Facile Synthesis of Iron- and Nitrogen-Doped Porous Carbon for Selective CO₂ Electroreduction

Abstract

A general and simple solvent-free procedure using direct heating of a ball-milled mixture of l-histidine-Fe ₂O ₃-FeCl ₃ is developed for the synthesis of iron- and nitrogen-doped porous carbon electrocatalysts. Through adjustment of the reactant ratios and the pyrolysis temperature, a series of electrocatalysts are easily obtained with varying activities for electrochemical CO ₂ reduction reaction (CO ₂RR). The electrocatalyst synthesized from l-histidine-Fe ₂O ₃-FeCl ₃ at a 4:1:0.25 component ratio at 1000 °C exhibits the highest Faradaic efficiency of 83% for CO ₂-to-CO conversion at a small overpotential (360 mV) in aqueous media. The use of a number of characterization techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, electron microscopy, and nitrogen sorption experiments, reveals that both Fe ₂O ₃ and FeCl ₃ contribute to the iron doping and formation of porosity. As a result, they are both crucial to produce the optimal CO ₂RR electrocatalyst. Correlation of the CO ₂RR activity with the carbon structure suggests that the degree of graphitization of the carbon electrocatalysts plays an important role in their CO ₂RR performance.