Multielectron transportation of polyoxometalate-grafted metalloporphyrin coordination frameworks for selective CO2-to-CH4 photoconversion |
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| Authors: | Qing Huang Jiang Liu Liang Feng Qi Wang Wei Guan Long-Zhang Dong Lei Zhang Li-Kai Yan Ya-Qian Lan Hong-Cai Zhou |
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| Affiliation: | 1. Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China;2. Department of Chemistry, Northeast Normal University, Changchun 130024, China;3. Department of Chemistry, Texas A&M University, College Station, TX 77843-3255, USA |
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| Abstract: | Photocatalytic CO2 reduction into energy carriers is of utmost importance due to the rising concentrations of CO2 and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH4), from CO2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H2TCPP) linkers, exhibiting high selectivity (>96%) for CH4 formation in a photocatalytic CO2-reduction system. To our knowledge, the high CH4 selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO2-to-CH4 conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH4 formation, considering that eight MoV atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO2-to-CH4 transformation. |
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| Keywords: | reductive polyoxometalate coordination frameworks CO2 photoreduction high selectivity methane |
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