Efficient and stable photocatalytic H2 evolution by self-assembly of zirconium(iv) coordination with perylene diimide supramolecules under visible light irradiation
- 15 February 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of Materials Chemistry A
- Vol. 9 (12), 7675-7683
- https://doi.org/10.1039/d1ta00464f
Abstract
Wide spectral response and rapid separation and transfer of charge carriers are critical to the high activity of photocatalysts. Metal ions can work as an electron mediator to promote charge transfer. Therefore, we adopted the strategy of forming coordination bonds between metal cations of zirconium(IV) with a perylene diimide (PDI)-based organic supramolecular system to broaden the absorption spectrum and facilitate separation of photoinduced charges. We successfully prepared a series of doped supramolecular photocatalysts P-PMPDI containing different contents of ZrIV cations via phosphonate/ZrIV coordination bonds, and among them, P-PMPDI-Zr (ZrIV : P-PMPDI = 0.25 : 1) exhibited the highest activity toward the hydrogen evolution reaction (HER) of 2.52 mmol h−1 (50.46 mmol g−1 h−1) with an apparent quantum yield of 11.7% at 630 nm and good stability. Besides, we also prepared Co, Ni, and Cu-doped P-PMPDI supramolecular catalysts (M : P-PMPDI = 0.25 : 1), all of which showed higher HER activity than the bare P-PMPDI, but still lower activity than P-PMPDI-Zr. X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR) and density functional theory (DFT) calculations further demonstrated that ZrIII ions formed in the photocatalytic process are the active sites, rendering the supramolecular photocatalyst P-PMPDI-Zr more favorable for photocatalytic H2 evolution.Keywords
Funding Information
- National Natural Science Foundation of China (21971064, 21825301, 21772040)
- Science and Technology Commission of Shanghai Municipality (17520750100)
- Fundamental Research Funds for the Central Universities (50321101918001, 222201717003)
This publication has 49 references indexed in Scilit:
- Studies on Photocatalytic CO2 Reduction over NH2‐Uio‐66(Zr) and Its Derivatives: Towards a Better Understanding of Photocatalysis on Metal–Organic FrameworksChemistry – A European Journal, 2013
- Infrared Probes for Studying the Structure and Dynamics of BiomoleculesChemical Reviews, 2013
- Self‐Assembled Bilayer Films of Ruthenium(II)/Polypyridyl Complexes through Layer‐by‐Layer Deposition on Nanostructured Metal OxidesAngewandte Chemie, 2012
- Amine-functionalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organic transformationsChemical Communications, 2012
- Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic PhotocatalysisJournal of the American Chemical Society, 2011
- Reversible Switching between Molecular and Charge Transfer Phases in a Liquid Crystalline Organic SemiconductorChemistry of Materials, 2008
- Structural study of vapour phase deposited 3,4,9,10-perylene tetracarboxylicacid diimide: Comparison between single crystal and ultra thin films grown on Pt(100)Thin Solid Films, 2006
- Density-functional exchange-energy approximation with correct asymptotic behaviorPhysical Review A, 1988
- Density-functional approximation for the correlation energy of the inhomogeneous electron gasPhysical Review B, 1986
- Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysisCanadian Journal of Physics, 1980