Unlocking Exceptional CO2 Reduction Selectivity at Neutral Conditions: A First-Principles Study on Chlorinated Single Iron Doped Graphitic Carbon Nitride

The electrochemical reduction of carbon dioxide (CO2RR) to useful fuels and chemicals using renewable energy sources presents a promising strategy for addressing energy security and environmental challenges. Single-metal atom catalysts have emerged as appealing alternatives due to their high efficiency in overcoming limitations associated with traditional metal nanocatalysts. This comprehensive study focuses on fine-tuning chlorinated single-atom-based active sites on a graphitic carbon nitride (g-C3N4) monolayer to achieve absolute selectivity for HCOOH. Previous research has demonstrated that halogenation significantly suppresses the hydrogen evolution reaction, which competes with the CO2RR. To achieve selectivity for a single product among all reduced products, the chemical environment of the catalyst was tuned to neutral conditions. Our results indicate that the catalyst exhibited higher selectivity for HCOOH, with a significantly low onset potential and a wide potential range where HCOOH selectivity was maintained at the FeCl site at pH 7 compared to the acidic region. These findings highlight the FeCl active site of FeCl-decorated g-C3N4 as a highly efficient and selective electrocatalyst for the CO2RR. The insights gained from our study offer valuable directions for designing new CO2RR catalysts with improved selectivity and efficiencies.

Shakir Renna, Komsa Hannu Pekka, Kumar Paswan Karan, Sinha A. S.K., Karthikeyan J.

A1 Journal article (peer-reviewed)

Shakir, R., Komsa, H.-P., Kumar Paswan, K., Sinha, A. S. K., & Karthikeyan, J. (2024). Unlocking exceptional co 2 reduction selectivity at neutral conditions: A first-principles study on chlorinated single iron doped graphitic carbon nitride. The Journal of Physical Chemistry C, 128(13), 5505–5514. https://doi.org/10.1021/acs.jpcc.3c07748

https://doi.org/10.1021/acs.jpcc.3c07748 https://urn.fi/URN:NBN:fi:oulu-202404162757