Facile and Scalable Synthesis of Metal- and Nitrogen-Doped Carbon Nanotubes for Efficient Electrochemical CO₂ Reduction

Abstract

Metal- and nitrogen-doped carbon (M-N-C) is a promising material to catalyze electrochemical CO₂ reduction reaction (CO₂RR). However, most M-N-C catalysts in the literature require complicated synthesis procedures and produce small quantities per batch, limiting the commercialization potential. In this work, we developed a simple and scalable synthesis method to convert metal-impurity-containing commercial carbon nanotubes (CNTs) and nitrogen-containing organic precursors into M-N-C via one-step moderate-temperature (650 °C) pyrolysis without any other treatment nor the need to add metal precursors. Batches of catalysts in varied mass up to 10 g (150 mL in volume) per batch were synthesized, and repeatable catalytic performances were demonstrated. To the best of our knowledge, the 10 g batch is one of the largest batches of CO₂RR catalysts synthesized in the literature while requiring minimal synthesis steps. The catalyst possessed single-atomic iron-nitrogen (Fe-N) sites, enabling a high performance of >95% CO product selectivity at a high current density of 400 mA/cm² and high stability for 45 h at 100 mA/cm² in a flow cell testing. The catalyst outperformed a benchmark noble-metal nanoparticle catalyst and achieved longer stability than many other reported M-N-C catalysts in the literature. The scalable and cost-effective synthesis developed in this work paves a pathway toward practical CO₂RR applications. The direct utilization of metal impurities from raw CNTs for efficient catalyst synthesis with minimal treatment is a green and sustainable engineering approach.