Mechanisms of CoIIand Acid Jointly Catalyzed Domino Conversion of CO2, H2, and CH3OH to Dialkoxymethane: A DFT Study

Zhihong Wei, Xinxin Tian, Michael Bender, Matthias Beller, Haijun Jiao

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9 Scopus citations

Abstract

The conversion mechanisms of CO2and H2in methanol to dimethoxymethane catalyzed jointly by metallic[P3Co-H]+catalyst and acidic HNTf2cocatalyst in a domino sequence were investigated at the M06L-SCRF level of density functional theory. The whole conversion has the steps of the Co-catalyzed hydrogenation (CO2+ H2= HCOOH; HCOOCH3+ H2= CH3OCH2OH) and acid-catalyzed esterification (HCOOH + CH3OH = HCOOCH3+ H2O; CH3OCH2OH + CH3OH = CH3OCH2OCH3+ H2O) reactions. The full Gibbs free energy profiles show that the bidentate formate complexκ2-[P3Co-OCHO]+is the resting state and methylating CH3OCH2OH with CH3-NTf2is the rate-determining step. The whole reaction kinetics is controlled by both[P3Co-H]+and HNTf2cocatalyst. Our study clearly shows the individual role of metal catalyst and acid cocatalyst and the need to combine both catalysts for this reaction and explains rationally why this process needs CO2+ H2+ CH3OH rather than only CO2+ H2. Compared to HNTf2as a cocatalyst, the lower activity ofp-TsOH is due to the weaker interaction between acid and substrate. A mechanism for the chain growth and termination of oxymethylene ether is proposed.

Original languageEnglish
Pages (from-to)6908-6919
Number of pages12
JournalACS Catalysis
Volume11
Issue number12
DOIs
StatePublished - 18 Jun 2021
Externally publishedYes

Keywords

  • CO hydrogenation
  • DFT
  • DMM formation
  • acid effect
  • cobalt complexes
  • triphos ligand

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