Self-assembly of anthraquinone covalent organic frameworks as 1D superstructures for highly efficient CO₂...

The design of selective and efficient covalent organic frameworks (COFs) based electrocatalysts with tunable morphology for efficient CO₂ reduction reaction (CO₂RR) to CH₄ is highly desirable. Here, two kinds of anthraquinone-based COFs (i.e., AAn-COF and OH-AAn-COF) with tunable 1D superstructures (e.g., nanofibers (NF) and hollow tubes (HT)) have been produced via Schiff-base condensation reaction. Interestingly, a rarely reported nanosheet-based self-template mechanism and a nanosheet-crimping mechanism have been demonstrated for the production of COF-based nanofibers and hollow tubes, respectively. Besides, the obtained COF-based superstructures can be post-modified with transition metals for efficient CO₂RR. Specifically, AAn-COF-Cu (NF) and OH-AAn-COF-Cu (HT) exhibit superior faradaic-efficiency with CH₄ (FE_CH4) of 77% (-128.1 mA cm^-2, -0.9 V) and 61% (-99.5 mA cm^-2, -1.0 V) in a flow-cell, respectively. Noteworthy, the achieved FE_CH4 of AAn-COF-Cu (NF) (77%) the is highest one among reported crystalline COFs. This work provides a general methodology in exploring morphology-controlled COFs for electrocatalytic CO₂RR.