UCLouvain: Heterogeneous catalysis

General expertise of the research group

The group of heterogeneous catalysis is led by Profs. Damien Debecker and Eric Gaigneaux.

Prof. Damien Debecker works mainly on the development of heterogeneous catalysts and biocatalysts, using innovative preparation routes. Strategies to do so involve sol-gel chemistry, enzyme immobilization and encapsulation, spray processing, surface grafting, impregnation, etc. Targeted applications include the greener synthesis of high value chemicals through chemo-enzymatic cascade reactions, the upgrading of biomass and bio-based chemicals (alcohols, sugars, aromatics, short acids, triglycerides), and carbon capture and utilization. In this latter field, the focus is on the hydrogenation of CO2 using green hydrogen, to obtain either methane or methanol. Beyond the catalytic reaction itself, the group investigates the chemical process as a whole, focusing also on in situ product separation/purification, carbon capture, biomass pre-treatments, enzyme selection, scale-up, transfer from batch to flow processes, assessment of new processes through sustainability metrics, etc.

The main scientific interests of Prof. Eric Gaigneaux are the preparation, scaling up and shaping of heterogeneous catalysts while controlling their morphology at the atomic and nanoscopic scales, their physicochemical characterization under operational in situ/operando conditions, and their applications in the production of bio- and e-fuels, abatement of air and water pollutants, transformation of hydrocarbons and (biomass derived) alcohols to more valuable molecules via selective oxidation / ammoxidation / dehydration / oxidative dehydrogenation / deoxydehydration, storage of hydrogen via the hydrogenation of nitrogen to ammonia and decomposition of the later, and (biomass related) fine chemistry with a particular interest for epoxidation, Friedel-Crafts reactions and the valorization of (unsaturated) fatty acids.

Specific hydrogen- related expertise & research topics

• Development (formulation, scaling up and shaping) of metal-based heterogeneous catalysts for the hydrogenation reactions of CO2 (e.g. methanation) and of N2 (to NH3 ) used as a mean to store H2 in the form of chemical energy vectors (CH4 , CH3 OH, NH3 , also called e-fuels).
• Experimental measurement of catalyst performance in the hydrogenation reactions of CO2 and N2 allowing kinetic and mechanistic studies on hydrogenation reactions
• Characterization of hydrogenation catalysts through various physico-chemical tools, to highlight the properties that decisively govern catalytic performance and unravel the structure-activity relationships in the perspective of further catalyst development
• Development of heterogeneous catalysts dedicated to the production of H2 through ethanol dry reforming
• Development of dual function materials for the combined capture and hydrogenation of CO2
• Development of catalysts dedicated to the enhancement of the hydrogenation of N2 to NH3 under plasma conditions
• Development of catalysts for the decomposition of NH3 , and the related production of H2

Available equipment/tools:

• Equipment to measure catalytic performance (continuous flow catalytic microreactors equipped with online gas chromatography and/or mass spectroscopy, batch catalytic microreactors with offline gas chromatography)
• Equipment for the preparation, scaling-up, shaping and regeneration of heterogeneous catalysts (precipitation/impregnation flasks, rotavapors, calcination furnaces, spray driers, pressurized autoclaves, plasma reactors, ball miller, pelletization etc.)
• Equipment(or access to) for the characterization of heterogenous catalysts: advanced spectroscopies (Raman, UV-Vis, IR, XPS, SIMS), microscopies (SEM, TEM), temperature-programmed-oxidation/reduction/desorption/etc experiments, textural measurements (specific surface area and porosity), chemisorption, thermogravimetry, X-ray diffraction, etc. Several techniques (UV-Vis, IR, Raman, XRD and soon XPS) are performed in situ / operando with the catalysts analyzed under realistic conditions (temperature, flow, pressure) of their use.

