Self-assembly of anthraquinone covalent organic frameworks as 1D superstructures for highly efficient CO2 electroreduction to CH4.

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 (FECH4) 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 FECH4 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.