Emerging Pt-based intermetallic nanoparticles for the oxygen reduction reaction.

The advancement of highly efficient and enduring platinum (Pt)-based electrocatalysts for the oxygen reduction reaction (ORR) is a critical determinant to enable broad utilization of clean energy conversion technologies. Pt-based intermetallic electrocatalysts offer durability and superior ORR activity over their traditional analogues due to their definite stoichiometry, ordered and extended structures, and favourable enthalpy of formation. With the advent in new synthetic methods, Pt-based intermetallic nanoparticles as a new class of advanced electrocatalysts have been studied extensively in recent years. This review discusses the preparation principles, representative preparation methods of Pt-based intermetallics and their applications in the ORR. Our review is focused on L10 Pt-based intermetallics which have gained tremendous interest recently due to their larger surface strain and enhanced M(3d)-Pt(5d) orbital coupling, particularly in the crystallographic c-axis direction. Additionally, we discuss future research directions to further improve the efficiency of Pt-based intermetallic electrocatalysts with the intention of stimulating increased research ventures in this domain.

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks.

The diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3-diaminopyridine-mediated supramolecular templating method, which facilitates the prefabrication of helical imine-linked polymer nanotubes using unprecedented achiral symmetric monomers. Through meticulous optimization of crystallization conditions, these helical polymer nanotubes are adeptly converted into imine-linked COF nanotubes boasting impressive surface areas, while well preserving their helical morphology and chiroptical properties. Furthermore, these helical imine-linked polymers or COFs could be subtly transformed into corresponding more stable and functional helical ß-ketoenamine-linked and hydrazone-linked COF nanotubes with transferred circular dichroism via monomer exchange. Notably, despite the involvement of covalent bonding breakage and reorganization, these exchange processes overcome thermodynamic disadvantages, allowing mesoscopic helical chirality to be perfectly preserved. This research highlights the potential of mesoscopic helicity in conferring COFs with favourable chiral properties, providing novel insights into the development of multifunctional COFs in the field of chiral materials chemistry.

Highly Permeable Sulfonated Polydopamine Integrated MXene Membranes for Efficient Surfactant-Stabilized Oil-in-Water Separation.

MXene is an incredibly promising two-dimensional material with immense potential to serve as a high-performing separating or barrier layer to develop advanced membranes. Despite the significant progress made in MXene membranes, two major challenges still exist: (i) effectively stacking MXene nanosheets into defect-free membranes and (ii) the high fouling tendency of MXene-based membranes. To address these issues, we employed sulfonated polydopamine (SPD), which simultaneously serves as a binding agent to promote the compact assembling of Ti3C2Tx MXenes (MX) nanosheets and improves the antifouling properties of the resulting sulfonated polydopamine-functionalized MX (SPDMX) membranes. The SPDMX membrane was tested for challenging surfactant-stabilized oil-in-water separation with an impressive efficiency of 98%. Moreover, an ultrahigh permeability of 1620 LMH/bar was also achieved. The sulfonation of PD helps in improving the antifouling characteristics of SPDMX by developing a strong hydration layer and enhancing the oleophobicity of the membrane. The underwater SPDMX membrane appeared superoleophobic with an oil contact angle of 153°, whereas the ceramic membrane exhibited an oil contact angle of 137°. The SPDMX membranes showed an improved flux recovery (31%) compared to the nonsulfonated counterpart. This work highlights the appropriate functionalization of MXene as a promising approach to developing MXene membranes with high permeation flux and better antifouling characteristics for oily wastewater treatment.

Anomalous correlation-induced dynamical phase transitions.

The nonanalyticity of the Loschmidt echo at critical times in quantum quenched systems is termed as the dynamical quantum phase transition, extending the notion of quantum criticality to a nonequilibrium scenario. In this paper, we establish a new paradigm of dynamical phase transitions driven by a sudden change in the internal spatial correlations of the disorder potential in a low-dimensional disordered system. The quench dynamics between prequenched pure and postquenched random system Hamiltonian reveals an anomalous dynamical quantum phase transition triggered by an infinite disorder correlation in the modulation potential. The physical origin of the anomalous phenomenon is associated with the overlap between the two distinctly different extended states. Furthermore, we explore the quench dynamics between the prequenched random and postquenched pure system Hamiltonian. Interestingly, the quenched system undergoes dynamical quantum phase transitions for the prequench white-noise potential in the thermodynamic limit. In addition, the quench dynamics also shows a clear signature of the delocalization phase transition in the correlated Anderson model.

