One-step conversion of methane and formaldehyde to ethanol over SA-FLP dual-active-site catalysts: A DFT study

• Published in: Chinese chemical letters 2024-04, Vol.35 (4), p.108549, Article 108549
• Main Authors: Ban, Tao, Yu, Xi-Yang, Tian, Hai-Kuo, Huang, Zheng-Qing, Chang, Chun-Ran
• Format: Article
• Language: English
• Subjects: Dual active sites; Ethanol synthesis; Frustrated Lewis pairs; Methane conversion; Single-atom
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2023.108549

One-step conversion of methane and formaldehyde into ethanol is a 100% atom-efficient process for carbon resources utilization and environment protection but still faces eminent challenges due to the lacking of efficient catalysts. Therefore, developing active and stable catalysts is crucial for the co-conversion of methane and formaldehyde. Herein, twelve kinds of “Single-Atom” - “Frustrated Lewis Pair” (SA-FLP) dual-active-site catalysts are designed for the direct conversion of methane and formaldehyde to ethanol based on density functional theory (DFT) calculations and microkinetic simulations. The results show that the SA-FLP dual active sites can simultaneously activate methane at the SA site and activate formaldehyde at the FLP site. Among the twelve designed SA-FLP catalysts, Fe1-FLP shows the best performance in the co-conversion of methane and formaldehyde to ethanol with the rate-determining barrier of 1.15 eV. Ethanol is proved as the main product with the turnover frequency of 1.32 × 10−4 s−1 at 573 K and 3 bar. This work provides a universal strategy to design dual active sites on metal oxide materials and offers new insights into the effective conversion of methane and formaldehyde to desired C2 chemicals. Designed SA-FLP dual-active-site catalysts can simultaneously activate methane and formaldehyde molecules and notably enhance the coupling of the two species to generate ethanol. [Display omitted]