CO₂ electroreduction on single atom catalysts: the role of the DFT functional

Area of Science:

• Computational Chemistry
• Catalysis Science
• Materials Science

Background:

• Single-atom catalysts (SACs) are pivotal in CO2 electroreduction to fuels.
• SAC chemistry diverges from extended surfaces, offering unique CO2 activation potential.
• The influence of computational functionals on SAC predictions requires further investigation.

Purpose of the Study:

• To investigate the impact of exchange-correlation functionals in density functional theory (DFT) on CO2 activation by SACs.
• To compare the predictive accuracy of PBE, PBE+U, and PBE0 functionals for SACs.
• To assess the suitability of different DFT functionals for screening and high-throughput calculations of SACs.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• CO2 activation on various single-atom catalysts (SACs) was studied.
• The performance of PBE, PBE+U, and PBE0 functionals was evaluated.

Main Results:

• The PBE functional provides reliable qualitative predictions for CO2 activation by SACs.
• PBE demonstrates inaccuracies in certain quantitative predictions.
• The PBE+U functional yields results comparable to the more robust PBE0 functional at a lower computational cost.

Conclusions:

• The choice of DFT functional significantly impacts the prediction of SAC activity.
• For accurate quantitative estimates, methods beyond PBE are necessary.
• PBE+U presents a computationally efficient alternative to PBE0 for reliable SAC activity predictions.