Transition metal doped pyrrole-NC for high-performance CO₂ reduction reaction to C1 products

The electrochemical CO₂ reduction reaction (CO₂RR) provides a potential to mitigate excessive carbon emission and achieve carbon neutrality eventually. Herein, 26 transition metal anchored pyrrole nitrogen doped carbon catalysts (TM-NCs) were proposed as high-performance single atom catalysts (SACs) for CO₂RR via a multi-level screening. The results revealed that 23 out of the 26 TM-NCs possessed superior thermodynamic and electrochemical stability, and 11 TM-NCs exhibited preferred CO₂RR selectivity over the side reactions. The reaction pathways of CO₂RR to C1 products, including CO, HCOOH, CH₃OH, and CH₄, on TM-NCs were explored. Considering the activity and product selectivity along CO2RR, Cr/Mn/Co-NCs were screened out as outstanding SACs in CO₂RR to HCOOH with low limiting potentials of − 0.18 to − 0.10 V, which surpassed most previously reported SACs. With the applied potentials over − 0.6 V, Cr/Mn/Co-NCs exhibited the advantages of yielding high-throughput reaction products of CH₄. The coordinated N-type analysis demonstrated that compared with pyridine-type TM-NCs, pyrrole-type TM-NCs possessed weaker binding strengths with intermediates but better or comparable CO₂RR activity. The results of this work highlighted pyrrole-type Cr/Mn/Co-NCs as ideal SACs for CO₂RR and uncovered the effect of coordinated N-type in TM-NCs on CO₂RR performance. © 2023 Elsevier B.V. All rights reserved.