Nitrogen-doped carbon (NC) for carbon dioxide reduction reaction (CO2RR) are promising candidates. However, its selectivity and activity are limited by the undeveloped pore and limited electronic effect. Herein, we propose a strategy of three birds with one stone to utilize the embedded nickel for inducing electron-rich pyridinic-NC with multimodal porous structure based on the hard template assisted sacrificial template method. Nickel acts as sacrificial agent and inducer to facilitate the formation of mesoporous and reactive nitrogen species for capturing and activating reactants, respectively. Besides, we find that nickel as electron donor endows the NC with electron accumulation for participating actively in PCET reaction. The resultant Ni0.87-NC-1-AE exhibits an eminent FECO of 97.6 % with excellent activity and stability. In-situ Raman spectroscopy and the projected crystal orbital Hamilton populations (pCOHP) confirm the accumulation of *COOH and the stable adsorption of *COOH on the surface. What’s more, the well-designed experiments and DFT calculations accurately locate pyridinic-N as the active site, where the aggregated electrons donated by nickel significantly reduce the energy barrier of rate-determining step and promote the desorption of CO. This work provides an instructive perspective to construct advanced NC electrocatalysts with high mass transfer efficiency and high catalytic activity.

https://www.sciencedirect.com/science/article/pii/S2211285524004087