Construction of organic semiconducting materials with in-plane π-conjugated structures and robustness through carbon-carbon bond linkages, alternatively as organic graphene analogs, is extremely desired for powerfully optoelectrical conversion. However, the poor reversibility for sp 2 carbon bond forming reactions makes them unavailable for building high crystalline well-defined organic structures through a self-healing process, such as covalent organic frameworks (COFs). Here we report a scalable solution-processing approach to synthesize a family of two-dimensional (2D) COFs with trans -disubstituted C = C linkages via condensation reaction at arylmethyl carbon atoms on the basis of 3,5-dicyano-2,4,6-trimethylpyridine and linear/trigonal aldehyde (i.e., 4,4″-diformyl- p -terphenyl, 4,4′-diformyl-1,1′-biphenyl, or 1,3,5-tris(4-formylphenyl)benzene) monomers. Such sp 2 carbon-jointed-pyridinyl frameworks, featuring crystalline honeycomb-like structures with high surface areas, enable driving two half-reactions of water splitting separately under visible light irradiation, comparable to graphitic carbon nitride (g-C 3 N 4 ) derivatives.
Establishing an sp2-carbon-bonding pattern is one of the efficient accesses to various organic semiconducting materials. However, the less-reversible carbon–carbon bond formation makes it still challenging to spatially construct a well-defined organic framework with π-extended two-dimensional (2D) structure through solution process. Here, a Knoevenagel condensation approach to synthesize two new 2D covalent organic frameworks (COFs) connected by unsubstituted carbon–carbon double bond linkages through activating the methyl carbons of a 2,4,6-trimethyl-1,3,5-triazine monomer is presented. The resulting sp2-carbon-linked triazine-cored 2D sheets are vertically stacked into high-crystalline honeycomb-like structures, endowing this kind of COF with extended π-delocalization, tunable energy levels, as well as high surface areas, regular open channels, and chemical stabilities. On the other hand, their microfibrillar morphologies allow for the facile manipulation of thin films as photoelectrodes without additive. Accordingly, such kinds of COF-based photoelectrodes exhibit photocurrents up to ∼45 μA cm–2 at 0.2 V vs RHE as well as rapid charge transfer rates, in comparison with imine-linked COF-based photoelectrodes. In addition, both COFs are applicable for conducting photocatalytic hydrogen generation from water splitting by visible-light irradiation.
2D conjugated COF based on olefin (CC) linkages has been readily synthesized using the Knoevenagel condensation reaction.
Vinylene-bridged covalent organic frameworks (COFs) have shown great potential for advanced applications because of their high chemical stability and intriguing semiconducting properties. Exploring new functional monomers available for the reticulation of vinylene-bridged COFs and establishing effective reaction conditions are extremely desired for enlarging the realm of this kind of material. In this work, a series of vinylene-bridged two-dimensional (2D) COFs are synthesized by Knoevenagel condensation of tricyanomesitylene with ditopic or tritopic aromatic aldehydes. With use of appropriate secondary amines as catalysts, high-crystalline vinylene-bridged COFs were achieved, exhibiting long-range ordered structures, well-defined nanochannels, high surface areas (up to 1231 m 2 g −1 ), and excellent photophysical properties. Under a low loading amount and short reaction time, they enable aerobic photocatalytic transformation of arylboronic acids to phenols with high efficiency and excellent recyclability. This work demonstrates a new functional monomer, tricyanomesitylene, feasible for the general synthesis of vinylene-bridged COFs with potential application in photocatalytic organic transformation, which instigates further research on such kind of material.
Electrochemically driven carbon dioxide (CO2) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO2; however, this reduction process suffers from tardy kinetics due to low local concentration of CO2 on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin‐based covalent triazine framework (NiPor‐CTF) with atomically dispersed NiN4 centers as an efficient electrocatalyst for CO2 reduction reaction (CO2RR). The high density and atomically distributed NiN4 centers are confirmed by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy and extended X‐ray absorption fine structure. As a result, NiPor‐CTF exhibits high selectivity toward CO2RR with a Faradaic efficiency of >90% over the range from −0.6 to −0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at −0.9 V with a high current density of 52.9 mA cm−2, as well as good long‐term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO2 transition to *COOH on NiN4 active sites boosts the performance.
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