Photo- or electroreduction of carbon dioxide into highly valued products offers a promising strategy to achieve carbon neutrality. Here, a series of polyoxometalate-based metal-organic frameworks (M-POMOFs) were constructed by metalloporphyrins [tetrakis(4-carboxyphenyl)-porphyrin-M (M-TCPPs)] and reductive POM for photo- and electrocatalytic carbon dioxide reductions (PCR and ECR, respectively), and the mysteries between the roles of single metal site and cluster in catalysis were disclosed. Iron-POMOF exhibited an excellent selectivity (97.2%) with high methane production of 922 micromoles per gram in PCR, together with superior Faradaic efficiency for carbon dioxide to carbon monoxide (92.1%) in ECR. The underlying mechanisms were further clarified. Photogenerated electrons transferred from iron-TCPP to the POM cluster for methane generation under irradiation, while the abundant electrons flowed to the center of iron-TCPP for carbon monoxide formation under the applied electric field. The specific multielectron products generated on iron-POMOF through switching driving forces to control electron flow direction between single metal site and cluster catalysis.
CITATION STYLE
Huang, Q., Niu, Q., Li, X. F., Liu, J., Sun, S. N., Dong, L. Z., … Lan, Y. Q. (2022). Demystifying the roles of single metal site and cluster in CO2 reduction via light and electric dual-responsive polyoxometalate-based metal-organic frameworks. Science Advances, 8(49). https://doi.org/10.1126/sciadv.add5598
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