Monolayer-Assisted Surface-Initiated Schiff-Base-Mediated Aldol Polycondensation for the Synthesis of Crystalline sp² Carbon-Conjugated Covalent Organic Framework Thin Films

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 5203 - 5210

Published: Feb. 13, 2023

sp2 carbon-conjugated covalent organic frameworks (sp2c-COFs) with superb in-plane π-conjugations, high chemical stability, and robust framework structure are expected to be ideal films/membranes for a wide range of applications including energy-related devices optoelectronics. However, so far, sp2c-COFs have been mainly limited microcrystalline powders, this consequently hampered their performances in devices. Herein, we report simple methodology fabricate large-area, free-standing, crystalline sp2c-COF films (TFPT–TMT TB–TMT) on various solid substrates (e.g., fluorine-doped tin oxide, aluminum sheet, polyacrylonitrile membrane) by self-assembly monolayer-assisted surface-initiated Schiff-base-mediated aldol polycondensation (namely, SI-SBMAP). The resultant show lateral sizes up 120 cm2 tunable thickness from tens nanometers few micrometers. Owing the highly ordered quasi-1D channels, membrane-based osmotic power generator presents an output density 14.1 W m–2 under harsh conditions, outperforming most reported COF membranes as well commercialized benchmark (5 m–2). This work demonstrates interfacial fabrication green energy potential

Language: Английский

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Optimizing Membranes for Osmotic Power Generation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 3, 2023

The design of ion-selective membranes is the key towards efficient reverse electrodialysis-based osmotic power conversion. tradeoff between ion selectivity (output voltage) and permeability current) in existing porous membranes, however, limits upgradation generation efficiency for practical applications. Thus, we provide simple guidelines based on fundamentals transport nanofluidics promoting In addition, discuss strategies optimizing membrane performance through analysis various material parameters design, such as pore size, surface charge, density, thickness, pathway, order, ionic diode effect. Lastly, a perspective future directions to further maximize conversion outlined.

Language: Английский

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3D covalent organic framework membrane with fast and selective ion transport

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 22, 2023

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able break the trade-off between ion conductivity and selectivity, waiting for exploitation. Herein, we report fabrication of a sulfonic acid-functionalized COF membrane (3D SCOF) efficient selective transport, using dual acid-mediated interfacial polymerization strategy. The SCOF membranes possess highly interconnected transport channels, ultramicroporous pore sizes (0.97 nm), abundant sulfonate groups (with high exchange capacity 4.1 mmol g-1), leading proton 843 mS cm-1 at 90 °C. When utilized in osmotic energy conversion, power density 21.2 W m-2, remarkable selectivity 0.976 thus an exceptional conversion efficiency 45.3% simultaneously achieved. This work provides alternative approach promotes applications COFs separation.

Language: Английский

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Continuous Covalent Organic Frameworks Membranes: From Preparation Strategies to Applications

Small, Journal Year: 2023, Volume and Issue: 19(44)

Published: June 28, 2023

Abstract Covalent organic frameworks (COFs) are porous crystalline polymeric materials formed by the covalent bonding of units. The abundant units library gives COFs species diversity, easily tuned pore channels, and sizes. In addition, periodic arrangement endows regular highly connected which has led to rapid development in membrane separations. Continuous defect‐free high crystallinity COF membranes is key their application separations, most important issue be addressed research. This review article describes linkage types bonds, synthesis methods, size regulation strategies materials. Further, preparation continuous highlighted, including layer‐by‐layer (LBL) stacking, situ growth, interfacial polymerization (IP), solvent casting. applications separation fields also discussed, gas separation, water treatment, nanofiltration, ion conduction, energy battery membranes. Finally, research results summarized future prospect for outlined. More attention may paid large‐scale conductive

Language: Английский

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In Situ Growth of Imine‐Bridged Anion‐Selective COF/AAO Membrane for Ion Current Rectification and Nanofluidic Osmotic Energy Conversion

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(36)

Published: May 8, 2023

Abstract Facing the energy crisis, using salinity gradient between seawater and freshwater for osmotic conversion is a direct way to obtain energy. So far, most nanofluidic membranes utilized generation are cation‐selective. Given that both anion‐ cation‐selective have identical importance devices, it of great significance develop anion‐selective membranes. Herein, an membrane synthesized by in situ growth imine‐bridged covalent organic framework (COF) on ordered anodic aluminum oxide (AAO) at room temperature. The imine groups residual amino COF can combine with protons neutral solution, enabling positively charged efficiently transport anions. Particularly, due asymmetry charge structure COF/AAO, as‐prepared exhibits excellent ionic current rectification property, which inhibit ion concentration polarization effectively possess high selectivity permeability. Using present COF/AAO membrane, be successfully harvested from solutions salt content, output power density reached 17.95W m −2 under 500‐fold gradient. study provides new avenue construction application smart efficient conversion.

