Citation: Hui-Ying Chen, Hao-Lin Zhu, Pei-Qin Liao, Xiao-Ming Chen. Integration of Ru(II)-Bipyridyl and Zinc(II)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction[J]. Acta Physico-Chimica Sinica, ;2024, 40(4): 230604. doi: 10.3866/PKU.WHXB202306046 shu

Integration of Ru(II)-Bipyridyl and Zinc(II)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction

School of Chemistry, MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Sun Yat-Sen University, Guangzhou 510275, China

Corresponding author: Hao-Lin Zhu, Pei-Qin Liao, Xiao-Ming Chen,
Received Date: 27 June 2023
Revised Date: 14 July 2023
Accepted Date: 14 July 2023

Fund Project: The project was supported by the National Key Research and Development Program of China (2021YFA1500401), the National Natural Science Foundation of China (21890380 and 21821003), the Local Innovative and Research Teams Project of the Guangdong Pearl River Talents Program, China (2017BT01C161), and the Technology Innovation Strategy Special City and County Science and Technology Innovation Support Project, China (STKJ2023078).

Efficiently converting CO₂ and H₂O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis. However, achieving artificial photocatalytic CO₂ reduction using H₂O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties. Metal-organic frameworks (MOFs) are promising candidates for overall CO₂ photoreduction due to their large surface area, diverse active sites, and excellent tailorability. In this study, we designed a metal-organic framework photocatalyst, named PCN-224(Zn)-Bpy(Ru), by integrating photoactive Zn(II)-porphyrin and Ru(II)-bipyridyl moieties. In comparison, two isostructural MOFs just with either Zn(II)-porphyrin or Ru(II)-bipyridyl moiety, namely PCN-224-Bpy(Ru) and PCN-224(Zn)-Bpy were also synthesized. As a result, PCN-224(Zn)-Bpy(Ru) exhibited the highest photocatalytic conversion rate of CO₂ to CO, with a production rate of 7.6 µmol·g⁻¹·h⁻¹ in a mixed solvent of CH₃CN and H₂O, without the need for co-catalysts, photosensitizers, or sacrificial agents. Mass spectrometer analysis detected the signals of ¹³CO (m/z = 29), ¹³C¹⁸O (m/z = 31), ¹⁶O¹⁸O (m/z = 34), and ¹⁸O₂ (m/z = 36), confirming that CO₂ and H₂O acted as the carbon and oxygen sources for CO and O₂, respectively, thereby confirming the coupling of photocatalytic CO₂ reduction with H₂O oxidation. In contrast, using PCN-224-Bpy(Ru) or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0 µmol·g⁻¹·h⁻¹, respectively. Mechanistic studies revealed that the lowest unoccupied molecular orbital (LUMO) potential of PCN-224(Zn)-Bpy(Ru) is more negative than the redox potentials of CO₂/CO, and the highest occupied molecular orbital (HOMO) potential is more positive than that of H₂O/O₂, satisfying the thermodynamic requirements for overall photocatalytic CO₂ reduction. In comparison, the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H₂O/O₂, indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO₂ reduction coupled with H₂O oxidation. Additionally, photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru) was almost completely quenched, and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru) was observed. These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru), which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru) compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru). In summary, the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru) play important roles of a photosensitizer and CO₂ reduction as well as H₂O oxidation sites, and their efficient cooperation optimizes the band structure, thereby facilitating the coupling of CO₂ reduction with H₂O oxidation and resulting in high-performance artificial photocatalytic CO₂ reduction.
- Metal-organic framework,
- Zn(II) porphyrin,
- Ru(II) bipyridyl complex,
- Photogenerated charge,
- CO₂ photoreduction
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Integration of Ru(II)-Bipyridyl and Zinc(II)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO2 Photoreduction

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通讯作者: 陈斌, bchen63@163.com

Integration of Ru(II)-Bipyridyl and Zinc(II)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction