Pd and Pd@PdO core–shell nanoparticles supported on Vulcan carbon XC-72R: comparison of electroactivity for methanol electro-oxidation reaction

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Nanomaterials based on Pd nanoparticles supported on Vulcan carbon (XC-72R) were prepared by the organometallic approach in one-pot and mild conditions (3 bar hydrogen and room temperature) using Pd(dba)2 (bis (dibenzylideneacetone) palladium (0)) as metal source and hexadecylamine (HDA) as stabilizer. High-resolution transmission electron microscopy (HR-TEM) evidenced the presence of well-dispersed Pd nanoparticles of ca. 4.5 nm mean size onto the carbon support (Pd/HDA/C). Scanning and transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) allowed to determine the chemical composition of the nanomaterials. When the Pd/HDA/C nanomaterial was submitted to heating treatment (ht) at 400 °C under air (referred as Pd/HDA/C@air-ht), X-ray photoelectron spectroscopy (XPS) and HR-TEM/STEM-EELS analyses suggested the presence of interactions between PdO and Pd(0) as a result of the formation of Pd@PdO core–shell nanoparticles. The highest oxidation current magnitude during methanol oxidation reaction is ascribed to the heat-treated material, linked with a better electron and mass transfer processes at the electrode interface. This can be attributed to electronic interactions at the core–shell formed, which might promote different redox processes at the electrode interface during CH3OH deprotonation in the alkaline electrolyte.

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The authors wish to acknowledge the financial support provided by CONACyT (Project 157613, 247208), Instituto Politécnico Nacional (COFAA, BEIFI-IPN-20180430) and SNI-CONACyT, Dirección de Investigación-Universidad Iberoamericana (UIA) F132021 project, C. Juárez-Balderas from the Departamento de Estudios en Ingeniería para la Innovación (UIA) for the heat treatments and fruitful comments, R. Borja-Urby from the Centro de Nanociencias y Micro Nanotecnologías (CNMN) and 2015 CONACyT–SEP basic research Project 257931 for HR-TEM/STEM-EELS analyses. This collaborative research was also conducted in the framework of the French-Mexican International Laboratory (LIA) devoted to Molecular Chemistry and its applications in Materials and Catalysis funded by CNRS and CONACyT. LPA G-O thanks the financial support from CONACyT within Doctor Fellowship.

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Guerrero-Ortega, L.P.A., Ramírez-Meneses, E., Cabrera-Sierra, R. et al. Pd and Pd@PdO core–shell nanoparticles supported on Vulcan carbon XC-72R: comparison of electroactivity for methanol electro-oxidation reaction. J Mater Sci 54, 13694–13714 (2019) doi:10.1007/s10853-019-03843-8

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