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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 for efficient usage of 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

Synthesis of Rh6(CO)16 in Supercages of Zeolite HY: Reaction Network and Kinetics of Formation from Mononuclear Rhodium Precursors via Rh4(CO)12 Facilitated by the Water Gas Shift Half Reaction

by Fang, Valecillos, Conley, Chen, Castaño, Gates
J. Phys. Chem. C Year: 2020

Abstract

Rh(I)(CO) 2complexes anchored to zeolite HY were converted into Rh4 (CO) 12 in the zeolite supercages upon exposure to flowing CO + H2 O at 35 °C, and the chemistry and kinetics were characterized with infrared spectroscopy. Rh6 (CO) 16 formed along with Rh4 (CO)12 , but only in low yield, although it is more stable than Rh4 (CO)12 . The formation of Rh6 (CO) 16 was hindered by trapping of Rh4 (CO) 12 in the supercages and by the low rate of transport of the mononuclear rhodium species. However, exposure of the sample to wet helium at 80 °C caused the Rh4 (CO) 12 to fragment, generating anchored Rh(I)(CO) 2 and also Rh6 (CO)16 . IR spectra recorded under various conditions led to elucidation of the reaction network for cluster formation and breakup and a strategy of repetitive treatments that boosted the yield of Rh6 (CO) 16 to >90%. The reversible formation and breakup of the rhodium carbonyl clusters were facilitated by the half-reactions of the water gas shift reaction, with gas-phase products identified by mass spectrometry. The results show how understanding of the reactions within a zeolite allows control of the nuclearity of encaged metal clusters, an important class of catalyst.

Keywords

CO2 HCE