Cooperative Copper Single Atom Catalyst in Two-dimensional Carbon Nitride for Enhanced CO 2 Electrolysis to Methane.

Renewable electricity powered carbon dioxide (CO 2 ) reduction (eCO 2 R) to high-value fuels like methane (CH 4 ) holds the potential to close the carbon cycle at meaningful scales. However, this kinetically staggered 8-electron multistep reduction still suffers from inadequate catalytic efficiency and current density. Atomic Cu-structures can boost eCO 2 R-to-CH 4 selectivity due to enhanced intermediate binding energies (BEs) resulting from favorably shifted d-band centers. Herein, we exploit two-dimensional carbon nitride (CN) matrices, viz. Na-polyheptazine (PHI) and Li-polytriazine imides (PTI), to host Cu-N 2 type single atom sites with high density (∼1.5 at%), via a facile metal ion exchange process. Optimized Cu loading in nanocrystalline Cu-PTI maximizes eCO 2 R-to-CH 4 performance with Faradaic efficiency (FE CH4 ) of ≈68% and a high partial current density of 348 mA cm -2 at a low potential of -0.84 V versus RHE, surpassing the state-of-the-art catalysts. Multi-Cu substituted N-appended nanopores in the CN frameworks yield thermodynamically stable quasi-dual/triple sites with large interatomic distances dictated by the pore dimensions. First-principles calculations elucidate the relative Cu-CN cooperative effects between the two matrices and how the Cu-Cu distance and local environment dictate the adsorbate BEs, density of states, and CO 2 -to-CH 4 energy profile landscape. The 9N pores in Cu-PTI yield cooperative Cu-Cu sites that synergistically enhance the kinetics of the rate-limiting steps in the eCO 2 R-to-CH 4 pathway. This article is protected by copyright. All rights reserved.