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MoO3–TiO2 synergy in oxidative dehydrogenation of lactic acid to pyruvic acid

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An efficient catalytic process for the oxidative dehydrogenation of biomass-derived lactic acid by earth-abundant MoO3/TiO2 mixed oxide catalysts is presented. A series of MoO3/TiO2 materials with varied MoO3 loadings were prepared and their performance in the aerobic and anaerobic conversion of lactic acid was evaluated. A strong synergistic effect between MoO3 and TiO2 components of the mixed oxide catalyst was observed. Optimum catalysts in terms of activity and pyruvic acid selectivity can be obtained by ensuring a high dispersion of MoOx species on the titania surface. Mo-oxide aggregates catalyze undesired side-reactions. XPS measurements indicate that the redox processes involving supported Mo ions are crucial for the catalytic cycle. A mechanism is proposed, in which lactic acid adsorbs onto basic sites of the titania surface and is dehydrogenated over the Mo[double bond, length as m-dash]O acid–base pair of a vicinal tetrahedral Mo site. The catalytic cycle closes by hydrolysis of surface pyruvate and water desorption accompanied by the reduction of the Mo center, which is finally oxidized by O2 to regenerate the initial active site. Under anaerobic conditions, a less efficient catalytic cycle is established involving a bimolecular hydrogen transfer mechanism, selectively yielding propionic and pyruvic acids as the major products. The optimum catalyst is 2 wt% MoO3/TiO2 predominantly containing tetrahedral Mo species. With this catalyst the oxidative conversion of lactic acid at 200 °C proceeds with a selectivity of ca. 80% to pyruvic acid. The pyruvic acid productivity is 0.56 g g−1 h−1.

Graphical abstract: MoO3–TiO2 synergy in oxidative dehydrogenation of lactic acid to pyruvic acid

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The article was received on 15 Mar 2017, accepted on 04 May 2017 and first published on 05 May 2017

Article type: Paper
DOI: 10.1039/C7GC00807D
Citation: Green Chem., 2017, Advance Article
  • Open access: Creative Commons BY-NC license
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    MoO3–TiO2 synergy in oxidative dehydrogenation of lactic acid to pyruvic acid

    K. Liu, X. Huang, E. A. Pidko and E. J. M. Hensen, Green Chem., 2017, Advance Article , DOI: 10.1039/C7GC00807D

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