Synergistic Dual-Atom Catalysts on Ceria for Enhanced CO Preferential Oxidation: Insights from High-Throughput First-Principles Microkinetics

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-12-24 DOI:10.1021/acscatal.4c05779

Zhang Liu, Yanwei Wen, Zhaojie Wang, Limin Guo, Rong Chen, Aimin Zhang, Bin Shan

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Abstract

Highly dispersed transition metal atoms supported by reducible ceria have garnered considerable attention as CO preferential oxidation (PROX) catalysts. Dual-atom catalysts (DACs), which effectively balance activity and selectivity through synergistic effects, are promising candidates for PROX catalysis. We report here the high-throughput screening of CeO₂(110)-supported DACs (M_A-M_B/CeO₂, M_A(B) = 3d, 4d, 5d transition metal) based on first-principles microkinetics. Reduced electronegativity and d-orbital population of metal atoms favor the stability of loaded DACs via binding energy and aggregation energy analyses. A state-to-state microkinetic analysis of the full PROX reaction network identifies that the O₂ -predissociated Mars–van Krevelen (MvK) pathway, characterized by direct oxidation, carbonate formation, and interfacial oxygen migration, is the predominant mechanism on M_A-M_B/CeO₂ under low temperatures. The key energetic routes of homogeneous DACs reveal that the oxygen removal energy of dissociated O₂ and adsorption energies of CO and H on transition metal sites serve as effective descriptors of PROX performance. Following these insights, high-throughput computations of PROX descriptors are carried out on a combination of 435 heterogeneous DACs to screen catalysts with balanced activity and selectivity. Au-based DACs, notably Fe–Au, stand out at room temperature for their facile activation of dissociated oxygen and moderated hydrogen affinity. Our study harnesses the unique properties of dual-atom configurations and paves way for the rational design of efficient PROX catalysts.

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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.