Abstract
Two dimensional polymers have emerged in recent years as useful materials for the development of catalysts for future energy demand. However, the synthesis of ultrathin organic two dimensional polymers is still limited and further development is necessary. Here we present the synthesis of nanometer-thick two-dimensional (2D) porphyrin polymer nanodisks via the exfoliation of covalent organic frameworks, and evaluate their performance in the hydrogen evolution reaction under irradiation with broadband light. The nanodisks are synthesized through the simultaneous axial coordination of pyridines and metal ions to produce 2D porphyrin nanodisks of 1 nm average thickness. Importantly, the polymer composite with platinum-reduced graphene oxide exhibits hydrogen evolution activity upon irradiation with visible and NIR light. These results represent the use of 2D ultrathin polymer nanodisks derived from covalent organic frameworks in heterogeneous photocatalytic processes.
Highlights
Two dimensional polymers have emerged in recent years as useful materials for the development of catalysts for future energy demand
In order to exfoliate the covalent organic frameworks (COFs) into two-dimensional (2D) polymer layers, we proposed that the coordination of axial ligands at the porphyrin centers of the COFs would disrupt the π-π interactions between the 2D-COF layers, resulting exfoliation (Fig. 1a)
We successfully synthesized a nanometer-thick 2D porphyrin polymer, by exfoliating COFs composed of porphyrin units, through the coordination of axial ligands
Summary
Two dimensional polymers have emerged in recent years as useful materials for the development of catalysts for future energy demand. The polymer composite with platinum-reduced graphene oxide exhibits hydrogen evolution activity upon irradiation with visible and NIR light These results represent the use of 2D ultrathin polymer nanodisks derived from covalent organic frameworks in heterogeneous photocatalytic processes. Dichtel et al reported that polar solvents, such as dioxane, water, and N,N-dimethylformamide (DMF), exfoliate COFs16 Most of these previous studies showed that the exfoliated COFs, comprised of 1,3,5-triphenylbenzene unit, still possess structures with several layers. It is still unclear whether or not it is possible to exfoliate COFs composed of π-conjugated molecules such as porphyrins for the synthesis of 2D polymer nanodisks. We describe the photocatalytic activity of these structures for H2 generation under irradiation with visible and near-infrared (NIR) light[23,24,25,26,27,28,29]
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