Revealing the Jahn–Teller Mitigating Complexity of Se-Anchored Mn Oxides for Superior SO2 Resistance in Gaseous Molecular Oxygen Activation

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-12-18 DOI:10.1021/acscatal.4c06268

Haomiao Xu, Qinyuan Hong, Jia’nan Wang, Jun Lei, Mingming Wang, Jiaxing Li, Zhisong Liu, Mingze Jiao, Wenjun Huang, Zan Qu, Naiqiang Yan

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Abstract

Manganese oxides have emerged as promising catalysts for the low-temperature activation of molecular oxygen (O₂), crucial for the catalytic oxidation and removal of gaseous pollutants. However, the undesired Jahn–Teller (J-T) effects associated with the Mn^iv/Mnⁱⁱⁱ redox couple, particularly under SO₂ poisoning, led to the effectiveness of Mn oxides in applications. Herein, we construct a highly covalent Se^iv-O-Mnⁱⁱⁱ structure via the introduction of selenium into α-MnO₂. Such a structure features high-valence Se^iv anchored on the oxygen-terminated (110) plane of α-MnO₂, facilitates the generation of more active oxygen species, and maintains the continuous cycling of oxygen-linked Mn^iv/Mnⁱⁱⁱ. Such dynamics are pivotal for stabilizing manganese activation and mitigating the J-T effect. Through a combination of experimental investigations and theoretical calculations, we demonstrate that the Se^iv-O-Mnⁱⁱⁱ configuration, characterized by a high degree of Mn–O hybridization, significantly enhances CO oxidation, NH₃ oxidation, and elemental mercury (Hg⁰) removal performances, and exhibits resistance to SO₂. This study paves the way for the development of efficient low-temperature O₂ activation processes for the removal of gaseous pollutants in real-world applications.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.