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Liquid Phase Oxidation of Benzyl Alcohol over Pt and Pt–Ni Alloy Supported on TiO2: Using O2 or H2O2 as Oxidant?

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Abstract

Benzyl alcohol can be oxidized selectively to benzaldehyde over platinum-based catalysts using either oxygen (O2, supplied in the form of synthetic air) or the more powerful hydrogen peroxide (H2O2) as the oxidant. Here we compare these oxidants in the aqueous phase oxidation of benzyl alcohol in a batch reactor at 363.15 K or 393.15 K over monodisperse Pt and Pt–Ni nanostructures synthesized with molybdenum hexacarbonyl (Mo(CO)6) as a reductant. The initial catalytic activity of either Pt or a Pt–Ni alloy anchored on titania support (TiO2) is much higher when using H2O2 than when using O2 (supplied in the form of synthetic air). However, the high initial activity using H2O2 is accompanied by a strong decrease in the activity over Pt. Alloying Pt with Ni results in a reduction in the activity in the benzyl alcohol oxidation when using O2 but enhances the initial activity when using H2O2. The results are rationalized based on a change in the relative surface concentration of oxygen-containing species upon changing the oxidant or alloying Pt with Ni.

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Notes

  1. The relative oxidation power of H2O vs O2 can be easily assessed by defining a common virtual oxygen species, ‘O’, which may be generated from either gaseous oxygen or hydrogen peroxide:\(1/2\;\text{O}_{2}(\text{g}) \rightarrow \text{`O'}\;\text{and\; at\; equilibrium}\;\mu_{{_{{{}^\backprime O^{\prime}}} }}^{{ex\;O_{2} (g)}} = \frac{1}{2}\mu_{{O_{2} (g)}}\)\(\text{H}_{2}\text{O}_{2}(\text{l}) \rightarrow \text{`O'}+\text{H}_{2}\text{O(l)}\;\text{and\; at\; equilibrium}\;\mu_{{{}^\backprime O^{\prime}}}^{{ex\;H_{2} O_{2} (l)}} = \mu_{{H_{2} O_{2} (l)}} - \mu_{{H_{2} O(l)}}\)

    Thus, the chemical potential of the oxygen species generated from hydrogen peroxide can be much higher than the chemical potential of the oxygen species generated from gaseous oxygen with: \(\mu_{{_{{{}^\backprime O^{\prime}}} }}^{{ex\;H_{2} O_{2} (l)}} - \mu_{{{}^\backprime O^{\prime}}}^{{ex\;O_{2} (g)}} = \mu_{{H_{2} O_{2} (l)}} - \mu_{{H_{2} O_{2} (l)}} - \frac{1}{2}\mu_{{O_{2} (g)}} = \Delta_{rxn}^{{}} \underline {G}^{0} + RT \cdot \ln \frac{{\gamma_{{H_{2} O_{2} }} \cdot x_{{H_{2} O_{2} }} }}{{\gamma_{{H_{2} O}} \cdot x_{{H_{2} O}} \cdot \left( {\frac{{p_{{O_{2} }} }}{1bar}} \right)^{0.5} }}\)

    with \(\Delta_{rxn} \underline {G}^{0} (298.15K) = 108.1 \cdot \frac{kJ}{{mol}}.\) An increase in the chemical potential may thus increase the equilibrium concentration of the active oxygen species. In heterogeneous catalysis, the surface coverage of the active oxygen is limited by saturation coverage and the effect of the higher chemical potential of the active oxygen species may be reduced, if both oxidants yield a high surface coverage of the active oxygen species.

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Funding

This study was supported in part by the National Research Foundation (Grant No. 114606).

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  1. Department of Chemical Engineering, Catalysis Institute, University of Cape Town, Private Bag X3, Rondebosch (Cape Town), 7701, South Africa

    Avela Kunene, Gerard Leteba & Eric van Steen

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  1. Avela Kunene
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  2. Gerard Leteba
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  3. Eric van Steen
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Correspondence to Eric van Steen.

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Kunene, A., Leteba, G. & van Steen, E. Liquid Phase Oxidation of Benzyl Alcohol over Pt and Pt–Ni Alloy Supported on TiO2: Using O2 or H2O2 as Oxidant?. Catal Lett 152, 1760–1768 (2022). https://doi.org/10.1007/s10562-021-03760-z

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