Speaker
Description
Theoretical Insights into CO₂ Activation on α-Bi₂O₃ under Operating Conditions
The increasing use of fossil fuels over recent decades has triggered a global energy crisis, marked by the rapid depletion of these resources and the substantial release of carbon dioxide (CO₂) into the atmosphere [1]. CO₂ levels are projected to reach 570 ppm by 2100, a rise that contributes to critical environmental challenges such as global warming, polar ice melt, and ocean acidification [2]. To mitigate these effects and move toward a carbon-neutral cycle, strategies that utilize CO₂ as a feedstock for producing value-added chemicals have become increasingly important. Among these, the electrochemical CO₂ reduction reaction (CO₂RR) has emerged as a promising approach for CO₂ conversion under mild conditions. However, several challenges need to be addressed: CO₂ activation is energy-demanding due to its high thermodynamic stability, CO2 conversion efficiency is generally limited by the competing Hydrogen Evolution Reaction (HER), and the selectivity towards specific products is low [3].
In recent years, bismuth-based electrocatalysts have gained much attention owing to their low toxicity, cost-effectiveness, abundance, and high selectivity for CO₂ conversion to formate or formic acid via electrochemical CO₂RR [4–6]. Nonetheless, achieving substantial progress requires a deeper microscopic understanding of the underlying processes. Due to their explicative and predictive power, ab initio calculations play a key role in the energy scenario as they characterize from an atomistic perspective the complex materials and give insights into the catalytic mechanisms. Previous computational studies on CO₂RR on Bi₂O₃ have focused on pristine and defective surfaces [6], or the influence of decorating metallic nanocluster (NC) [7]. In this work, we extend these efforts by investigating the thermodynamically stable α-phase of Bi₂O₃ as a potential electrocatalyst for CO₂RR, taking into account the impact of oxygen vacancies and the role of an externally applied bias (i.e., operating electrochemical conditions) [8].
[1] Duan, X.; Xu, J.; Wei, Z.; Ma, J.; Guo, S.; Wang, S.; Liu, H.; Dou, S. Adv. Mater. 2017, 29, 1701784.
[2] Appel, A. M.; Bercaw, J. E.; Bocarsly, A. B.; Dobbek, H.; DuBois, D. L.; Dupuis, M.; Ferry, J. G.; Fujita, E.; Hille, R.; Kenis, P. J. A.; Kerfeld, C. A.; Morris, R. H.; Peden, C. H. F.; Portis, A. R.; Ragsdale, S. W.; Rauchfuss, T. B.; Reek, J. N. H.; Seefeldt, L. C.; Thauer, R. K.; Waldrop, G. L. Chem. Rev. 2013, 113, 6621-6658.
[3] Jones, J. P.; Prakash, G. S.; Olah, G. A. Isr. J. Chem. 2014, 54, 1451-1466.
[4] Deng, P.; Wang, H.; Qi, R.; Zhu, J.; Chen, S.; Yang, F.; Zhou, L.; Qi, K.; Liu, H.; Xia, B. Y. ACS Catal. 2019, 10, 743-750.
[5] Fan, K.; Jia, Y.; Ji, Y.; Kuang, P.; Zhu, B.; Liu, X.; Yu, J. ACS Catal. 2019, 10, 358-364
[6] Fao, G. D.; Yizengaw, K. W.; Jiang, J. C. Mol. Cat. 2023, 539, 113012.
[7] Dai, W.; Wang, P.; Long, J.; Xu, Y.; Zhang, M.; Yang, L.; Zou, J.; Luo, X.; Luo, S. ACS Catal. 2023, 13, 2513-2522.
[8] Fasulo, F.; Massaro, A.; Muñoz-García, A. B.; Pavone, M. J. Mater. Res. 2022, 37, 3216-3226.