Participating in FL/B/EU funded projects with H2 related research:

• HEAT (FSR 2023-2025) High Entropy Alloys for Thermocatalytic hydrogenation of CO2
• CO2-spark (FNRS– CR Dr. P. Hongmanorom 2022-2025) Spark ablation technology for the design of efficient CO2 methanation catalysts
• Recovery plan (2023): acquisition of equipment to support research in the framework of the Energy Transition: XPS with high-pressure introduction and pretreatment chamber, hydrogenation reactors, IR spectrometer, temperature-programmed reactor.
• 2 CSC fellowships (Y. Zhao and F. Yang) on CO2 methanation and on the dry reforming of ethanol- NanoCatCO2 (2020-2025) Joined research program between UCLouvain, ETH Zürich and Chulalongkorn University on the understanding of interfacial effects in CO2 methanation catalysts
• CATALYSTNH3SYNTHESIS (H2020-Marie S Curie Action, 2019-2020): Synthetically Tuned Atomic Ordering and Electronic Properties of Nano-Intermetallic Compounds for the Ammonia Synthesis
• Industrial project (confidential, 2019-2024): formulation, scaling-up and shaping of novel catalysts for the production of ammonia via the hydrogenation of N2
• FEDER Synfonhy (2023-2025): formulation and shaping of catalysts to enhance the chemical storage of H2 in ammonia under plasma conditions, and the decomposition of the later

