An Atom-Pair Design Strategy for Optimizing the Synergistic Electron Effects of Catalytic Sites in NO Selective Reduction

Weiye Qu; Haiyang Yuan; Zhouhong Ren; Jizhen Qi; Dongrun Xu; Junxiao Chen; Liwei Chen; Huagui Yang; Zhen Ma; Xi Liu; Haifeng Wang; Xingfu Tang

doi:10.1002/anie.202212703

An Atom-Pair Design Strategy for Optimizing the Synergistic Electron Effects of Catalytic Sites in NO Selective Reduction

Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202212703. doi: 10.1002/anie.202212703. Epub 2022 Nov 28.

Authors

Weiye Qu¹, Haiyang Yuan^{2

3}, Zhouhong Ren⁴, Jizhen Qi⁵, Dongrun Xu¹, Junxiao Chen¹, Liwei Chen^{4

5

6}, Huagui Yang³, Zhen Ma^{1

7}, Xi Liu⁴, Haifeng Wang², Xingfu Tang^{1

7}

Affiliations

¹ Department of Environmental Science and Engineering, Fudan University, Shanghai, 200438, China.
² Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis and Centre for Computational Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China.
³ Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
⁴ In situ Center for Physical Sciences, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁵ i-Lab, CAS Center for Excellence in Nanoscience Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO), Chinese Academy of Sciences, Suzhou, 215123, China.
⁶ Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
⁷ Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, China.

PMID: 36321806
DOI: 10.1002/anie.202212703

Abstract

Effective adsorption and speedy surface reactions are vital requirements for efficient active sites in catalysis, but it remains challenging to maximize these two functions simultaneously. We present a solution to this issue by designing a series of atom-pair catalytic sites with tunable electronic interactions. As a case study, NO selective reduction occurring on V₁ -W₁ /TiO₂ is chosen. Experimental and theoretical results reveal that the synergistic electron effect present between the paired atoms enriches high-energy spin charge around the Fermi level, simultaneously rendering reactant (NH₃ or O₂ ) adsorption more effective and subsequent surface reactions speedier as compared with single V or W atom alone, and hence higher reaction rates. This strategy enables us to rationally design a high-performance V₁ -Mo₁ /TiO₂ catalyst with optimized vanadium(IV)-molybdenum(V) electronic interactions, which has exceptional activity significantly higher than the commercial or reported catalysts.

Keywords: Atom-Pair Catalytic Sites; Reaction Mechanisms; Selective Catalytic Reduction; Surface Reactions; Synergistic Electron Effects.

Abstract

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