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
1. [1]
  (1) Hansen, J.; Johnson, D.; Lacis, A.; Lebedeff, S.; Lee, P.; Rind, D.; Russell, G. Science 1981, 213, 957. doi: 10.1126/science.213.4511.957
2. [2]
  (2) Mercer, J. H. Nature 1978, 271, 321. doi: 10.1038/271321a0
3. [3]
  (3) Lacis, A. A.; Schmidt, G. A.; Rind, D.; Ruedy, R. A. Science 2010, 330, 356. doi: 10.1126/science.1190653
4. [4]
  (4) Li, R.; Zhang, W.; Zhou, K. Adv. Mater. 2018, 30, e1705512. doi: 10.1002/adma.201705512
5. [5]
  (5) Mertens, J.; Breyer, C.; Arning, K.; Bardow, A.; Belmans, R.; Dibenedetto, A.; Erkman, S.; Gripekoven, J.; Léonard, G.; Nizou, S.; et al. Joule 2023, 7, 442. doi: 10.1016/j.joule.2023.01.005
6. [6]
  (6) Tooru, I.; Akira, F.; Satoshi, K.; Kenichi, H. Nature 1979, 277, 637. doi: 10.1038/277637a0
7. [7]
8. [8]
  (8) Xiong, X. Y.; Mao, C. L.; Yang, Z. J.; Zhang, Q. H.; Waterhouse, G. I. N.; Gu, L.; Zhang, T. R. Adv. Energy Mater. 2020, 10, 2002928. doi: 10.1002/aenm.202002928
9. [9]
  (9) Lan, G. X.; Fan, Y. J.; Shi, W. J.; You, E.; Veroneau, S. S.; Lin, W. B. Nat. Catal. 2022, 5, 1006. doi: 10.1038/s41929-022-00865-5
10. [10]
  (10) Sun, K.; Qian, Y.; Jiang, H. L. Angew. Chem. Int. Ed. 2023, 62, e202217565. doi: 10.1002/anie.202217565
11. [11]
  (11) Dong, L. Z.; Zhang, L.; Liu, J.; Huang, Q.; Lu, M.; Ji, W. X.; Lan, Y. Q. Angew. Chem. Int. Ed. 2020, 59, 2659. doi: 10.1002/anie.201913284
12. [12]
  (12) Fang, Z. B.; Liu, T. T.; Liu, J.; Jin, S.; Wu, X. P.; Gong, X. Q.; Wang, K.; Yin, Q.; Liu, T. F.; Cao, R.; et al. J. Am. Chem. Soc. 2020, 142, 12515. doi: 10.1021/jacs.0c05530
13. [13]
  (13) Huang, N. Y.; Shen, J. Q.; Zhang, X. W.; Liao, P. Q.; Zhang, J. P.; Chen, X. M. J. Am. Chem. Soc. 2022, 144, 8676. doi: 10.1021/jacs.2c01640
14. [14]
  (14) Jiang, Z.; Xu, X.; Ma, Y.; Cho, H. S.; Ding, D.; Wang, C.; Wu, J.; Oleynikov, P.; Jia, M.; Cheng, J.; et al. Nature 2020, 586, 549. doi: 10.1038/s41586-020-2738-2
15. [15]
  (15) Li, X. X.; Zhang, L.; Liu, J.; Yuan, L.; Wang, T.; Wang, J. Y.; Dong, L. Z.; Huang, K.; Lan, Y. Q. JACS Au 2021, 1, 1288. doi: 10.1021/jacsau.1c00186
16. [16]
  (16) Lu, M.; Zhang, M.; Liu, J.; Yu, T. Y.; Chang, J. N.; Shang, L. J.; Li, S. L.; Lan, Y. Q. J. Am. Chem. Soc. 2022, 144, 1861. doi: 10.1021/jacs.1c11987
17. [17]
  (17) Tan, L. L.; Ong, W. J.; Chai, S. P.; Mohamed, A. R. Chem. Eng. J. 2017, 308, 248. doi: 10.1016/j.cej.2016.09.050
18. [18]
  (18) Wu, L. Y.; Mu, Y. F.; Guo, X. X.; Zhang, W.; Zhang, Z. M.; Zhang, M.; Lu, T. B. Angew. Chem. Int. Ed. 2019, 58, 9491. doi: 10.1002/anie.201904537
19. [19]
  (19) Zhang, L.; Li, R. H.; Li, X. X.; Liu, J.; Guan, W.; Dong, L. Z.; Li, S. L.; Lan, Y. Q. Proc. Natl. Acad. Sci. U.S.A. 2022, 119, e2210550119. doi: 10.1073/pnas.2210550119
20. [20]
  (20) Zhao, C.; Jiang, Z.; Liu, Y.; Zhou, Y.; Yin, P.; Ke, Y.; Deng, H. J. Am. Chem. Soc. 2022, 144, 23560. doi: 10.1021/jacs.2c10687
21. [21]
  (21) Zhou, J.; Li, J.; Kan, L.; Zhang, L.; Huang, Q.; Yan, Y.; Chen, Y.; Liu, J.; Li, S. L.; Lan, Y. Q. Nat. Commun. 2022, 13, 4681. doi: 10.1038/s41467-022-32449-z
22. [22]
  (22) Navalon, S.; Dhakshinamoorthy, A.; Alvaro, M.; Ferrer, B.; Garcia, H. Chem. Rev. 2023, 123, 445. doi: 10.1021/acs.chemrev.2c00460
23. [23]
  (23) Qian, Z. P.; Zhang, R.; Xiao, Y.; Huang, H. W.; Sun, Y.; Chen, Y.; Ma, T. Y.; Sun, X. D. Adv. Energy Mater. 2023, 13, 2300086. doi: 10.1002/aenm.202300086
24. [24]
  (24) Ezugwu, C. I.; Liu, S. W.; Li, C. H.; Zhuiykov, S.; Roy, S.; Verpoort, F. Coord. Chem. Rev. 2022, 450, 214245. doi: 10.1016/j.ccr.2021.214245
25. [25]
  (25) Mo, G. L.; Wang, Q.; Lu, W. Y.; Wang, C.; Li, P. Chin. J. Chem. 2022, 41, 335. doi: 10.1002/cjoc.202200571
26. [26]
  (26) Zhu, L. X.; Hu, F. L.; Sun, B.; Gu, S. N.; Gao, T. T.; Zhou, G. W. Adv. Sustain. Syst. 2022, 7, 2200394. doi: 10.1002/adsu.202200394
27. [27]
  (27) Bonin, J.; Robert, M.; Routier, M. J. Am. Chem. Soc. 2014, 136, 16768. doi: 10.1021/ja510290t
