Construction of Layer-Blocked Covalent Organic Framework Heterogenous Films via Surface-Initiated Polycondensations with Strongly Enhanced Photocatalytic Properties.

Imine-linked covalent organic frameworks (COFs) usually show high crystallinity and porosity, while vinyl-linked COFs have excellent semiconducting properties and stability. Therefore, achieving the advantages of imine- and vinyl-linkages in a single COF material is highly interesting but remains challenging. Herein, we demonstrate the fabrication of a layer-blocked COF (LB-COF) heterogeneous film that is composed of imine- and vinyl-linkages through two successive surface-initiated polycondensations. In brief, the bottom layer of imine-linked COF film was constructed on an amino-functionalized substrate via Schiff-base polycondensation, in which the unreacted aldehyde edges could be utilized for initiating aldol polycondensation to prepare the second layer of vinyl-linked COF film. The resultant LB-COF film displays excellent ordering due to the crystalline templating effect from the bottom imine-linked COF layer; meanwhile, the upper vinyl-linked COF layer could strongly enhance its stability and photocatalytic properties. The LB COF also presents superior performance in photocatalytic uranium extraction (320 mg g-1), which is higher than the imine-linked (35 mg g-1) and the vinyl-linked (295 mg g-1) counterpart. This study provides a novel surface-initiated strategy to synthesize layer-blocked COF heterogeneous films that combine the advantages of each building block.

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

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

Galvanic-Replacement-Assisted Synthesis of Nanostructured Silver-Surface for SERS Characterization of Two-Dimensional Polymers.

Surface-enhanced Raman scattering (SERS) spectroscopy is a powerful technology in trace analysis. However, the wide applications of SERS in practice are limited by the expensive substrate materials and the complicated preparation processes. Here we report a simple and economical galvanic-replacement-assisted synthesis route to prepare Ag nanoparticles on Cu(0) foil (nanoAg@Cu), which can be directly used as SERS substrate. The fabrication process is fast (ca. 10 min) and easily scaled up to centimeters or even larger. In addition, the morphology of the nanoAg@Cu (with Ag particles size from 30 nm to 160 nm) can be adjusted by various additives (e.g., amino-containing ligands). Finally, we show that the as-prepared nanoAg@Cu can be used for SERS characterization of two-dimensional polymers, and ca. 298 times relative enhancement of Raman intensity is achieved. This work offers a simple and economical strategy for the scalable fabrication of silver-based SERS substrate in thin film analysis.

Construction of Thiadiazole-Bridged sp2-Carbon-Conjugated Covalent Organic Frameworks with Diminished Excitation Binding Energy Toward Superior Photocatalysis.

Sp2-carbon-conjugated covalent organic frameworks (sp2c-COFs) have emerged as promising platforms for phototo-chemical energy conversion due to their tailorable optoelectronic properties, in-plane π-conjugations, and robust structures. However, the development of sp2c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp2c-COF (sp2c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp2c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp2c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp2c-COF-ST exhibits a significant photocurrent up to ∼14.5 µA cm-2 at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT ∼ 9.5 µA cm-2) and full imine linkages (imi-COF-SNNT ∼ 4.9 µA cm-2), emphasizing the importance of the structure-property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp2c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp2c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp2c-COFs with promising photocatalytic performance.

Two-Dimensional Conjugated Polymers: a New Choice For Organic Thin-Film Transistors.

Organic thin-film transistors (OTFTs) as a vital component among transistors have shown great potential in smart sensing, flexible displays, and bionics due to their flexibility, biocompatibility and customizable chemical structures. Even though linear conjugated polymer semiconductors are common for constructing channel materials of OTFTs, advanced materials with high charge carrier mobility, tunable band structure, robust stability, and clear structure-property relationship are indispensable for propelling the evolution of OTFTs. Two-dimensional conjugated polymers (2DCPs), featured with conjugated lattice, tailorable skeletons, and functional porous structures, match aforementioned criteria closely. In this review, we firstly introduce the synthesis of 2DCP thin films, focusing on their characteristics compatible with the channels of OTFTs. Subsequently, the physics and operating mechanisms of OTFTs and the applications of 2DCPs in OTFTs are summarized in detail. Finally, the outlook and perspective in the field of OTFTs using 2DCPs are provided as well.

Ice-Inspired Polymeric Slippery Surface with Excellent Smoothness, Stability, and Antifouling Properties.

Ice is omnipresent in our daily life and possesses intrinsic slipperiness as a result of the formation of a quasi-liquid layer. Thus, the functional surfaces inspired by ice show great prospects in widespread fields from surface lubrication to antifouling coatings. Herein, we report an ice-inspired polymeric slippery surface (II-PSS) constructed by a self-lubricating liquid layer and a densely surface-grafted polymer brush. The polymer brush layer could act as a homogeneous matrix to capture lubricant molecules via strong and dynamic dipole-dipole interactions to form a stable quasi-liquid layer that resembles the ice surface. The II-PSS can be easily fabricated on various solid substrates (e.g., silicon, glass, aluminum oxide, plastics, etc.) with excellent smoothness (roughness of ∼0.4 nm), optical transmittance (∼94.5%), as well as repellence toward diverse liquids with different surface tensions (22.3-72.8 mN m-1), pH values (1-14), salinity, and organic pollutants. Further investigation shows that the II-PSS exhibits extremely low attachment for proteins and marine organisms (e.g., algae and mussels) for over one month. These results demonstrate a robust and promising strategy for high-performance antifouling coatings.

