocytosis and macropinocytosis, but clathrin-dependent endocytosis was not an option for Curcin. The low-density lipoprotein receptor-related protein 1 (LRP1) was found to mediate clathrin-dependent endocytosis of Curcin C. After LRP1 silencing, there was no significant difference in the 50% inhibitory concentration (IC50) and endocytosis efficiency between Curcin and Curcin C on U2OS cells. These results indicate that LRP1-mediated endocytosis is specific to Curcin C, thus leading to higher U2OS endocytosis efficiency and cytotoxicity than Curcin.

An Ionic Diode Covalent Organic Framework Membrane for Efficient Osmotic Energy Conversion.

Heterogeneous membranes that exhibit an ionic diode effect are promising candidates for osmotic energy conversion. However, existing heterogeneous membranes lack molecular-level designed ion channels, thereby limiting their power densities. Here, we demonstrate ionic diode covalent organic framework (COF) membranes with well-defined ion channels, asymmetric geometry and surface charge polarity as high-performance osmotic power generators. The COF diode membranes are comprised of heterojunctions combining a positively charged ultrathin COF layer and a negatively charged COF layer supported by a porous COF nanofiber scaffold, exhibiting an ionic diode effect that effectuates fast unidirectional ion diffusion and anion selectivity. Density functional theory calculations reveal that the differentiated interactions between anions and COF channels contributed to superior I- transport over other anions. Consequently, the COF diode membranes achieved high output power densities of 19.2 and 210.1 W m-2 under a 50-fold NaCl and NaI gradient, respectively, outperforming state-of-the-art heterogeneous membranes. This work suggests the great potential of COF diode membranes for anion transport and energy-related applications.

Correction: Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol.

Correction for 'Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol' by Saikiran Pendem et al., Dalton Trans., 2019, 48, 8791-8802, https://doi.org/10.1039/C9DT01190K.

Scalable fabrication of Solvent-Free composite solid electrolyte by a continuous Thermal-Extrusion process.

Composite solid-state electrolytes (CSEs) are regarded as a promising alternative for the next-generation lithium-ion batteries because they integrate the advantages of inorganic electrolytes and organic electrolytes. However, there are two issues faced by current CSEs: 1) a green and feasible approach to prepare CSEs in large scales is desired; and 2) the trace solvents, remaining from the preparation processes, lead to some serious concerns, such as safety hazard issues, electrolyte-electrode interfacial issues, and reduced durability of batteries. Here, a continuous thermal-extrusion process is presented to realize the large-scale fabrication of solvent-free CSE. A 38.7-meter CSE membrane was prepared as a demonstration in this study. Thanks to the elimination of residual solvents, the electrolyte membrane exhibited a high tensile strength of 3.85 MPa, satisfactory lithium transference number (0.495), and excellent electrochemical stability (5.15 V). Excellent long-term stability was demonstrated by operating the symmetric lithium cell at a stable current density of 0.1 mA cm-2 for over 3700 h. Solvent-free CSE lithium metal batteries showed a discharge capacity of 155.7 - 25.17 mAh g-1 at 0.1 - 2.0C, and the discharge capacity remained 78.1% after testing for 380cycles.

Giant Osmotic Energy Conversion through Vertical-Aligned Ion-Permselective Nanochannels in Covalent Organic Framework Membranes.

Nanofluidic membranes have been demonstrated as promising candidates for osmotic energy harvesting. However, it remains a long-standing challenge to fabricate high-efficiency ion-permselective membranes with well-defined channel architectures. Here, we demonstrate high-performance osmotic energy conversion membranes based on oriented two-dimensional covalent organic frameworks (COFs) with ultrashort vertically aligned nanofluidic channels that enabled efficient and selective ion transport. Experiments combined with molecular dynamics simulations revealed that exquisite control over channel orientation, charge polarity, and charge density contributed to high ion selectivity and permeability. When applied to osmotic energy conversion, a pair of 100 nm thick oppositely charged COF membranes achieved an ultrahigh output power density of 43.2 W m-2 at a 50-fold salinity gradient and up to 228.9 W m-2 for the Dead Sea and river water system. The achieved power density outperforms the state-of-the-art nanofluidic membranes, suggesting the great potential of oriented COF membranes in the fields of advanced membrane technology and energy conversion.

Conjugated microporous polymer membranes for light-gated ion transport.

Inspired by the light-gated ion channels in cell membranes that play important roles in many biological activities, herein, we developed an artificial light-gated ion channel membrane out of conjugated microporous polymers. Through bottom-up design of the monomer molecular structure and by the electropolymerization method, the membrane pore size and thickness were precisely controlled on the molecular level. The obtained membrane exhibited uniform pore size and highly sensitive light-switchable response. The photoisomerization of the polymer chain resulted in a reversible "on and off" light control over the pore size and subsequently led to light-gated ion transport across the membrane for a series of ions including hydrogen, potassium, sodium, lithium, calcium, magnesium, and aluminum ions.

Foldable Solid-State Batteries Enabled by Electrolyte Mediation in Covalent Organic Frameworks.

Solid-state electrolytes with high Li+ conductivity, flexibility, durability, and stability offer an attractive solution to enhance safety and energy density. However, meeting these stringent requirements poses challenges to the existing solid polymeric or ceramic electrolytes. Here, an electrolyte-mediated single-Li+ -conductive covalent organic framework (COF) is presented, which represents a new category of quality solid-state Li+ conductors. In situ solidification of a tailored liquid electrolyte boosts the charge-carrier concentration in the COF channels, decouples Li+ cations from both COF walls and molecular chains, and eliminates defects by crystal soldering. Such an altered microenvironment activates the motion of Li+ ions in a directional manner, which leads to an increase in Li+ conductivity by 100 times with a transference number of 0.85 achieved at room temperature. Moreover, the electrolyte conversion cements the ultrathin COF membrane with fortified mechanical toughness. With the COF membrane, foldable solid-state pouch cells are demonstrated.

Carbon nanotube supported oriented metal organic framework membrane for effective ethylene/ethane separation.

Zeolitic imidazolate framework 8 (ZIF-8) is effective for C3H6/C3H8 separation because of the "sieving effect" of a six-membered (6-M) window. Here, we demonstrate that ZIF-8 is a versatile material that could effectively separate C2H4 from C2H6 via its 4-M window along the <100> direction. We established a facile and environmentally friendly carbon nanotube (CNT)-induced oriented membrane (CNT-OM) approach to fabricate a {100}-oriented ZIF-8 membrane (100-M). In this approach, 2-methyimidazole was anchored onto the CNT surface followed by 3-hour in situ growth in aqueous solution at room temperature. The obtained 100-M, whose 4-M window is aligned along the transport pathway, showed ~3 times higher C2H4/C2H6 selectivity than a randomly oriented membrane. Thus, this work demonstrates that the membrane orientation plays an important role in tuning selectivity toward different gas pairs. Furthermore, 100-M exhibited excellent mechanical stability that could sustain the separation performance after bending at a curvature of ~109 m-1.