(605h) Tuning Ni-Catalyzed CO2 Hydrogenation Pathways Via Ni-Ceria Support Interactions and Ni-Fe Bimetallic Formation

Winter, L., Institut de Recherche de Chimie Paris, Chimie ParisTech/CNRS
Chen, J. G., Columbia University
Conversion of CO2 to CO for use as a Fischer-Tropsch feedstock provides an attractive option for offsetting CO2 emissions.1,2 Non-precious Ni catalysts are active for the reduction of CO2 by H2, but the catalysts are highly selective to CH4 production.1,3,4 We investigated the coordinated mechanistic contributions of the CeO2 support and Ni admetal. We then modified Ni catalysts with Fe in order to tune the CO selectivity while maintaining high activity.

CO2 hydrogenation over Fe-modified Ni/CeO2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy and in a pulse reactor using mass spectrometry. Low loading of Ni/CeO2 was associated with high selectivity to CO over CH4, while higher Ni loading improved CO2 hydrogenation activity but reduced CO selectivity. In situ XANES and AP-XPS revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. Isotope studies using C18O2 revealed that oxygen exchange with the CeO2 support occurs beyond the surface layer. Subsurface oxygen participates in the reaction, and oxygen exchange is fast with respect to the reaction time. The results suggest that H2 dissociation by metallic Ni promotes C-O bond breaking of CO2 adsorbed on reduced ceria, and that oxygen vacancies are filled by oxygen from the adsorbed CO2.5

Bimetallic Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. TPR results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that the majority of Fe in the bimetallic catalysts was oxidized.6

The trends in bimetallic modification and support effects should guide efforts to develop non-precious metal catalysts for the selective production of CO from CO2 hydrogenation.

  1. Porosoff, M. D., Yan, B. & Chen, J. G. Catalytic reduction of CO2 by H2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities. Energy Environ. Sci. 9, 62–73 (2016).
  2. Perathoner, S. & Centi, G. CO2 recycling: A key strategy to introduce green energy in the chemical production chain. ChemSusChem 7, 1274–1282 (2014).
  3. Sehested, J., Dahl, S., Jacobsen, J. & Rostrup-Nielsen, J. R. Methanation of CO over nickel: Mechanism and kinetics at high H2/CO ratios. J. Phys. Chem. B 109, 2432–2438 (2005).
  4. Tada, S., Shimizu, T., Kameyama, H., Haneda, T. & Kikuchi, R. Ni/CeO2 catalysts with high CO2 methanation activity and high CH4 selectivity at low temperatures. Int. J. Hydrogen Energy 37, 5527–5531 (2012).
  5. Winter, L. R., Chen, X., Chang, K. & Chen. J. G. Coordinated effects of metallic Ni and reduced CeO2 for subsurface oxygen exchange during the reduction of CO2 by hydrogen. Chem. Eur. J. (2018) In preparation.
  1. Winter, L. R., Gomez, E., Yan, B., Yao, S. & Chen, J. G. Tuning Ni-catalyzed CO2 hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation. Appl. Catal. B Environ. 224, 442–450 (2018).