Water/Vapor Assisted Fabrication of Large-Area Superprotonic Conductive Covalent Organic Framework Membranes.

Fabrication of large-area ionic covalent organic framework membranes (iCOMs) remains a grand challenge. Herein, the authors report the liquid water and water vapor-assisted fabrication of large-area superprotonic conductive iCOMs. A mixed monomer solution containing 1,3,5-triformylphloroglucinol (TFP) in 1,4-dioxane and p-diaminobenzenesulfonic acid (DABA) in water is first polymerized to obtain a pristine membrane which subsequently underwent crystallization process in mixed vapors containing water vapor. During the polymerization stage, water played a role of a diluting agent, weakening the Coulombic repulsion between sulfonic acid groups. During the crystallization stage, water vapor played a role of a structure-directing agent to facilitate the formation of highly crystalline, large-area iCOMs. The resulting membranes achieved a proton conductivity value of 0.76 S cm-1 at 90 °C under 100% relative humidity, which is among the highest ever reported. Using liquid water and water vapor as versatile additives open a novel avenue to the fabrication of large-area membranes from covalent organic frameworks and other kinds of crystalline organic framework materials.

Emerging covalent triazine framework-based nanomaterials for electrochemical energy storage and conversion.

Recently, the increasing concerns regarding environmental and energy-related issues due to the use of fossil fuels have triggered extensive research on sustainable electrochemical energy storage and conversion (EESC). In this case, covalent triazine frameworks (CTFs) possess a large surface area, tailorable conjugated structures, electron donating-accepting/conducting moieties, and excellent chemical and thermal stabilities. These merits make them leading candidates for EESC. However, their poor electrical conductivity impedes electron and ion conduction, leading to unsatisfactory electrochemical performances, which limit their commercial applications. Thus, to overcome these challenges, CTF-based nanocomposites and their derivatives such as heteroatom-doped porous carbons, which inherit most of the merits of pristine CTFs, lead to excellent performances in the field of EESC. In this review, initially, we briefly highlight the existing strategies for the synthesis of CTFs with application-targeted properties. Next, we review the contemporary progress of CTFs and their derivatives related to electrochemical energy storage (supercapacitors, alkali-ion batteries, lithium-sulfur batteries, etc.) and conversion (oxygen reduction/evolution reaction, hydrogen evolution reaction, carbon dioxide reduction reaction, etc.). Finally, we discuss perspectives on current challenges and recommendations for the further development of CTF-based nanomaterials in burgeoning EESC research.

Photo-tailored heterocrystalline covalent organic framework membranes for organics separation.

Organics separation for purifying and recycling environment-detrimental solvents is essential to sustainable chemical industries. Covalent organic framework (COF) membranes hold great promise in affording precise and fast organics separation. Nonetheless, how to well coordinate facile processing-high crystalline structure-high separation performance remains a critical issue and a grand challenge. Herein, we propose a concept of heterocrystalline membrane which comprises high-crystalline regions and low-crystalline regions. The heterocrystalline COF membranes are fabricated by a two-step procedure, i.e., dark reaction for the construction of high-crystalline regions followed by photo reaction for the construction of low-crystalline regions, thus linking the high-crystalline regions tightly and flexibly, blocking the defect in high-crystalline regions. Accordingly, the COF membrane exhibits sharp molecular sieving properties with high organic solvent permeance up to 44-times higher than the state-of-the-art membranes.

Assembling covalent organic framework membranes via phase switching for ultrafast molecular transport.

Fabrication of covalent organic framework (COF) membranes for molecular transport has excited highly pragmatic interest as a low energy and cost-effective route for molecular separations. However, currently, most COF membranes are assembled via a one-step procedure in liquid phase(s) by concurrent polymerization and crystallization, which are often accompanied by a loosely packed and less ordered structure. Herein, we propose a two-step procedure via a phase switching strategy, which decouples the polymerization process and the crystallization process to assemble compact and highly crystalline COF membranes. In the pre-assembly step, the mixed monomer solution is casted into a pristine membrane in the liquid phase, along with the completion of polymerization process. In the assembly step, the pristine membrane is transformed into a COF membrane in the vapour phase of solvent and catalyst, along with the completion of crystallization process. Owing to the compact and highly crystalline structure, the resultant COF membranes exhibit an unprecedented permeance (water ≈ 403 L m-2 bar-1 h-1 and acetonitrile ≈ 519 L m-2 bar-1 h-1). Our two-step procedure via phase switching strategy can open up a new avenue to the fabrication of advanced organic crystalline microporous membranes.

