Methanoic acid dehydrogenation catalyst and application thereof

Abstract

The invention relates to a methanoic acid dehydrogenation catalyst. The catalyst comprises metal and ligand, wherein the metal is iridium, rhodium, ruthenium, cobalt and the like, the ligand is an amino substituted oxime ether compound; the catalyst is firstly applied to dehydrogenation reaction of methanoic acid, TON can maximally achieve 505*104 which is the currently reported maximum value at 70 DEG C, and the TON can maximally achieve 400*104 which is the reported maximum value at 90 DEG C.

Description

technical field [0001] The present invention relates to a kind of catalyst that is used for the dehydrogenation of formic acid, specifically by a kind of bidentate or polydentate ligand of oxime ether imine structure that contains amino substitution and various metals of iridium, rhodium, ruthenium and cobalt Catalysts for precursor formation. Background technique [0002] Formic acid, as a liquid hydrogen storage material, has attracted widespread attention. An ideal formic acid decomposition hydrogen production catalytic system should meet the following conditions: (1) the catalyst is stable, the raw materials are easy to obtain, and the preparation is simple; (2) the reaction is solvent-free or uses water as a solvent; (3) without any additives; (4) can Decompose pure formic acid or relatively concentrated formic acid; (5) High catalytic efficiency; (6) The reaction can be carried out in large quantities, and the operation is simple, without additional operations such as...

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Problems solved by technology

In 2015, Himeda, Fujita, Mucherman and others reported that TON of 2,050,000 can be obtained (ACS Catal.2015,5, 5496-5504), but the reaction is carried out at 60°C, and it takes 580 hours to complete the reaction. The reaction efficiency is low and it is not suitable for large quantities. Practical applications requiring hydrogen rapidly

Later, they reported another type of catalyst, a complex formed by pyridine and imidazoline ligands and iridium (Catal.Sci.Technol., 2016, 6, 988-992), which shortened the reaction time of formic acid dehydrogenation to 363h , but the catalytic activity is still low

In 2016, Kawanami's research group reported that the dehydrogenation of formic acid can reach TON of 5,000,000 (ChemSusChem 2016,9,2749-2753), but it requires a reaction time of 2600h and the catalytic activity is lower

The raw materials for synthesizing this type of catalyst are cheap, the synthesis steps are simple, and are suitable for mass production; this type of catalyst can be generated in situ, and the complex can also be prepared before the reaction. The reaction operation is simple, no protection and dehydrogenation treatment are required, and the stability is good. , the application in the formic acid dehydrogenation reaction has not been reported at home and abroad

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