Steering the Selectivity of Carbon Dioxide Electroreduction from Single-Carbon to Multicarbon Products on Metal-Organic Frameworks via Facet Engineering.

Lu, Pengyi; Lv, Jia; Chen, Yu; Ma, Yangbo; Wang, Yunhao; Lyu, Weichao; Yu, Jinli; Zhou, Jingwen et al. · Nano Lett · 2024

basic_science · Level V

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Abstract

Although metal-organic frameworks (MOFs) have attracted more attention for the electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR), obtaining multicarbon products with a high Faradaic efficiency (FE) remains challenging, especially under neutral conditions. Here, we report the controlled synthesis of stable Cu(I) 5-mercapto-1-methyltetrazole framework (Cu-MMT) nanostructures with different facets by rationally modulating the reaction solvents. Significantly, Cu-MMT nanostructures with (001) facets are acquired using isopropanol as a solvent, which favor multicarbon production with an FE of 73.75% and a multicarbon:single-carbon ratio of 3.93 for CO<sub>2</sub>RR in a neutral electrolyte. In sharp contrast, Cu-MMT nanostructures with (100) facets are obtained utilizing water, promoting single-carbon generation with an FE of 63.98% and a multicarbon: single-carbon ratio of only 0.18. Furthermore, this method can be extended to other Cu-MMT nanostructures with different facets in tuning the CO<sub>2</sub> reduction selectivity. This work opens up new opportunities for the highly selective and efficient CO<sub>2</sub> electroreduction to multicarbon products on MOFs via facet engineering.