Metal–organic frameworks (MOFs) have proved to be particularly appropriate for CO₂ conversion. In the present work, we report metalloporphyrin-based MOFs, PCN-222(M) (M = Fe, Co, Ni, and Cu), which promote photocatalytic CO₂ conversion to valuable chemicals. These ultra-highly stable frameworks are constructed from Zr₆ clusters and metalloporphyrin linkers. Metalloporphyrinic MOF has been synthesized and employed as a visible-light photocatalyst for carbon dioxide to form formate. The effect of metalloporphyrinic PCN-222(M) on CO₂ reduction has been studied. Remarkably, PCN-222(M) is highly efficient in visible light-driven CO₂ reduction into formate ion compared with the nonmetal porphyrinic PCN-222. Metal ions of porphyrinic linkers play a great role in CO₂ sorption, light harvesting, bandgap, photoluminescence (pL) intensity, and charge transfer, which influence CO₂ reduction. CO₂ adsorption and activation over metal ions of porphyrinic linkers play a significant part in the improvement of the conversion efficiency; the product obtained was characterized by gas chromatography/mass spectrometry (GC/MS) and ion mobility spectrometry (IMS) analyses. The reaction mechanism has been discussed in detail.

中文翻译：

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在（金属）卟啉基金属有机骨架上进行有效的可见光 CO2 光还原以获得有用的碳氢化合物

金属有机框架 (MOF) 已被证明特别适用于 CO ₂转化。在目前的工作中，我们报告了基于金属卟啉的 MOF，PCN-222(M)（M = Fe、Co、Ni 和 Cu），它们促进光催化 CO ₂转化为有价值的化学品。这些超高稳定性框架由 Zr ₆簇和金属卟啉连接体构成。金属卟啉 MOF 已被合成并用作二氧化碳形成甲酸盐的可见光光催化剂。已经研究了金属卟啉 PCN-222(M) 对 CO ₂还原的影响。值得注意的是，PCN-222(M) 在可见光驱动的 CO _{2 中}非常高效与非金属卟啉 PCN-222 相比，还原成甲酸根离子。卟啉连接体的金属离子在 CO ₂吸附、光收集、带隙、光致发光 (pL) 强度和电荷转移中发挥重要作用，这些都影响 CO ₂还原。CO ₂对卟啉连接体金属离子的吸附和活化对提高转化效率起着重要作用；所得产物通过气相色谱/质谱 (GC/MS) 和离子迁移谱 (IMS) 分析进行表征。已经详细讨论了反应机理。