摘要
Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mechanism remains under debate. With the aid of density functional theory(DFT) calculations, an updated and self-consistent mechanism which involves Me OH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formic- acid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol solvent are used.
Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mech- anism remains under debate. With the aid of density functional theory （DFT） calculations, an updated and self-consistent mechanism which involves MeOH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formic- acid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol sol- vent are used.
基金
supported by the National Basic Research Program (2012CB215306)
the National Natural Science Foundation of China (21325208, 21361140372, 21572212)
Chinese Academy of Sciences (KFJ-EW-STS-051)
Fundamental Research Funds for the Central Universities (WK2060190025)
Scientific research funds of Anhui University (J10117700074)
