1. Lattice Oxygen and Feed Oxygen Exchange for the High Rate of H2 + O2 Recombination on Ti1-xPdxO2-x Catalyst at Room Temperature.
- Author
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Prasanna, Usha, K. M., Jain, Manish, and Hegde, M. S.
- Subjects
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FOREIGN exchange rates , *CATALYSTS , *OXYGEN , *CORDIERITE , *IONS - Abstract
The Pd ion substituted TiO2, synthesized by solution combustion method crystallizes in anatase structure with stable composition Ti1-xPdxO2-x (x = 0.01–0.03) creating an oxide ion vacancy per Pd2+ ion substitution. Over 1.35 mol of H2 per mole of bulk Pd ions, in ~ 5 nm nanocrystalline catalyst Ti1-xPdxO2-x (x = 0.03) is adsorbed at 300 K. On exposure of only hydrogen to Ti0.98Pd0.02O1.98 at 300 K, water is formed making the catalyst wet. On heating in a vacuum, mass loss due to water is 0.026 mol /mole of catalyst meaning 1.3 mol of hydrogen per mole of Pd ion in the catalyst. Pd ion substitution in TiO2 anatase activates lattice oxygen leading to the formation of H2O on exposure to H2 gas at 300 K utilizing lattice oxygen. On heating in air at 650 K the reduced catalyst is regenerated. The catalyst produces a high rate of H2 + O2 recombination up to 9 µmoles−1 g−1 at 300 K, and over 230 µmoles−1 g−1 at 330 K with a TOF of 2000 h−1. The catalyst is coated on cordierite honeycomb avoiding handling of powder catalyst. The rates are highest compared to any catalyst for H2 + O2 recombination known so far. Extensive DFT calculation on (101) surface in Ti31Pd1O63 slab confirmed (a) one oxygen out of 4 bonded to Pd ion in nearly square geometry is fully activated to form water molecule creating an oxide ion vacancy; (b) dissociative adsorption of H2 on one of the Pd as well as oxide ion and not both on Pd ion; (c) exchange of feed oxygen with lattice oxygen during 2H2 + O2 recombination; (d) 2H2 + O2 → 2H2O molecules form per Pd ion in one cycle regenerating the catalyst, Ti0.97Pd0.03O1.97 surface explaining high rates of recombination and (e) Pd ion undergoes redox cycle with Ti and oxide ions acting as charge reservoirs. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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