Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.013
Publication date: 16th December 2024
The electrochemical reduction of CO2 offers a promising route for converting renewable energy into carbon-based fuels through CO2 hydrogenation, creating a net-zero carbon emissions energy cycle. Formate is one of the important value-added CO2 reduction products. It is highly demanded in textile and food preserving industries. So, we targeted formate as selective product in CO2 reduction in aqueous electrolyte.[1] Among the catalysts explored, Bismuth (Bi) stands out for being earth-abundant, environmentally friendly, cost-effective, and highly stable, with excellent selectivity for formate production. We developed a controlled synthesis process to produce uniform height 2D Bi flakes with (012) facets, using the chemical reduction of a sacrificial 2D BiOCl template under ambient conditions.[2] These Bi flakes demonstrate an impressive formate partial current density of 18.7 mA/cm² at -1.14 VRHE during chronoamperometry, along with a peak formate Faradaic Efficiency (FE) of around 90% at -0.84 VRHE. However, due to weak solubility of CO2 in water, at higher potential, CO2 saturation at the electrode surface drops which cause severe formate selectivity drop, giving rise to competitive Hydrogen Evolution Reaction (HER). To address this, we strategically modified the 2D Bi flakes with an ultrathin coating of Polyaniline (PANI), a redox-active conducting polymer. The basic amine groups in the polymer chain of PANI attract weakly acidic CO2 molecules to the electrode surface. We found, PANI is not at all active for CO2RR but when it is coated on 2D Bi flakes, it significantly improved performance, increasing the formate partial current density to 35.5 mA/cm² at -1.14 VRHE. Moreover, this modification also reduced the formate selectivity drop at higher potentials in comparison to bare 2D bismuth flakes, demonstrating the synergy between PANI and 2D Bi flakes in enhancing CO2 reduction. We also have postulated a different mechanistic path that shows the role of PANI which is working behind this enhanced activity.
We acknowledges financial support from the Department of Science and Technology (Grant No. DST/TMD/HFC/2k18/138), SERB Project “ECR/2018/0014”. We especially thank Prof. Rajaram Bal, IIP Dehradun, for allowing us to use the CO2 TPD
analysis facility.
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