Language: Английский

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Nanoarchitectonics in Advanced Membranes for Enhanced Osmotic Energy Harvesting

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(35)

Published: June 22, 2024

Osmotic energy, often referred to as "blue energy", is the energy generated from mixing of solutions with different salt concentrations, offering a vast, renewable, and environmentally friendly resource. The efficacy osmotic power production considerably relies on performance transmembrane process, which depends ionic conductivity capability differentiate between positive negative ions. Recent advancements have led development membrane materials featuring precisely tailored ion transport nanochannels, enabling high-efficiency harvesting. In this review, diffusion in confined nanochannels rational design optimization architecture are explored. Furthermore, structural mitigate resistance concentration polarization effect for enhancing harvesting highlighted. Finally, an outlook challenges that lie ahead provided, potential applications conversion outlined. This review offers comprehensive viewpoint evolving prospects conversion.

Language: Английский

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High-performance solid-state proton gating membranes based on two-dimensional hydrogen-bonded organic framework composites

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 17, 2025

Biological ion channels exhibit strong gating effects due to their zero-current closed states. However, the capabilities of artificial nanochannels have typically fallen short biological channels, primarily owing larger nanopores that fail completely block transport in off-states. Here, we demonstrate solid-state hydrogen-bonded organic frameworks-based membranes achieve high-performance ambient humidity-controlled proton gating, accomplished by switching pathway instead relying on conventional blockage/activation effects. Density functional theory calculations reveal reversible formation and disruption humidity-induced water bridges within frameworks facilitates mode from adsorption site hopping Grotthuss mechanism. This transition, coupled with introduction bacterial cellulose enhance desorption/adsorption clusters, enables us a superior ratio up 5740, surpassing state-of-the-art devices. Moreover, developed membrane operates entirely principles, rendering it highly versatile for myriad applications environmental detection human health monitoring. study offers perspectives design efficient systems.

Language: Английский

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Nanomaterials‐Based Nanochannel Membrane for Osmotic Energy Harvesting

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(4)

Published: Oct. 12, 2023

Abstract Harvesting clean and renewable osmotic energy through reverse electrodialysis (RED) technology offers a promising solution to address crisis problems. The development of nanochannel membranes constructed from diverse nanomaterials plays crucial role in enabling efficient conversion. In this review, first an overview the mechanism RED process is provided physicochemical properties nanomaterials, covering 0D, 1D, 2D conversion performances membranes. Then, relationship between chemical structural features specifically highlighted, including surface charge property geometric structure, efficiency. Additionally, introduction external stimuli, such as light, temperature, pH, pressure, changes electrolyte environments, are also discussed. Finally, research directions future challenges field harvesting using based on presented. focus refining mechanism, well optimizing structure design.

Language: Английский

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Robust Cellulose Nanocrystal‐Based Self‐Assembled Composite Membranes Doped with Polyvinyl Alcohol and Graphene Oxide for Osmotic Energy Harvesting

Small, Journal Year: 2023, Volume and Issue: 19(50)

Published: Aug. 27, 2023

Osmotic energy from the salinity gradients represents a promising resource with stable and sustainable characteristics. Nanofluidic membranes can be considered as powerful alternatives to traditional low-performance ion exchange membrane achieve high-efficiency osmotic harvesting. However, development of highly efficient easily scalable core component low-cost raw materials remains challenging. Here, composite based on self-assembly cellulose nanocrystals (CNCs) polyvinyl alcohol (PVA) graphene oxide (GO) nanoflakes additives is developed provide solution. The introduction soft PVA polymer significantly improves mechanical strength water stability by forming nacre-like structure. Benefiting abundant negative charges CNC nanorods GO generated network nanochannels, demonstrates good cation-selective transport capacity, thus contributing an optimal conversion 6.5 W m-2 under 100-fold gradient exemplary throughout 25 consecutive days operation. This work provides option for nanofluidic that produced large scale well-resourced biomass conversion.

Language: Английский

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Engineered Heterogenous Subnanochannel Membranes with a Tri‐Continuous Pore Structure of Large Geometry Gradient for Massively Enhanced Osmotic Power Conversion from Organic Solutions

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 8, 2023

Abstract Heterogenous nanofluidic membranes with bi‐layer structures and ionic diode effect are shown great potential in efficiently harvesting the energy existing a salinity gradient (or called osmotic power conversion). However, exploitation of heterogenous membrane superior ion selectivity, excellent conductance, strong characteristics has remained challenge. Here, novel subnanochannel tri‐continuous pore structure large geometry ranging from sub‐nanoscale to nanoscale sub‐microscale, which is composed thin crack‐free layer zeolitic imidazolate framework‐8 (ZIF‐8)/polystyrene sulfonate (PSS) an aligned branch‐type alumina nanochannel (B ANM ) reported. It demonstrated that such can endow exploited membrane, ZIF‐8/PSS@B , enhanced current rectification, ultrafast transport properties, organic electrolyte solutions. Thus, amazingly high ≈50.5 W m −2 produced by mixing 2 LiCl‐methanol pure methanol solutions, over 45‐fold higher than membranes. Realizing selectivity amplified directional at sub‐nanoconfined spaces solvents paves new way develop ion‐channel‐mimetic toward efficient separation high‐performance harvesters for battery applications.

Language: Английский

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