Cascade Catalysis for the Hydrogenation of Carbon Dioxide to Methyl Formate Using a Molecular Ru–Phosphine Complex and the Metal–Organic Framework UiO-66 as Heterogeneous Acid

Abstract

The direct incorporation of CO2 into value-added base chemicals, such as methyl formate (MF), is a grand challenge to chemical science. In this work, a base-free cascade catalysis system is described to effectively convert carbon dioxide into MF. In the initial step a well-established Ru complex (i.e., RuHCl(dppm)2, dppm = 1,1-bis(diphenylphosphino)methane) is able to hydrogenate CO2 into formic acid, which subsequently undergoes a heterogeneous acid catalyzed esterification with methanol to selectively produce MF. Here, the small pore MOF UiO-66, a Zr-terephthalate, is identified as a promising heterogeneous acid and its Zr6 cluster is modified to understand the effect of Brønsted/Lewis acidity on the performance. Moreover, this heterogeneous acid catalyst could be reused for multiple times without significantly losing its activity.

Recent Progress in Thermocatalytic Liquid Phase CO2 Conversion to Bulk Chemicals and Fuels

“…Recently, Vos et al reported a combination of an organometallic Ru–phosphine complex (homogeneous catalyst) and UiO-66 metal organic framework (heterogeneous catalyst) for the conversion of CO 2 into MF at 140 °C and 6 MPa resulting in 80% MF selectivity. The Ru catalyst promoted formic acid formation while the acid sites on UiO-66 promoted methyl formate synthesis via esterification reaction Table summarizes the catalysts and reactions conditions reported in the literature for methyl formate synthesis.…”

“…The Ru catalyst promoted formic acid formation while the acid sites on UiO-66 promoted methyl formate synthesis via esterification reaction. 127 Table 8 summarizes the catalysts and reactions conditions reported in the literature for methyl formate synthesis.…”

A comparative overview of the electrochemical valorization and incorporation of CO2 in industrially relevant compounds

“…[24][25][26] Additionally, developing new materials and chemicals that have a lower carbon footprint, as well as recycling and reusing materials to reduce waste and emissions are important aspects towards closing the carbon loop. [27][28][29][30][31] A most viable strategy for CO 2 valorization is to use it as a building block towards value-added chemicals, [32][33][34][35][36] fuels 37,38 and construction materials. 39,40 This way, a sustainable source of chemicals and materials is provided by introducing generated CO 2 back in the production processes as an elementary building block, gradually transforming the typical linear production chain to a more sustainable production loop.…”