Preparation and Characterization of Hydrophilic Polymer Based Sustained-Release Matrix Tablets of a High Dose Hydrophobic Drug.

The objective of this study was the preparation and characterization of a sustained-release matrix tablet containing a high-dose hydrophobic drug and its comparison with marketed products. In the present study, HPMC was applied as the matrix-forming polymer for the sustained release of clarithromycin (500 mg). The compatibility of clarithromycin and excipients was studied using a binary mixture approach and compatible excipients were selected. Matrix tablets were prepared using the high-shear wet granulation technique. Tablets were compressed using oblong (19 mm), shallow concave punches, under a compression weight of 900 mg/tablet. The flow of granules was evaluated by determining their bulk density, tapped density, angle of repose, Hausner ratio, and Car's index. Compressed tablets were tested for their physical parameters, mechanical characteristics, drug content, and in vitro drug release, as per United States Pharmacopeia (USP). Clarithromycin is a drug having poor water solubility and showed compatibility with all the excipients used in the formulation of polymeric matrix tablets. FTIR spectra of clarithromycin, before and after being subjected to the stress conditions, confirmed the compatibility of clarithromycin and other ingredients of the matrix tablets. All the formulations exhibited good rheological characteristics and all the parameters related to flow showed results in the acceptable range. Physically, matrix tablets were smooth and shiny, without any surface defects. Weight variation (±5%) and drug content of the tablets (95-102%) were within the pharmacopeial limits. HPMC successfully sustained the drug release for 24 h. It is concluded from the study that dissolution rate of clarithromycin can be sustained using hydrophilic polymer (HPMC) as a release-controlling agent.

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes.

Covalent organic framework (COF) membranes hold potential for widespread applicability, but scalable fabrication is challenging. Here, we demonstrate the disorder-to-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allow the extraneous monomers to replace the pristine monomers within amorphous membrane, driving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology. The COF membranes harvest proton conductivity up to 0.53 S cm-1 at 80 °C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.

Antifouling and Flux Enhancement of Reverse Osmosis Membrane by Grafting Poly (3-Sulfopropyl Methacrylate) Brushes.

A commercial thin film composite (TFC) polyamide (PA) reverse osmosis membrane was grafted with 3-sulfopropyl methacrylate potassium (SPMK) to produce PA-g-SPMK by atom transfer radical polymerization (ATRP). The grafting of PA was done at varied concentrations of SPMK, and its effect on the surface composition and morphology was studied by Fourier-Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), optical profilometry, and contact angle analysis. The grafting of hydrophilic ionically charged PSPMK polymer brushes having acrylate and sulfonate groups resulted in enhanced hydrophilicity rendering a reduction of contact angle from 58° of pristine membrane sample labeled as MH0 to 10° for a modified membrane sample labeled as MH3. Due to the increased hydrophilicity, the flux rate rises from 57.1 L m-2 h-1 to 71.2 L m-2 h-1, and 99% resistance against microbial adhesion (Escherichia coli and Staphylococcus aureus) was obtained for MH3 after modification.

Solid-Vapor Interface Engineered Covalent Organic Framework Membranes for Molecular Separation.

Covalent organic frameworks (COFs) with intrinsic, tunable, and uniform pores are potent building blocks for separation membranes, yet poor processing ability and long processing time remain grand challenges. Herein, we report an engineered solid-vapor interface to fabricate a highly crystalline two-dimensional COF membrane with a thickness of 120 nm in 9 h, which is 8 times faster than that in the reported literature. Due to the ultrathin nature and ordered pores, the membrane exhibited an ultrahigh permeance (water, ∼411 L m-2 h-1 bar-1 and acetonitrile, ∼583 L m-2 h-1 bar-1) and excellent rejection of dye molecules larger than 1.4 nm (>98%). The membrane exhibited long-term operation which confirmed its outstanding stability. Our solid-vapor interfacial polymerization method may evolve into a generic platform to fabricate COFs and other organic framework membranes.

Covalent Organic Framework Nanosheets as Reactive Fillers To Fabricate Free-Standing Polyamide Membranes for Efficient Desalination.

