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Photo-generated dinuclear {Eu(II)}2 active sites for selective CO2 reduction in a photosensitizing metal-organic framework.

ABSTRACT: Photocatalytic reduction of CO2 is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that a large porous and stable metal-organic framework featuring dinuclear Eu(III)2 clusters as connecting nodes and Ru(phen)3-derived ligands as linkers is constructed to catalyze visible-light-driven CO2 reduction. Photo-excitation of the metalloligands initiates electron injection into the nodes to generate dinuclear {Eu(II)}2 active sites, which can selectively reduce CO2 to formate in a two-electron process with a remarkable rate of 321.9??mol?h-1?mmolMOF-1. The electron transfer from Ru metalloligands to Eu(III)2 catalytic centers are studied via transient absorption and theoretical calculations, shedding light on the photocatalytic mechanism. This work highlights opportunities in photo-generation of highly active lanthanide clusters stabilized in MOFs, which not only enables efficient photocatalysis but also facilitates mechanistic investigation of photo-driven charge separation processes.

SUBMITTER: Yan ZH

PROVIDER: S-EPMC6105582 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Photo-generated dinuclear {Eu(II)}2 active sites for selective CO2 reduction in a photosensitizing metal-organic framework.

Yan Zhi-Hao ZH Du Ming-Hao MH Liu Junxue J Jin Shengye S Wang Cheng C Zhuang Gui-Lin GL Kong Xiang-Jian XJ Long La-Sheng LS Zheng Lan-Sun LS

Nature communications 20180822 1

Photocatalytic reduction of CO2 is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that a large porous and stable metal-organic framework featuring dinuclear Eu(III)2 clusters as connecting nodes and Ru(phen)3-derived ligands as linkers is constructed to catalyze visible-light-driven CO2 reduction. Photo-excitatio ...[more]

PMID: 30135431

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Project description:Metal-organic frameworks (MOFs) have been an excellent platform for carbon dioxide reduction reactions (CO2RR). In this work, the feasibility of electrochemical reduction of CO2 to obtain C2-deep value-added products was investigated by the preparation of Mg-containing MOF-74 samples combined with transition metal cations (Ni2+, Co2+ and Zn2+). The prepared MOFs were used as electrocatalysts in CO2RR. Chronoamperometric analysis coupled to ATR-FTIR spectroscopy was employed to characterize the CO2 reduction products and subsequently via 1H NMR. Although an isostructural crystalline structure was observed in all synthesized MOFs, the pore diameter distribution was significantly affected due to the Mg coordination along with each transition metal nuclei with the organic ligand to form the MOF-74. Our results showed that Mg-containing MOF-74 electrocatalysts combined with Ni, Co and Zn ions successfully reduced CO2 to C2-deep products, while the monometallic Mg-MOF-74 showed only CO2 mineralization. An ester acetate, isopropyl alcohol, and formic acid were produced by Mg/Ni-MOF-74; isopropyl alcohol was provided by Mg/Co-MOF-74, and ethanol was generated by Mg/Zn-MOF-74. We observed that the change of the transition cation was a key factor in the selectivity of the obtained products, while the degree of Mg ions effectively incorporated into the MOF structure tuned the porosity and the electrocatalytic activity. Among them, Mg/Zn-MFOF-74 showed the highest Mg content loaded after synthesis and thus the most favorable electrocatalytic behavior towards CO2 reduction. Highlights • CO2-derived C2-deep reduction products were obtained by Mg-containing MOF-74 bimetallic electrocatalysts.• Mg-containing MOF-74 bimetallic electrocatalysts reduced CO2 to ester acetate, isopropanol, formic acid, and ethanol.• Mg/Zn-MOF-74 displayed the highest current density at a lower onset potential in CO2-saturated electrolyte.• The pore network could be tuned by the effective Mg content on a MOF-74 bimetallic sample.• Mg/Zn-MOF-74 showed the highest Mg content among all bimetallic electrocatalysts after the synthesis.

Dataset Information

Photo-generated dinuclear {Eu(II)}2 active sites for selective CO2 reduction in a photosensitizing metal-organic framework.

Publications

Photo-generated dinuclear {Eu(II)}<sub>2</sub> active sites for selective CO<sub>2</sub> reduction in a photosensitizing metal-organic framework.

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