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Towards a feasible and stable thermocatalytic conversion of CO₂ to methanol and E-fuels

Problem statement

Unarguably, CO₂ is a crucial concern affecting climate change. To cope with or solve the issue, viable valorization strategies are required to efficiently use CO₂, allowing for a circular economy. We aim to convert CO₂ into CO, methane, methanol, dimethyl ether, or E-fuels.

Our activities in CO2 conversion are related to (i) analyzing the stability of industrially relevant catalysts under realistic conditions and (ii) developing new catalytic materials based on Cu. In (i), we are developing reactors that augment the kinetic information: (a) in situ and operando spectroscopic reactors that work under (close to) working conditions to study structure-performance relationships, (b) periodic reactors with transient or variable conditions over time or space. In (ii), we work mainly with novel materials such as metal-organic frameworks (MOFs).

We guide the design of these catalysts based on stability and using density functional theory (DFT) and microkinetic modeling.

Goals

  • Develop advanced structure-function-deactivation relationships of industrially relevant catalysts
  • Analyze the effect of “activity modifiers,” such as sulfur species, aromatics, chlorine, etc., on the catalyst structure and performance
  • Improve the catalyst structure-function correlations using in-situ, operando, and dynamic techniques and reactors
  • Synthesize new catalytic materials with enhanced stability and selectivity
  • Develop a microkinetic-based modeling framework to analyze the catalyst performance
CO2-2023

Related People

Gontzal Lezcano
Juan David Trueba
Pia Dally
Zainab Almoruhen

Related Publications

Mechanistic and kinetic effects of Ga on a Cu catalyst for CO₂ hydrogenation to methanol

by Yerrayya, Lezcano, Velisoju, Trueba, Kulkarni, Almofleh, Aljama, Castaño
J. CO2 Util. Year: 2025 DOI: https://doi.org/10.1016/j.jcou.2025.103086

Abstract

This work investigates the mechanistic and kinetic effects of gallium (Ga) promotion on copper (Cu) catalysts for carbon dioxide hydrogenation using the density functional theory (DFT), in situ infrared spectroscopy, and mean-field microkinetic simulations. The DFT calculations reveal potential reaction pathways for methanol synthesis, emphasizing the role of formate (HCOO) and carboxyl (COOH) intermediates on Cu (111) and Ga–Cu (111) surfaces. The in situ infrared spectroscopic analysis identifies surface intermediates, validating DFT-predicted mechanistic trends and confirming the preferential COOH pathway on unpromoted Cu catalysts and the HCOO pathway on Ga–Cu catalysts. Microkinetic simulations demonstrate how Ga promotion alters reaction kinetics, favoring the HCOO pathway via H₂COO** formation and explaining the enhanced methoxy intermediate generation on Ga–Cu, which is critical for dimethyl ether production. The temperature effects demonstrate a kinetic shift toward the COOH pathway on Cu catalysts, contrasting with the stability of the HCOO pathway on Ga–Cu. This integrative study demonstrates the significance of Ga in modulating surface chemistry and reaction mechanisms, offering a foundation for designing efficient methanol synthesis catalysts.

Keywords

MKM HCE CO2