4.6 Article

Glycerol aerobic oxidation to glyceric acid over Pt/hydrotalcite catalysts at room temperature

Journal

SCIENCE BULLETIN
Volume 64, Issue 23, Pages 1764-1772

Publisher

ELSEVIER
DOI: 10.1016/j.scib.2019.10.003

Keywords

Rehydrated hydrotalcites; Interfacial structure; Support basicity; Active sites; Rate-determining step

Funding

  1. National Natural Science Foundation of China [21871021, 21521005]
  2. National Key Research and Development Program [2017YFA0206804]
  3. Fundamental Research Funds for the Central Universities [buctylkxj01, XK1802-6]

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Glycerol (GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals (mainly Au, Pd, Pt) are most commonly employed. Herein, Pt nanoparticles supported on rehydrated MgxAl1-hydrotalcite (denoted as re-MgxAl1-LDH-Pt) were prepared via impregnation-reduction method followed by an in situ rehydration process, which showed high activity and selectivity towards GLY oxidation to produce glyceric acid (GLYA) at room temperature. The metal-support interfacial structure and catalyst basicity were modulated by changing the Mg/Al molar ratio of the hydrotalcite precursor, and the optimal performance was achieved on re-Mg6Al1-LDH-Pt with a GLY conversion of 87.6% and a GLYA yield of 58.6%, which exceeded the traditional activated carbon and oxide supports. A combinative study on structural characterizations (XANES, CO-FTIR spectra, and benzoic acid titration) proves that a higher Mg/Al molar ratio promotes the formation of positively charged Pt delta+ species at metal-support interface, which accelerates bond cleavage of alpha-C-H and improves catalytic activity. Moreover, a higher Mg/Al molar ratio provides a stronger basicity of support that contributes to the oxidation of terminal-hydroxyl and thus enhances the selectivity of GLYA. This catalyst with tunable metal-support interaction shows prospective applications toward transformation of biomass-based polyols. (C) 2019 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

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