Catalysis

In silico investigation of ligand-regulated palladium-catalysed formic acid dehydrative decomposition under acidic conditions

Authors

  • Chaoren Shen Chang-Kung Chuang Institute, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University ,
  • Kaiwu Dong Chang-Kung Chuang Institute, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University ,
  • Zhihong Wei Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University ,
  • Xinxin Tian Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University

Abstract

In silico investigation of ligand-regulated palladium-catalysed formic acid dehydrative decomposition to carbon monoxide under acidic conditions was conducted. Two types of bidentate tertiary phosphine ligands were selected on the basis of previous experimental study. And the promoting effect of para-toluenesulfonic acid (PTSA) was specifically investigated. The pyridyl group implanted in pytbpx ligand is found to mainly contribute on enhancing the activity of palladium catalyst. The PTSA promoter displays specific role for regenerating active species and supressing dehydrogenation during Pd-pytbpx/Pd-dtbpx catalysed dehydration process. CO releasing process catalysed by Pd-dtbpx also facilitated by adding PTSA. According to the mechanism hereby supposed, introducing electron-withdrawing substitution at para-position of pyridyl rings may further improve the dehydrative decomposition activity of Pd-pytbpx.

Version notes

Result disscussion about path F/H and path A/F of Pd-pytbpx in the presence of excess PTSA has been added.

Content

Thumbnail image of Manuscript-ChemRxiv-R2-20211018.pdf

Supplementary material

Thumbnail image of SI20211016-ChemRxiv-R2.pdf
Supporting Information
Fig. S1-4 and Cartesian coordinate of geometry-optimized structures