C1 Feedstock; Heterogeneous Catalyst; Carbon Dioxide Hydrogenation; high pressure microsystem; First Principles Molecular Modelling
Copéret Christophe, Hung-Kun Lo (2018), CO2 Hydrogenation to Formate with Immobilized Ru-Catalysts based on Hybrid Organo-Silica Mesostructured Materials, in ChemCatChem
Reymond Helena, Amado-Blanco Victor, Lauper Andreas, Rudolf von Rohr Philipp (2017), Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol, in ChemSusChem
, 10(6), 1166-1174.
Reymond Helena, Vitas Selin, Vernuccio Sergio, von Rohr Philipp Rudolf (2017), Reaction Process of Resin-Catalyzed Methyl Formate Hydrolysis in Biphasic Continuous Flow, in Industrial & Engineering Chemistry Research
, 56(6), 1439-1449.
Reymond H., Rudolf von Rohr P. (2017), Micro-view-cell for phase behaviour and in situ Raman analysis of heterogeneously catalysed CO2 hydrogenation, in Review of Scientific Instruments
, 88(11), 114103-1.
Praveen C. S., Comas-Vives A., Copéret C., VandeVondele J., Role of Water, CO2, and Noninnocent Ligands in the CO2 Hydrogenation to Formate by an Ir(III) PNP Pincer Catalyst Evaluated by Static-DFT and ab Initio Molecular Dynamics under Reaction Conditions, in Organometallics
The hydrogenation of CO2 into chemicals and fuels is an innovative technology to mitigate CO2 emissions by the conversion of waste CO2 to methanol and formic acid. Because hydrogen production is an established, efficient process powered by renewable energy, large-scale CO2 hydrogenation can provide a green process for producing those alternative fuels/C1 feedstocks. The demand of methanol and formic acid in the near future is expected to drastically increase as methanol is a key C1 building block that can also be used in direct fuel cells and formic acid is considered as an efficient hydrogen carrier. While synthesis of methanol from syngas is a robust commercial process that can be readily adapted to CO2/H2 feeds, CO2 hydrogenation to formic acid is limited by thermodynamics and the facile decomposition of formic acid back to CO2 and H2. Furthermore, formic acid derivatives can only be produced using homogeneous catalysts, limiting process efficiency. The objective of this project is a direct conversion of CO2-derived methanol and formic acid to methyl formate intermediate in order to overcome thermodynamic constraints and to generate methanol and formic acid through its hydrolysis in a consecutive step. While methanol production and methyl formate hydrolysis are already well understood, an efficient overall process requires the development of robust heterogeneous CO2 hydrogenation catalysts selective for formic acid. Hence, the detailed understanding of the overall process, from the catalyst design to the process engineering, remains a formidable challenge. This project encompasses the development of efficient heterogeneous catalysts where two strategies will be evaluated: 1) the immobilization of homogeneous catalysts, which involves the understanding of the best ligand sets through a combined experimental and computational approaches and the subsequent development of the most promising immobilized catalysts, and 2) the tuning of selectivity of more classical heterogeneous catalysts for methanol synthesis towards methyl formate production, which involves both catalyst development and a detailed understanding of the surface chemistry of supported metal particles through in situ and computational studies. Additional critical aspects of this project are process engineering, microreactor and high-pressure technology under continuous operation (up to 1000 bar), which will bring advantages in catalyst screening, evaluating thermodynamic limits (the comprising reactions are known to be boosted at high pressure) and a simulation-based design of in situ cells for spectroscopic and visual inspection of phase behavior to identify possible phase separation during the reaction. It is thus not surprising that the project requires a synergistic approach, which combines the expertise across the scale of catalyst design and evaluation: from molecular chemistry and immobilization of homogeneous catalysts (group of Prof. Copéret), surface chemistry and classical heterogeneous catalysis including spectroscopy (group of Dr. A. Urakawa), computational chemistry (group of Prof. J. VandeVondele) and process engineering (Prof. P. Rudolf von Rohr).