Efficient CO2 Electroreduction by Highly Dense and Active Pyridinic Nitrogen on Holey Carbon Layers with Fluorine Engineering
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© 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 with∗COOH intermediate. The discovery of dopant-induced synergistic interaction may create a path for manipulating catalytic CO 2 reduction properties.
author list (cited authors)
Pan, F., Li, B., Xiang, X., Wang, G., & Li, Y
complete list of authors
Pan, Fuping||Li, Boyang||Xiang, Xianmei||Wang, Guofeng||Li, Ying