Issue 12, 2023

Rational design of active sites in alumina-based catalysts to optimize antibonding-orbital occupancy for tetrafluoromethane decomposition

Abstract

Tetrafluoromethane (CF4) is a potent greenhouse gas with high stability, thus its effective decomposition is crucial for mitigating its environmental impact. However, the lack of chemical understanding and efficient catalysts impedes the development of CF4 decomposition reactions. Herein, this work elucidates the fundamental interactions between the active center and CF4 by density functional theory (DFT). Our research reveals that the key to activating CF4 lies in the antibonding-orbital occupancy of the active center, particularly within the context of the commonly used Al2O3 catalyst. A comprehensive theoretical calculation was undertaken to optimize the antibonding-orbital occupancy, revealing that Zr and Hf could potentially function as novel active sites, thereby augmenting the antibonding-orbital occupancy on the Al2O3 surface. This augmentation effectively enhances the electronic interaction between CF4 and the active sites, paving the way for subsequent reaction dynamics. Accordingly, we synthesized Al2O3, Zr–Al2O3 and Hf–Al2O3 catalysts, and observed CF4 conversions of 34.8%, 54.5%, and 100% at 650 °C, respectively, which is consistent with the theoretical results. This result aligns with the theoretical findings, demonstrating the practical applicability of our research. These findings provide a basis for rational catalyst design towards efficient CF4 decomposition, and can be extended to other robust molecules.

Graphical abstract: Rational design of active sites in alumina-based catalysts to optimize antibonding-orbital occupancy for tetrafluoromethane decomposition

Supplementary files

Article information

Article type
Paper
Submitted
12 Jul 2023
Accepted
16 Oct 2023
First published
18 Oct 2023

Environ. Sci.: Nano, 2023,10, 3307-3316

Rational design of active sites in alumina-based catalysts to optimize antibonding-orbital occupancy for tetrafluoromethane decomposition

T. Luo, Y. Chen, K. Liu, J. Fu, H. Zhang, S. Chen, Q. Wang, K. Chen, J. Wang, W. Liao, H. Li, Z. Lin and M. Liu, Environ. Sci.: Nano, 2023, 10, 3307 DOI: 10.1039/D3EN00473B

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