Porous crystalline materials for memories and neuromorphic computing systems

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(20), P. 7071 - 7136

Published: Jan. 1, 2023

This review highlights the film preparation methods and application advances in memory neuromorphic electronics of porous crystalline materials, involving MOFs, COFs, HOFs, zeolites.

Language: Английский

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Boosting CO₂ Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Language: Английский

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Design and synthesis of broadband absorption covalent organic framework for efficient artificial photocatalytic amine coupling

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 7, 2024

Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report new donor-acceptor (D-A) covalent organic framework (COF) with wide absorption range from 200 nm to 900 (ultraviolet-visible-near infrared light). We find the thiophene functional group accurately introduced into electron acceptor units of TpDPP-Py (TpDPP: 5,5'-(2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral capacity also endows them two-photon and three-photon effects, greatly enhancing utilization rate sunlight. The selective coupling benzylamine as target reactant used assess photocatalytic activity COFs, showing high conversion 99% selectivity 98% in 20 min. Additionally, exhibit universality other imine derivatives ~100% efficiency. Overall, this work brings significant strategy developing enhance activity.

Language: Английский

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Surfactant-assisted interfacial polymerization towards high-crystallinity COF membranes for organic solvent nanofiltration

Journal of Membrane Science, Journal Year: 2024, Volume and Issue: 694, P. 122404 - 122404

Published: Jan. 3, 2024

Language: Английский

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Photoelectric Multilevel Memory Device based on Covalent Organic Polymer Film with Keto–Enol Tautomerism for Harsh Environments Applications

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(1)

Published: Sept. 15, 2023

Abstract Covalent organic polymers (COPs) memristors with multilevel memory behavior in harsh environments and photoelectric regulation are crucial for high‐density storage high‐efficiency neuromorphic computing. Here, a donor–acceptor (D–A)‐type COP film (Py‐COP‐3), which is initiated by keto–enol tautomerism, proposed high‐performance memristors. Satisfactorily, the indium tin oxide (ITO)/Py‐COP‐3/Ag device demonstrates performance, even high temperatures, acid‐base corrosion, various solvents. Moreover, performance can be modulated effect to maintain great switching behavior. By contrast, Py‐COP‐0, similar structure chemical composition Py‐COP‐3 but without exhibits binary performance. Further studies unravel that both formation of conductive filaments charge transfer within D‐A contribute resistive devices.

Language: Английский

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Covalent Organic Frameworks for the Purification of Recombinant Enzymes and Heterogeneous Biocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 858 - 867

Published: Dec. 30, 2023

Recombinant enzymes have gained prominence due to their diverse functionalities and specificity are often a greener alternative in biocatalysis. This context makes purifying recombinant from host cells other impurities crucial. The primary goal is isolate the pure enzyme of interest ensure its stability under ambient conditions. Covalent organic frameworks (COFs), renowned for well-ordered structure permeability, offer promising approach histidine-tagged (His-tagged) enzymes. Furthermore, immobilizing within COFs represents growing field heterogeneous In this study, we developed flow-based technology utilizing nickel-infused covalent framework (Ni-TpBpy COF) combine two distinct processes: purification His-tagged immobilization simultaneously. Our work primarily focuses on three β-glucosidase, cellobiohydrolase, endoglucanase as well proteins with varying molecular weights, namely, green fluorescent protein (27 kDa) BG Rho (88 kDa). We employed Ni-TpBpy column matrix showcase versatility our system. Additionally, successfully obtained COF immobilized enzymes, which can serve catalyst hydrolysis p-nitrophenyl-β-d-glucopyranoside carboxymethylcellulose. These demonstrated catalytic activity comparable that free counterparts, added advantages recyclability enhanced conditions an extended period, ranging 60 90 days. contrasts do not maintain effectively over time.

Language: Английский

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Tailoring COFs: Transforming Nonconducting 2D Layered COF into a Conducting Quasi-3D Architecture via Interlayer Knitting with Polypyrrole

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 487 - 499

Published: Dec. 29, 2023

Improving the electronic conductivity and structural robustness of covalent organic frameworks (COFs) is paramount. Here, we covalently cross-link a 2D COF with polypyrrole (Ppy) chains to form quasi-3D COF. The 3D shows well-defined reflections in SAED patterns distinctly indexed its modeled crystal structure. This knitting layers conjugated units improves from 10–9 10–2 S m–1. boost affirmed by presence density states near Fermi level COF, this elevates COF's valence band maximum 0.52 eV respect parent pyrrole-functionalized which agrees well opto–electro gaps. extent HOMO elevation suggests predominant existence polaron state (radical cation), giving rise strong EPR signal, most likely sourced cross-linking chains. A supercapacitor devised COF20-Ppy records high areal capacitance 377.6 mF cm–2, higher than that loaded noncovalently linked Thus, acts as "conjugation bridge" across layers, lowering gap providing polarons additional conduction pathways. marks far-reaching approach converting many COFs into highly ordered conducting ones.

Language: Английский

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Regioisomerism in Thienothiophene-Based Covalent Organic Frameworks─A Tool for Band-Gap Engineering

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15869 - 15878

Published: June 3, 2024

The craft of tuning optical properties is well-established for crystalline inorganic and hybrid solids. However, a far greater challenge to tune the organic materials systematically by design. We now introduce synthesis concept that enables us alter covalent frameworks (COFs) using isomeric structures thienothiophene-based building blocks (T23/32T) combined with variety tetratopic aromatic amines, e.g., Wurster moiety (W–NH2). This demonstrated COFs in bulk film forms provides highly porous featuring predesigned photophysical properties. band gap framework can be tuned continuously precisely chemically doping pristine W23TT COF its related constitutional isomer block. Density-functional theory investigations model compounds indicate extent π-conjugation among key characteristics enabling band-gap engineering.

Language: Английский

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'Honeycomb-like' triazine-based covalent organic framework derivative for remarkably improving both flame retardancy and mechanical properties of epoxy resin

Construction and Building Materials, Journal Year: 2024, Volume and Issue: 426, P. 136166 - 136166

Published: April 13, 2024

Language: Английский

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2D Conjugated Polymer Thin Films for Organic Electronics: Opportunities and Challenges

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: March 29, 2024

2D conjugated polymers (2DCPs) possess extended in-plane π-conjugated lattice and out-of-plane π-π stacking, which results in enhanced electronic performance potentially unique band structures. These properties, along with predesignability, well-defined channels, easy postmodification, order structure attract extensive attention from material science to organic electronics. In this review, the recent advance interfacial synthesis conductivity tuning strategies of 2DCP thin films, as well their application electronics is summarized. Furthermore, it shown that, by combining topology design targeted adjustment, researchers have fabricated films predesigned active groups, highly ordered structures, conductivity. exhibit great potential for various thin-film electronics, such transistors, memristors, electrochromism, chemiresistors, photodetectors. Finally, future research directions perspectives 2DCPs are discussed terms synthetic engineering fabrication fully functional manipulation applications

Language: Английский

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