Tuning selectivity in the direct conversion of methane to methanol: bimetallic synergistic effects on the cleavage of C-H and O-H bonds over NiCu/CeO₂ catalysts
Creators
- 1. Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain
- 2. Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET, S2000EKF Rosario, Santa Fe, Argentina
- 3. Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States
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Description
The efficient activation of methane and simultaneous water dissociation are crucial in many catalytic reactions on oxide-supported transition metal catalysts. On very low-loaded Ni/CeO₂ surfaces, methane easily fully decomposes, CH₄ -> C + 4H, and water dissociates, H₂O -> OH + H. However, in important reactions such as the direct oxidation of methane to methanol (MTM), where complex interplay exists between reactants (CH₄, O₂), it is desirable to avoid the complete dehydrogenation of methane to carbon. Remarkably, the barrier for the activation of C-H bonds in CHx (x= 1-3) species on Ni/CeO₂ surfaces can be manipulated by adding Cu, forming bimetallic NiCu clusters, whereas the ease for cleavage of O-H bonds in water, is not affected by ensemble effects, as obtained from density functional theory-based calculations. CH4 activation occurs only on Ni sites and H₂O activation on both Ni and Cu sites. The MTM reaction pathway for the example of the Ni₃Cu₁/CeO₂ model catalyst predict higher selectivity and a lower activation barrier for methanol production, compared with that for Ni₄-CeO₂. These findings point toward a possible strategy to design active and stable catalysts which can be employed for methane activation and conversions.
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References
Journal reference (Paper in which the data is described and analysed) P. G. Lustemberg, S. D. Senanayake, J. A. Rodriguez, M. V. Ganduglia-Pirovano, J. Phys. Chem. Lett. 13, 24, 5589–5596 (2022), doi: 10.1021/acs.jpclett.2c00885