Improved Pt/C electrocatalysts for methanol oxidation prepared by different reducing agents and surfactants and DFT studies on it


JOURNAL OF NANOPARTICLE RESEARCH, vol.19, no.10, 2017 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 19 Issue: 10
  • Publication Date: 2017
  • Doi Number: 10.1007/s11051-017-4044-y
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Middle East Technical University Affiliated: Yes


In this work, PtCl4 as precursor; sodium borohydride (Cat I), hydrazinium hydroxide (Cat II), and formaldehyde (Cat III) as reducing agents; and 1-heptanamine (a), N-methyl-1-heptanamine (b), and N, N-dimethyl-1-heptanamine (c) as surfactants were used to prepare platinum nanoparticles which were then dispersed on carbon XC-72 for use as catalysts in the methanol oxidation reaction. XRD and TEM results indicate that the platinum has a face-centered cubic structure and is found as small and agglomerated particles in different shapes, sizes, and densities. Cat I comprises small (similar to 5 nm) cubic and formless agglomerated (similar to 20-similar to 300 nm) particles, Cat II is composed of small (similar to 5 nm) and a significant number of quite dense spherical agglomerated (similar to 20-similar to 150 nm) particles, and Cat III contains large number of small (similar to 5 nm) and a small number of spherical, less dense, and agglomerated (similar to 20-similar to 200 nm) particles. XPS data shows that the platinum exists in two different oxidation states Pt(0) (similar to 64.5-similar to 69.6%) and Pt(IV) (similar to 35.5-similar to 30.4%), and platinum surface also contains OH, H2O, C-O, C=O, and carbon. DFT and FTIR show that the surfactants decompose to form partially crystalline carbon. Electrochemical studies reveal that performance order of the catalysts towards the methanol oxidation reaction is Cat II < Cat I < Cat III, and that Cat IIIc has the highest performance, which is 2.23 times larger than E-TEK catalysts. It was found that the performance of the catalysts depends on the kind of surfactant, reducing agent, electrochemical surface area, percent platinum utility, roughness factor, and If/(I)r ratio.