Self-Supported Pd x Bi Catalysts for the Electrooxidation of Glycerol in Alkaline Media

• Published in: Journal of the American Chemical Society 2014-03, Vol.136 (10), p.3937-3945
• Main Authors: Zalineeva, Anna, Serov, Alexey, Padilla, Monica, Martinez, Ulises, Artyushkova, Kateryna, Baranton, Stève, Coutanceau, Christophe, Atanassov, Plamen B
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja412429f

Highly active self-supported Pd x Bi catalysts are synthesized by the sacrificial support method. Self-supported Pd x Bi catalysts have a porous nanostructured morphology with high surface areas (in the range from 75 to 100 m2 g–1), making Pd x Bi a state-of-the-art catalyst. Pd4Bi displays the highest activity toward glycerol oxidation. In situ Fourier transform infrared spectroscopy highlights the unique catalytic behavior of self-supported Pd x Bi materials due to their particular structure and morphology. The confinement of reactants and intermediates in pores acting as nanoreactors is responsible for the high selectivity as a function of the electrode potential: aldehyde and ketone at low potentials, hydroxypyruvate at moderate potentials, and CO2 at high potentials. Moreover, the selectivity depends on the electrode history: it is different for the positive potential scan direction than for the reverse direction, where the catalyst becomes selective toward the production of carboxylates.