Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution
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Open Access
- 1 March 2021
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Communications
- Vol. 12 (1), 1-9
- https://doi.org/10.1038/s41467-021-21527-3
Abstract
Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H2, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < H2Por-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis.Funding Information
- National Natural Science Foundation of China (21572170, 21772149 and 21975188)
This publication has 58 references indexed in Scilit:
- Chemical sensing in two dimensional porous covalent organic nanosheetsChemical Science, 2015
- Photogenerated Excitons in Plain Core CdSe Nanocrystals with Unity Radiative Decay in Single Channel: The Effects of Surface and LigandsJournal of the American Chemical Society, 2015
- A hydrazone-based covalent organic framework for photocatalytic hydrogen productionChemical Science, 2014
- Covalent organic frameworks (COFs): from design to applicationsChemical Society Reviews, 2012
- High‐Rate Charge‐Carrier Transport in Porphyrin Covalent Organic Frameworks: Switching from Hole to Electron to Ambipolar ConductionAngewandte Chemie, 2012
- Light-Harvesting Metal–Organic Frameworks (MOFs): Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-Based MOFsJournal of the American Chemical Society, 2011
- Crystalline Covalent Organic Frameworks with Hydrazone LinkagesJournal of the American Chemical Society, 2011
- Hydrogen: An OverviewChemical Reviews, 2007
- Excited-state photophysics of donor-appended cobalt(II) porphyrins from picosecond transient absorption spectroscopyThe Journal of Physical Chemistry, 1993
- Spectra of porphyrinsJournal of Molecular Spectroscopy, 1961