Chen Hui-Ying, Huang Jia-Run, Liu Jia-Chuan, Huang Ning-Yu, Chen Xiao-Ming, Liao Pei-Qin
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME, Sun Yat-Sen University, Guangzhou, 510275, China.
Department of Chemistry and Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202412553. doi: 10.1002/anie.202412553. Epub 2024 Oct 14.
Efficient photocatalytic CO reduction coupled with the photosynthesis of pure HO is a challenging and significant task. Herein, using classical CO photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal-organic framework (MOF), namely AgTPyP-Fe. With water as electron donors, AgTPyP-Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g h and ca. 100 % selectivity, as well as HO evolution rate of 35.9 μmol g h. Since HO in the liquid phase can be more readily separated from the gaseous products of CO photoreduction, high-purity HO with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity.
高效的光催化CO还原与纯H₂O的光合作用相结合是一项具有挑战性且意义重大的任务。在此，以经典的CO光还原位点铁卟啉作为连接体，Ag(I)簇在一种新型金属有机框架（MOF）即AgTPyP-Fe中实现了空间分离且均匀分布。以水作为电子供体，AgTPyP-Fe在人工光合总反应中表现出卓越的性能，CO产率为36.5 μmol g⁻¹ h⁻¹，选择性约为100%，H₂O生成速率为35.9 μmol g⁻¹ h⁻¹。由于液相中的H₂O可以更易于从CO光还原的气态产物中分离出来，因此获得了浓度高达0.1 mM的高纯度H₂O。经理论计算和所建立的能级图证实，在一个集成框架内的还原性铁(II)卟啉和氧化性Ag(I)簇协同发挥作用以实现人工光合作用。此外，光致发光光谱和光电化学测量表明，Ag(I)簇与铁卟啉配体的稳固连接促进了有效的电荷分离和快速的电子转移，从而提高了光催化活性。