Mixed matrix membranes (MMMs) have been increasingly utilized in membrane processes. Covalent organic frameworks (COFs) hold great promise as emergent nanofillers to fabricate high-performance MMMs; however, only few studies about COF materials in MMMs have been reported where COFs are all used as nonreactive fillers. Herein, we propose using -NH2-functionalized COF nanosheets as reactive fillers (rCON) to fabricate MMMs. rCON altered the morphology and chemistry of MMMs by controlling the diffusion rate of piperazine through hydrogen bonding prior to the interfacial polymerization process and inducing the creation of ridges in the MMMs with subsequent increase in surface area (∼24%). rCON was chemically cross-linked to the trimesoyl chloride through amide bonding, subsequently elevating the hydrophilicity (∼35%) and fouling resistance of MMMs. The presence of -NH2 groups elevated the rCON-PA compatibility, ensuring the high rCON loading of 5 wt % in the MMMs without sacrificing salt rejection. Accordingly, the PA-rCON MMMs exhibited a flux of 46.5 L m-2 h-1 bar-1, which is 6.8 times higher than that of the pristine PA membrane, with a high rejection rate of 93.5% for Na2SO4.

Mixed Nanosheet Membranes Assembled from Chemically Grafted Graphene Oxide and Covalent Organic Frameworks for Ultra-high Water Flux.

2D graphene oxide (GO) membranes attract great attention because of their ultrathin thickness and superior molecular sieving ability, but their low flux and instability in aqueous environments are still the major challenges for practical applications. In this study, we designed hybrid nanosheets from chemically grafted GO and covalent organic frameworks (COFs) as building blocks to fabricate mixed nanosheet membranes. The covalent triazine framework (CTF), a triazine-based COF, is exfoliated into nanosheets and then reacted with GO to form the GO-CTF hybrid nanosheets, which are then assembled into GO-CTF mixed nanosheet membranes. The GO-CTF membranes show a layered configuration of ca. 32 nm thickness. The incorporation of CTF nanosheets inappreciably changes the interlayer distance of GO-CTF membranes, ensuring high rejections to organic dyes (>90%); meanwhile, the CTF nanosheets afford extra through-plane channels that significantly shorten the water transport pathway. The GO-CTF membranes exhibit a water flux of 226.3 L m-2 h-1 bar-1, more than 12-fold higher than pure GO membranes. Besides, the strong chemical bonds between GO and COF render the GO-CTF membranes notably enhanced stability. Grafting of porous nanosheets onto nonporous nanosheets to acquire hybrid nanosheets as building blocks opens a new avenue to the fabrication of 2D membranes with promising application potential.

Microporous membranes comprising conjugated polymers with rigid backbones enable ultrafast organic-solvent nanofiltration.

Conventional technology for the purification of organic solvents requires massive energy consumption, and to reduce such expending calls for efficient filtration membranes capable of high retention of large molecular solutes and high permeance for solvents. Herein, we report a surface-initiated polymerization strategy through C-C coupling reactions for preparing conjugated microporous polymer (CMP) membranes. The backbone of the membranes consists of all-rigid conjugated systems and shows high resistance to organic solvents. We show that 42-nm-thick CMP membranes supported on polyacrylonitrile substrates provide excellent retention of solutes and broad-spectrum nanofiltration in both non-polar hexane and polar methanol, the permeance for which reaches 32 and 22 l m-2 h-1 bar-1, respectively. Both experiments and simulations suggest that the performance of CMP membranes originates from substantially open and interconnected voids formed in the highly rigid networks.

MoS2 /Celgard Separator as Efficient Polysulfide Barrier for Long-Life Lithium-Sulfur Batteries.

A high lithium conductive MoS2 /Celgard composite separator is reported as efficient polysulfides barrier in Li-S batteries. Significantly, thanks to the high density of lithium ions on MoS2 surface, this composite separator shows high lithium conductivity, fast lithium diffusion, and facile lithium transference. When used in Li-S batteries, the separator is proven to be highly efficient for depressing polysulfides shuttle, leading to high and long cycle stability. With 65% of sulfur loading, the device with MoS2 /Celgard separator delivers an initial capacity of 808 mAh g-1 and a substantial capacity of 401 mAh g-1 after 600 cycles, corresponding to only 0.083% of capacity decay per cycle that is comparable to the best reported result so far. In addition, the Coulombic efficiency remains more than 99.5% during all 600 cycles, disclosing an efficient ionic sieve preventing polysulfides migration to the anode while having negligible influence on Li+ ions transfer across the separator. The strategy demonstrated in this work will open the door toward developing efficient separators with flexible 2D materials beyond graphene for energy-storage devices.