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In-situ/operando Techniques, Catalyst & Reactor development

Dr. Albert Gili de Villasante

The work aims at generating knowledge of heterogeneous catalysts for carbon dioxide activation. To achieve this goal, synchrotron-based in situ/operando techniques are fundamental: The development of reaction cells has been one of Albert’s activities. The first cell was developed in the Advanced Light Source synchrotron in Berkeley1, which allowed to perform transmission powder diffraction under gas flow at high temperature. This setup was upgraded to a high-pressure plug-flow system in the PETRA III synchrotron in Germany (Figure-C)2. More recently, Albert has transferred the concept to a thin film geometry within the CatLab project in the BESSY-II synchrotron (Figure-A)3. Besides cell design, Albert is responsible for the commissioning and operation of reactors, including multi-parallel reactors for thin-film catalysis (Figure-B).

The tools developed represent unique opportunities to reveal the structure and dynamics of catalysts. A very recent example is the understanding of the subsurface chemistry of palladium and palladium-gold thin films during acetylene semihydrogenation, the first choice of reaction by CatLab. Figure-D shows the contour map of the hydrogenation of a 20 nm Pd/SiO2/Si catalyst, displaying a clear expansion of the unit cell volume upon intercalation of H in the subsurface of palladium. The cell developed allows to disentangle, with 1 s resolution time, the transformation of Pd(metallic)→PdHα→PdHβ. TEM (Figure-F) complements the synchrotron observations. Beyond palladium, Albert and his team are developing thin films of ceria as non-innocent support for carbon dioxide activation.


The structure-activity correlations for heterogeneous catalysts are established using a combination of different methods, including catalytic tests, several synchrotron scattering and spectroscopic techniques, electron microscopy (SEM/TEM/STEM) and often theory: the focus is carbon dioxide activation for the energy transition. Thus, the discovery of a metastable nickel-carbon cubic system during methane decomposition has recently been reported4, with clear implication for the dry reforming of methane5,6; the superior selectivity and stability of phase-pure rhombohedral In2O3 for the carbon dioxide hydrogenation to methanol was demonstrated7, in cooperation with UniSysCat researchers; a one-pot synthesized iron-doped ceria catalyst was investigated for the carbon dioxide tandem hydrogenation to hydrocarbons, in a cooperation with UniSysCat and BasCat.

Activities in-operando

Figure. (A) 3D CAD representation of the GIXRD operando cell at the μSpot beamline of the BESSY-II synchrotron3; (B) CatLab’s Parallel reactor setup 3D CAD; (C) operando cell for pXRD and XAFS developed at the DESY synchrotron2; (D) contour map of the in situ GIXRD experiment with a 20 nm Si/SiO2/Si catalytic thin film sample during room temperature hydrogenation; (E) PdHα and PdHβ formation from panel C; (F) TEM of a 3 nm Pd/SiO2/Si catalytic thin film after acetylene semihydrogenation; (G) NiC0.3  discovery4; (H) Rhombohedral In2O3 as selective catalyst for carbon dioxide hydrogenation to methanol7; (I) Iron-doped ceria as tandem system for carbon dioxide hydrogenation to hydrocarbons8.

Selected Publications

  1. Schlicker, L.; Doran, A.; Schneppmüller, P.; Gili, A.; Czasny, M.; Penner, S.; Gurlo, A. Transmission in-situ and operando high temperature X-ray powder diffraction in variable gaseous environments. Rev. Sci. Instrum. 2018, 89 (3), 033904. DOI: 10.1063/1.5001695.
  2. Bischoff, B.; Bekheet, M. F.; Dal Molin, E.; Praetz, S.; Kanngießer, B.; Schomäcker, R.; Etter, M.; Jeppesen, H. S.; Tayal, A.; Gurlo, A.; Gili, A. In situ/operando plug-flow fixed-bed cell for synchrotron PXRD and XAFS investigations at high temperature, pressure, controlled gas atmosphere and ultra-fast heating. J. Synchrotron Rad. 2024 (31). DOI: 10.1107/S1600577523009591.
  3. Thum, L.; Arztmann, M.; Zizak, I.; Grüneberger, R.; Steigert, A.; Grimm, N.; Wallacher, D.; Schlatmann, R.; Amkreutz, D.; Gili, A. In situ cell for grazing-incidence x-ray diffraction on thin films in thermal catalysis. Rev. Sci. Instrum. 2024, 95 (3). DOI: 10.1063/5.0179989.
  4. Gili, A.; Kunz, M.; Gaissmaier, D.; Jung, C.; Jacob, T.; Lunkenbein, T.; Hetaba, W.; Dembélé, K.; Selve, S.; Schomäcker, R.; Gurlo, A.; Bekheet, M. F. Discovery and Characterization of a Metastable Cubic Interstitial Nickel-Carbon System with an Expanded Lattice. ACS nano 2025, 19 (2), 2769–2776. DOI: 10.1021/acsnano.4c15300.
  5. Gili, A.; Schlicker, L.; Bekheet, M. F.; Görke, O.; Penner, S.; Grünbacher, M.; Götsch, T.; Littlewood, P.; Marks, T. J.; Stair, P. C.; Schomäcker, R.; Doran, A.; Selve, S.; Simon, U.; Gurlo, A. Surface Carbon as a Reactive Intermediate in Dry Reforming of Methane to Syngas on a 5% Ni/MnO Catalyst. ACS Catal. 2018 (8), 8739-8750. DOI: 10.1021/acscatal.8b01820.
  6. Gili, A.; Schlicker, L.; Bekheet, M.; Görke, O.; Kober, D.; Simon, U.; Littlewood, P.; Schomäcker, R.; Doran, A.; Gaissmaier, D.; Jacob, T.; Selve, S.; Gurlo, A. Revealing the Mechanism of Multiwalled Carbon Nanotube Growth on Supported Nickel Nanoparticles by In situ Synchrotron X-ray Diffraction, Density Functional Theory, and Molecular Dynamics Simulations. ACS Catal. 2019, 9, 6999-7011. DOI: 10.1021/acscatal.9b00733.
  7. Gili, A.; Brösigke, G.; Javed, M.; Dal Molin, E.; Isbrücker, P.; Repke, J.-U.; Hess, F.; Gurlo, A.; Schomäcker, R.; Bekheet, M. F. Performance and Stability of Corundum-type In2O3 Catalyst for Carbon Dioxide Hydrogenation to Methanol. Angewandte Chemie (International ed. in English) 2025, 64 (5), e202416990. DOI: 10.1002/anie.202416990.
  8. Gili, A.; Bekheet, M. F.; Thimm, F.; Bischoff, B.; Geske, M.; Konrad, M.; Praetz, S.; Schlesiger, C.; Selve, S.; Gurlo, A.; Rosowski, F.; Schomäcker, R. One-pot synthesis of iron-doped ceria catalysts for tandem carbon dioxide hydrogenation. Catal. Sci. Technol. 2024. DOI: 10.1039/D4CY00439F