Efficient CO2 Electroreduction by Highly Dense and Active Pyridinic Nitrogen on Holey Carbon Layers with Fluorine Engineering
Academic Article
Overview
Research
Identity
Additional Document Info
Other
View All
Overview
abstract
2019 American Chemical Society. Electrocatalytic CO 2 reduction by metal-free nitrogen-doped carbon (N-C) catalysts provides a solution for CO 2 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 CO 2 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 CO 2 activation on the highly dense and active pyridinic N sites by facilitating the electron transfer and strengthening the binding interaction withCOOH intermediate. The discovery of dopant-induced synergistic interaction may create a path for manipulating catalytic CO 2 reduction properties.