Donor–acceptor covalent organic frameworks-confined ultrafine bimetallic Pt-based nanoclusters for enhanced photocatalytic H2 generation
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Shengbo Zhang1,2(
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Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals. However, the lower photocatalytic efficiency due to the limited light trapping capacity, low electron transfer rate, and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application. Herein, we constructed a series of donor–acceptor (D–A) type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane (AB) hydrolysis. Under visible light irradiation at 20 °C, PtCo2@covalent organic framework (COF) showed the highest photocatalytic activity with a turnover frequency (TOF) of 486 min−1. Experiments and density functional theory (DFT) calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo2 nanoclusters. Specifically, the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework, and accelerate the photogenerated electron transfer from D–A type COF to PtCo2 nanocluster, which promotes the adsorption and activation of H2O and AB molecules and accelerates hydrogen release. Furthermore, PtCo2@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF. We believe that this work will provide a theoretical guide for the rational design of efficient D–A COF-based catalysts for photocatalysis.
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Donor–acceptor covalent organic frameworks-confined ultrafine bimetallic Pt-based nanoclusters for enhanced photocatalytic H2 generation
), Shengbo Zhang1,2(
)
Abstract
Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals. However, the lower photocatalytic efficiency due to the limited light trapping capacity, low electron transfer rate, and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application. Herein, we constructed a series of donor–acceptor (D–A) type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane (AB) hydrolysis. Under visible light irradiation at 20 °C, PtCo2@covalent organic framework (COF) showed the highest photocatalytic activity with a turnover frequency (TOF) of 486 min−1. Experiments and density functional theory (DFT) calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo2 nanoclusters. Specifically, the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework, and accelerate the photogenerated electron transfer from D–A type COF to PtCo2 nanocluster, which promotes the adsorption and activation of H2O and AB molecules and accelerates hydrogen release. Furthermore, PtCo2@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF. We believe that this work will provide a theoretical guide for the rational design of efficient D–A COF-based catalysts for photocatalysis.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 22178266), the Fundamental Research Funds for the Central Universities, and China Postdoctoral Science Foundation (Nos. 2021M691754 and 2023T160369). We acknowledge the Tianjin University for their help in sample characterization.
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