Main relevant publications

1. Effect of the size and distribution of supported Ru nanoparticles on their activity in ammonia synthesis under mild reaction conditions C. Fernández, C. Sassoye, C. Sanchez, D.P. Debecker, P. Ruiz* Applied Catalysis A: General, 474 (2014) 194-202
2. Insights in the mechanism of deposition and growth of RuO2 colloidal nanoparticles over alumina. Implications on the activity for ammonia synthesis Camila Alejandra Fernández, Capucine Sassoye, Nicolas Flores, Néstor Escalona, Eric M Gaigneaux, Clément Sanchez and Patricio Ruiz Applied Catalysis A, 502 (2015) 48-56.
3. Disclosing the synergistic mechanism in the catalytic activity of different-sized Ru nanoparticles for ammonia synthesis at mild reaction conditions Camila Fernández, Chiara Pezzotta, Eric M. Gaigneaux, Nicolas Bion, Daniel Duprez and Patricio Ruiz Catalysis Today, 251 (2015) 88-95.
4. CO2hydrogenation with shape-controlled Pd nanoparticles embedded in mesoporous silica: Elucidating stability and selectivity issues J. Martins, N. Batail, S. Silva, S. Rafik-Clement, A. Karelovic, D.P. Debecker, A. Chaumonnot, D. Uzio* Catalysis Communications, 58 (2015) 11-15
5. TheActive State of Supported Ruthenium Oxide Nanoparticles during Carbon Dioxide Methanation Sophie Carenco*, Capucine Sassoye, Marco Faustini, Pierre Eloy, Damien P. Debecker, Hendrik Bluhm, Miquel Salmeron Journal of Physical Chemistry C, 120 (2016) 15354−15361
6. Selective CO2 methanation on Ru/TiO2 catalyst: unravelling the decisive role of the TiO2 support crystal structure Ara Kim,Clément Sanchez,Gilles Patriarche, Ovidiu Ersen,Simona Moldovan, Andreas Wisnet, Capucine Sassoye, Damien P. Debecker* Catalysis Science & Technology, 6 (2016) 8117-8128
7. Kinetics of hydrogen adsorption and mobility on Ru nanoparticles supported on alumina: Effects on the catalytic mechanism of ammonia synthesis Camila Alejandra Fernández, Nicolas Bion, Eric M. Gaigneaux, Daniel Duprez and Patricio Ruiz Journal of Catalysis, 344 (2016) 16-28.
8. The inhibitor role of NH3 on its synthesis process at low temperature, over Ru catalytic nanoparticles Charles Leterme, Camila Fernández, Pierre Eloy, Eric M. Gaigneaux and Patricio Ruiz Catalysis Today, 286 (2017) 85-100.
9. CO2methanation on Ru/TiO2 catalysts: on the effect of mixing anatase and rutile TiO2 supports Ara Kim, Damien P. Debecker,* François Devred, Vincent Dubois, Clément Sanchez, Capucine Sassoye* Applied Catalysis B: Environmental, 220 (2018) 615-625
10. Combining CO2 capture and catalytic conversion to methane Paulina Melo Bravo, Damien P. Debecker* Waste Disposal & Sustainable Energy, 1 (2019) 53-65
11. Mesoporous TiO2 Support Materials for Ru-Based CO2 Methanation Catalysts Ara Kim, Clément Sanchez, Bernard Haye, Cédric Boissière, Capucine Sassoye,* Damien P. Debecker* ACSApplied Nano Materials, 2 (2019) 3220-3230
12. CO2 hydrogenation to methanol with Ga‐ and Zn‐doped mesoporous Cu/SiO2 catalysts prepared by the aerosol‐assisted sol‐gel process Charlie Paris, Alejandro Karelovic,* Raydel Manrique, Solène Le Bras, François Devred, Vit Vykoukal, Ales Styskalik, Pierre Eloy, Damien P. Debecker* ChemSusChem, 13 (2020) 6409-6417
13. Recent Advances in Heterogeneous Catalyst for Ammonia Synthesis Vijaykumar Marakatti and Eric Gaigneaux ChemCatChem, 12 (2020) 5838-5857.
14. Abiotic Transformation of H2 and CO2 into Methane on a Natural Chromitite Rock Patricio Ruiz, Camila Fernández, Elena Ifandi, Pierre Eloy, Isaac Meza-Trujillo, François Devred, Eric M. Gaigneaux, and Basilios Tsikouras ACSEarth and Space Chemistry, 5 (2021) 1695–1708.
15. Can CO2 and Renewable Carbon Be Primary Resources for Sustainable Fuels and Chemicals? M. M.Faruque Hasan, Liane M. Rossi, Damien P. Debecker, Kevin C. Leonard, Zhenxing Li, Banothile C. E. Makhubela, Chuan Zhao, Arjan Kleij ACSSustainable Chem. Eng., 9 (2021) 12427–12430
16. Immobilization of carbonic anhydrase in an hydrophobic poly(ionic liquid): a new functional solid for CO2 capture Christian Molina Fernández, Ariane Péters, Damien P. Debecker, Patricia Luis* Biochemical Engineering Journal, 187 (2022) 108639
17. Highly Active and Stable Co (Co3O4)_Sm2O3 Nano-crystallites Derived from Sm2Co7 and SmCo5 Intermetallic Compounds in NH3 Synthesis and CO2 Conversion Marakatti, Vijaykumar; Ronda-Lloret, Maria; Krajčí, Marian; Joseph, Boby; Marini, Carlo; Delgado, Juan; Devred, François; Shiju, N. Raveendran; Gaigneaux, Eric Catalysis Science & Technology, 12 (2022) 686-706.
18. Patent on ammonia synthesis with industrial partner Y. Yyyyy, X. Xxxxx, V. Smeets, E. Gaigneaux. EP xxxxxxxx.x, filled on xx/xx/2022
19. CO2 Methanation with Ru@MIL-101 Nanoparticles Fixated on Silica Nanofibrous Veils as structured Catalytic Carrier Eva Loccufier, Geert Watson, Yingrui Zhao, Maria Meledina, Robbe Denis, Parviz Gohari Derakhshandeh, Pascal Van Der Voort, Karen Leus, Damien P. Debecker,* Klaartje De Buysser, Karen De Clerck* Applied Catalysis B: Environmental, 320 (2023) 121972
20. CO2 Methanation over Cobalt Nanoparticles Embedded in ZIF-L-Derived Porous Carbon Nadia Gholampour, Yingrui Zhao, François Devred, Capucine Sassoye, Sandra Casale, Damien P. Debecker* ChemCatChem, 15 (2023) e202201338
21. CO2 methanation with high-loading mesoporous Ni/SiO2 catalysts: toward high specific activity and new mechanistic insights Yingrui Zhao, Valentina Girelli, Ovidiu Ersen, Damien P. Debecker,* Journal of Catalysis, 426 (2023) 283-293
22. Solvent-free preparation of Ru/Al2O3 catalysts for CO2 methanation: an example of frugal innovation Ryma Haddad, Yingrui Zhao, Antoine Miche, Ferdaous Benromdhane, Nivedita Sudheer, Ovidiu Ersen, François Devred, François Ribot, Capucine Sassoye, Clement Sanchez, Damien P. Debecker, Corinne Chaneac,* Cédric Boissière* Chemistry of Materials, 35 (2023) 8248–8260