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

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 and optoelectronics. However, so far, sp2c-COFs have been mainly limited to microcrystalline powders, and this consequently hampered their performances in devices. Herein, we report a simple and robust methodology to fabricate large-area, free-standing, and crystalline sp2c-COF films (TFPT-TMT and 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 sp2c-COF films show lateral sizes up to 120 cm2 and tunable thickness from tens of nanometers to a few micrometers. Owing to the robust framework and highly ordered quasi-1D channels, the sp2c-COF membrane-based osmotic power generator presents an output power density of 14.1 W m-2 under harsh conditions, outperforming most reported COF membranes as well as commercialized benchmark devices (5 W m-2). This work demonstrates a simple and robust interfacial methodology for the fabrication of sp2c-COF films/membranes for green energy applications and potential optoelectronics.

Engineering of Graphdiyne-Based Functional Coatings for the Protection of Arbitrary Shapes of Copper Substrates.

Copper-based materials are very important for many application fields from marine industry to energy management and electronic devices. For most of these applications, the copper objects require long-term contact to a wet and salty environment, which leads to serious corrosion of copper. In this work, we report a thin graphdiyne layer directly grown on arbitrary shapes of copper objects at mild conditions, which could function as a protective coating for the copper substrates in artificial seawater with corrosion inhibition efficiency of ∼99.75%. To further improve the protective performance of the coating, the graphdiyne layer is fluorinated and followed by infusion with a fluorine-containing lubricant (i.e., perfluoropolyether). As a result, a slippery surface is obtained, which shows enhanced corrosion inhibition efficiency of ∼99.99% as well as excellent antibiofouling properties against microorganisms, such as protein and algae. Finally, the coatings are successfully applied in the protection of a commercial copper radiator from long-term attack of artificial seawater without disturbing its thermal conductivity. These results demonstrate the great potential of graphdiyne-based functional coatings for the protection of copper devices in aggressive environments.

Tinware-Inspired Aerobic Surface-Initiated Controlled Radical Polymerization (SI-Sn0CRP) for Biocompatible Surface Engineering.

Surface anchored polymer brushes prepared by surface-initiated controlled radical polymerization (SI-CRP) have raised considerable interest in biomaterials and bioengineering. However, undesired residues of noxious transition metal catalysts critically restrain their widespread biomedical applications. Herein, we present a robust and biocompatible surface-initiated controlled radical polymerization catalyzed by a Sn(0) sheet (SI-Sn0CRP) under ambient conditions. Through this approach, microliter volumes of vinyl monomers with diverse functions (heterocyclic, ionic, hydrophilic, and hydrophobic) could be efficiently converted to homogeneous polymer brushes. The excellent controllability of SI-Sn0CRP strategy is further demonstrated by the exquisite fabrication of predetermined block and patterned polymer brushes through chain extension and photolithography, respectively. Additionally, in virtue of intrinsic biocompatibility of Sn, the resultant polymer brushes present transcendent affinity toward blood and cell, in marked contrast to those of copper-based approaches. This strategy could provide an avenue for the controllable fabrication of biocompatible polymer brushes toward biological applications.

Seawater-Boosting Surface-Initiated Atom Transfer Radical Polymerization for Functional Polymer Brush Engineering.

Iron-mediated surface-initiated reversible deactivation radical polymerization (Fe0 SI-RDRP) is an appealing approach to produce robust polymer surfaces with low toxicity and biocompatibility, while its application has been limited so far due to the poor activity of iron-based catalysts. Herein, we show that the iron(0)-mediated surface-initiated atom transfer radical polymerization (Fe0 SI-ATRP) could be significantly enhanced by simply using seawater as reaction media. In comparison, there was no polymer brush formation in deionized water. This method could convert a range of monomers to well-defined polymer brushes with unparalleled speed (up to 31.5 nm min-1) and a minor amount of monomer consumption (µL). Moreover, the resultant polymer brush shows chain-end fidelity which could be exemplified by repetitive Fe0 SI-ATRP to obtain tetrablock brushes. Finally, we show the preparation of polymer-brush-gated ion-selective membranes by Fe0 SI-ATRP for osmotic energy conversion, which gives excellent power densities of 5.93 W m-2, outperforming the most reported as well as commercialized benchmark (5 W m-2).

Galvanic-Replacement-Assisted Surface-Initiated Atom Transfer Radical Polymerization for Functional Polymer Brush Engineering.

Here we present a facile and robust strategy, namely, galvanic-replacement-assisted surface-initiated Cu(0)-mediated atom transfer radical polymerization (gr-SI-Cu0ATRP, or gr-SI-Cu0CRP) for polymer brush engineering under ambient conditions. In gr-SI-Cu0ATRP, highly active and nanostructured Cu(0) surfaces are obtained by a simple galvanic replacement on zinc/aluminum surfaces in dilute Cu2+ solution. Polymer brush growth rate is extremely high (up to ∼904 nm in 30 min polymerization); meanwhile, both nano Cu(0) surfaces and Cu2+ solution can be reused multiple times without losing grafting efficiency. We also demonstrate that the gr-SI-Cu0ATRP is advantageous for polymer brush engineering on arbitrary substrates, including flexible (polyethylene terephthalate), curved (polycarbonate), and porous (anodic aluminum oxide), and endow the substrates with various functionalities, for example, anti-icing, antifogging, and ion selectivity.