28. [28]
  (28) Nikoloudakis, E.; Lopez-Duarte, I.; Charalambidis, G.; Ladomenou, K.; Ince, M.; Coutsolelos, A. G. Chem. Soc. Rev. 2022, 51, 6965. doi: 10.1039/d2cs00183g
29. [29]
  (29) Jing, J.; Yang, J.; Li, W.; Wu, Z.; Zhu, Y. Adv. Mater. 2022, 34, e2106807. doi: 10.1002/adma.202106807
30. [30]
  (30) Qian, Y.; Li, D.; Han, Y.; Jiang, H. L. J. Am. Chem. Soc. 2020, 142, 20763. doi: 10.1021/jacs.0c09727
31. [31]
  (31) Xiong, X. Y.; Zhao, Y. F.; Shi, R.; Yin, W. J.; Zhao, Y. X.; Waterhouse, G. I. N.; Zhang, T. R. Sci. Bull. 2020, 65, 987. doi: 10.1016/j.scib.2020.03.032
32. [32]
  (32) Limburg, B.; Bouwman, E.; Bonnet, S. ACS Catal. 2016, 6, 5273. doi: 10.1021/acscatal.6b00107
33. [33]
  (33) Xie, Y.; Shaffer, D. W.; Lewandowska-Andralojc, A.; Szalda, D. J.; Concepcion, J. J. Angew. Chem. Int. Ed. 2016, 55, 8067. doi: 10.1002/anie.201601943
34. [34]
  (34) Zhang, L.; Yuan, S.; Fan, W.; Pang, J.; Li, F.; Guo, B.; Zhang, P.; Sun, D.; Zhou, H. C. ACS Appl. Mater. Interfaces 2019, 11, 22390. doi: 10.1021/acsami.9b05091
35. [35]
  (35) Sullivan, B. P.; Salmon, D. J.; Meyer, T. J. Inorg. Chem. 1977, 17, 3335. doi: 10.1021/ic50190a006
36. [36]
  (36) Xie, P. H.; Hou, Y. J.; Zhang, B. W.; Cao, Y.; Wu, F.; Tian, W. J.; Shen, J. C. J. Chem. Soc., Dalton Trans. 1999, 4217. doi: 10.1039/A907621B
37. [37]
  (37) Zhang, Z. J.; Liu, H.; Xu, J. Y.; Zeng, H. B. J. Photochem. Photobiol. A 2017, 336, 25. doi: 10.1016/j.jphotochem.2016.12.020
38. [38]
  (38) Akl, A. A.; Kamal, H.; Abdel-Hady, K. Appl. Surf. Sci. 2006, 252, 8651. doi: 10.1016/j.apsusc.2005.12.001
39. [39]
  (39) Jiao, X.; Zheng, K.; Hu, Z.; Sun, Y.; Xie, Y. ACS Cent. Sci. 2020, 6, 653. doi: 10.1021/acscentsci.0c00325
40. [40]
  (40) Joshi, U. A.; Maggard, P. A. J. Phys. Chem. Lett. 2012, 3, 1577. doi: 10.1021/jz300477r
41. [41]
  (41) Wang, C.; Wang, S. J.; Kong, F. G. Inorg. Chem. 2021, 60, 5034. doi: 10.1021/acs.inorgchem.1c00063
1. [1]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
2. [2]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
3. [3]
  Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO₂/BiOBr S-Scheme Heterostructure for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-. doi: 10.3866/PKU.WHXB202407021
4. [4]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
5. [5]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
6. [6]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
7. [7]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
8. [8]
  Fan Wu , Wenchang Tian , Jin Liu , Qiuting Zhang , YanHui Zhong , Zian Lin . Core-Shell Structured Covalent Organic Framework-Coated Silica Microspheres as Mixed-Mode Stationary Phase for High Performance Liquid Chromatography. University Chemistry, 2024, 39(11): 319-326. doi: 10.12461/PKU.DXHX202403031
9. [9]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
10. [10]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
11. [11]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
12. [12]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
13. [13]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
14. [14]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
15. [15]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050
16. [16]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
17. [17]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
18. [18]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
19. [19]
  Jiaxing Cai , Wendi Xu , Haoqiang Chi , Qian Liu , Wa Gao , Li Shi , Jingxiang Low , Zhigang Zou , Yong Zhou . 具有0D/2D界面的InOOH/ZnIn₂S₄空心球S型异质结用于增强光催化CO₂转化性能. Acta Physico-Chimica Sinica, 2024, 40(11): 2407002-. doi: 10.3866/PKU.WHXB202407002
20. [20]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(418)
HTML views(42)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

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