(569er) CO Reduction to Multicarbon Chemicals on 2D Covalent-Organic Framework-Based Bimetallic Catalysts

Covalent-organic frameworks (COFs) have shown great promise as catalyst substrates due to their abundant surface sites for anchoring metal atoms with appreciable strength. Especially, two-dimensional (2D) COF-based metal-nitrogen-carbon (M-N-C) have been widely explored for CO₂/CO reduction to high value-added chemicals. Currently, most of these catalysts rely on metallo-phthalocyanine/porphyrin as active centers, where only one metal atom is anchored at the center of phthalocyanine/porphyrin; consequently, C₁ chemicals are the main reductive products. However, multicarbon (C₂₊) chemicals have higher energy density, wider applications despite lower selectivity than C₁ chemicals.

In this work, we conduct a theoretical exploration of C-C coupling and production of C₂₊ chemicals by reducing CO on a series of 2D COF-based bimetallic catalysts with experimentally reported salphen-COF as the substrate. By introducing Cu and other transition metal (TM) atoms on the salphen-COF, several TMCu-N-C are found to exhibit exciting catalytic activity towards C₂₊ chemical production. To our knowledge, this is the first time where 2D COFs is brought to the field of C₂₊ chemical production by CO reduction. Our work might be conducive to the development of this type of fascinating materials in catalysis.