Electrocatalytic
CO2 reduction by metal-free nitrogen-doped
carbon (N-C) catalysts provides a solution for CO2 reuse;
however, it suffers a large overpotential and poor selectivity due
to the low intrinsic reactivity of N dopants. Herein, we report the
promotion of CO2 reduction on N-C through the integration
of increasing the numbers and inherent catalytic reactivity and selectivity
of pyridinic N dopants. A novel sacrificial soft-templating approach
was developed to construct a two-dimensional holey carbon nanostructure
to preferentially host dense edge-located pyridinic N, and electron-rich
fluorine (F) was simultaneously incorporated to activate pyridinic
N sites by engineering their electronic properties. Consequently,
the resultant N,F-codoped holey carbon layers achieve a CO Faradaic
efficiency of 90% at a low overpotential of 490 mV for 40 h without
decay, significantly surpassing the F-free N-C counterpart. Density
functional theory (DFT) calculations reveal that the electron donation
from a nearby F atom increases the charge density and delocalizes
electronic density of states of pyridinic N. These electronic benefits
thus greatly promote the CO2 activation on the highly dense
and active pyridinic N sites by facilitating the electron transfer
and strengthening the binding interaction with *COOH intermediate.
The discovery of dopant-induced synergistic interaction may create
a path for manipulating catalytic CO2 reduction properties.
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