CO2-assisted rapid synthesis of porphyrin-based Bi-MOFs for photocatalytic CO2 reduction: An efficient strategy for carbon cycle

• Published in: Applied catalysis. B, Environmental Environmental, 2024-09, Vol.353, p.124097, Article 124097
• Main Authors: Cheng, Mingjie, Gao, Bo, Zheng, Xiaoli, Wu, Wenzhuo, Kong, Weiqian, Yan, Pengfei, Wang, Zubin, An, Bin, Zhang, Yunpeng, Li, Qingchao, Xu, Qun
• Format: Article
• Language: English
• Subjects: Carbon cycle; CO2 coordination; Metal-organic frameworks; Photocatalytic CO2 reduction; Supercritical CO2
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2024.124097

Exploring a facile, rapid and efficient route to produce metal-organic frameworks (MOFs) with highly accessible active sites is of great importance for catalysis. Here we demonstrate the CO2 coordination can drive low temperature rapid synthesis of porphyrin-based bismuth-MOFs (Bi-PMOFs) by utilizing synergistic physical and chemical properties of supercritical CO2 (SC-Bi-PMOFs). The molecular-level role of scCO2 in the synthesis of SC-Bi-PMOFs have been investigated through a series of characterizations including in-situ time-dependent infrared spectroscopy, wherein chemical coordination of CO2 promotes to fabricate 2D SC-Bi-PMOFs nanosheets. Moreover, the formation of Cu-PMOFs and Fe-PMOFs proves the universal scCO2 strategy for synthesizing PMOFs. Density functional theory (DFT) calculations together with experiments results confirm the SC-Bi-PMOFs with abundant active sites guarantee efficient ligand-to-metal charge transfer and reduction efficiency of CO2. The high-efficiency utilization of CO2 for synthesizing a series of MOFs and subsequent catalysis on photocatalytic CO2 reduction for valuable chemicals realize the carbon recycle. [Display omitted] •CO2-assisted rapid synthesis of Bi-PMOFs with well-exposed active site at low temperature.•CO2 chemical coordination facilitates the synthesis of 2D Bi-PMOF nanosheets.•SC-Bi-PMOFs exhibit superior photocatalytic CO2 reduction activity, an efficient strategy for realizing carbon cycle.•A series of M-PMOFs (M= Cu and Fe) were synthesized, verifying the universal prospect of scCO2 in the synthesis of PMOFs.