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 CO coordination can drive low temperature rapid synthesis of porphyrin-based bismuth-MOFs (Bi-PMOFs) by utilizing synergistic physical and chemical properties of supercritical CO (SC-Bi-PMOFs). The molecular-level role of scCO 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 CO promotes to fabricate 2D SC-Bi-PMOFs nanosheets. Moreover, the formation of Cu-PMOFs and Fe-PMOFs proves the universal scCO 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 CO. The high-efficiency utilization of CO for synthesizing a series of MOFs and subsequent catalysis on photocatalytic CO reduction for valuable chemicals realize the carbon recycle.

中文翻译：

---

CO2辅助快速合成卟啉基Bi-MOFs用于光催化CO2还原：碳循环的有效策略


探索一种简便、快速、有效的途径来生产具有易于接近的活性位点的金属有机框架（MOF）对于催化具有重要意义。在这里，我们证明了利用超临界CO（SC-Bi-PMOFs）的协同物理和化学性质，CO配位可以驱动卟啉基铋-MOFs（Bi-PMOFs）的低温快速合成。通过一系列表征，包括原位时间依赖性红外光谱，研究了 scCO 在 SC-Bi-PMOF 合成中的分子水平作用，其中 CO 的化学配位促进了 2D SC-Bi-PMOF 纳米片的制造。此外，Cu-PMOFs和Fe-PMOFs的形成证明了合成PMOFs的通用scCO策略。密度泛函理论（DFT）计算和实验结果证实，SC-Bi-PMOFs具有丰富的活性位点，保证了配体到金属的有效电荷转移和CO的还原效率。CO的高效利用合成了一系列MOFs以及随后催化光催化CO还原有价值的化学品实现碳的回收利用。