Solid-Liquid Interfacial Engineered Large-Area Two-Dimensional Covalent Organic Framework Films.

Constructing uniform covalent organic framework (COF) film on substrates for electronic devices is highly desirable. Here, a simple and mild strategy is developed to prepare them by polymerization on a solid-liquid interface. The universality of the method is confirmed by the successful preparation of five COF films with different microstructures. These films have large lateral size, controllable thickness, and high crystalline quality. And COF patterns can also be directly achieved on substrates via hydrophilic and hydrophobic interface engineering, which is in favor of preparing device array. For application studies, the PyTTA-TPA (PyTTA: 4,4',4'',4'''-(1,3,6,8-Tetrakis(4-aminophenyl)pyrene and TPA: terephthalaldehyde) COF film has a high photoresponsivity of 59.79 µA W-1 at 420 nm for photoelectrochemical (PEC) detection. When employed as an active material for optoelectronic synaptic devices for the first attempt, it shows excellent light-stimulated synaptic plasticity properties such as short-term plasticity (STP), long-term plasticity (LTP), and the conversion of STP to LTP, which can be used to simulate biological synaptic functions.

Topology-Selective Manipulation of Two-Dimensional Covalent Organic Frameworks.

The manipulation of topological architectures in two-dimensional (2D) covalent organic framework (COF) materials for different applications is promising but remains a great challenge. Here, we first report the topology-selective synthesis of two distinct varieties of 2DCOFs, imine-based HT-COFs and benzimidazole-fused BI-HT-COFs, by simply altering acid catalysts. To HT-COFs, a superlattice of 1D channel with a persistent triangular shape is formed via Schiff base reaction, while to BI-HT-COFs, a hexagonal lattice structure with a highly conjugated structure and imidazole linkages is constructed due to an imine-based cyclization reaction. The two COFs exhibited marked differences in their bandgap, chemical stability, molecular adsorption, and catalytic activity, which make them have different fields of application. This work not only diversifies the hexaaminotriphenylene-based 2DCOF topologies but also provides vivid examples of structure-property relationships, which would facilitate fundamental research and potential applications of 2DCOFs.

Recrystallization of 2D C-MOF Films for High-Performance Electrochemical Sensors.

Two-dimensional (2D) conjugated metal-organic framework (c-MOF) films bring a completely new opportunity in the fields of catalysis, energy, and sensors, but preparing large-area continuous 2D c-MOF films remains a tremendous challenge. Here, we report a universal recrystallization strategy to synthesize large-area continuous 2D c-MOF films, revealing that the recrystallization strategy can significantly improve the electrochemical sensor sensitivity. Applying the 2D Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) c-MOF film as the active layer, the electrochemical sensor for glucose detection shows a high sensitivity of 20600 µA mM-1 cm-2, which is the best compared with the active materials reported previously. Most importantly, the as-made Cu3(HHTP)2 c-MOF-based electrochemical sensor possesses excellent stability. Overall, this work brings a brand-new universal strategy to prepare large-area continuous 2D c-MOF films for electrochemical sensors.