Amine-functionalized graphene nanosheet-supported PdAuNi alloy nanoparticles: efficient nanocatalyst for formic acid dehydrogenation

Bulut A., Yurderi M., Kaya M., Aydemir M., Baysal A., Durap F., ...More

NEW JOURNAL OF CHEMISTRY, vol.42, no.19, pp.16103-16114, 2018 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 42 Issue: 19
  • Publication Date: 2018
  • Doi Number: 10.1039/c8nj03117g
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.16103-16114
  • Van Yüzüncü Yıl University Affiliated: Yes


Formic acid (HCOOH), a major by-product of biomass processing with high energy density, stability and non-toxicity, has a great potential as a safe and a convenient liquid hydrogen (H-2) storage material for combustion engines and fuel cell applications. However, high-purity hydrogen release from the catalytic decomposition of aqueous formic acid solution at desirable rates under mild conditions stands as a major challenge that needs to be solved for the practical use of formic acid in on-demand hydrogen generation systems. Described herein is a new nanocatalyst system comprised of 3-aminopropyltriethoxysilane-functionalized graphene nanosheet-supported PdAuNi alloy nanoparticles (PdAuNi/f-GNS), which can reproducibly be prepared by following double solvent method combined with liquid-phase chemical reduction, all at room temperature. PdAuNi/f-GNS selectively catalyzes the decomposition of aqueous formic acid through the dehydrogenation pathway (similar to 100% H-2 selectivity), in the absence of any promoting additives (alkali formates, Bronsted bases, Lewis bases, etc.). PdAuNi/f-GNS nanocatalyst provides CO-free H-2 generation with a turnover frequency of 1090 mol H-2 mol metal(-1) h(-1) in the additive-free dehydrogenation of formic acid at almost complete conversion (>= 92%) even at room temperature. The catalytic activity provided by PdAuNi/f-GNS nanocatalyst is higher than those obtained with the heterogeneous catalysts reported to date for the additive-free dehydrogenation of formic acid. Moreover, PdAuNi/f-GNS nanoparticles show high durability against sintering, clumping and leaching throughout the catalytic runs, so that the PdAuNi/f-GNS nanocatalyst retains almost its inherent catalytic activity and selectivity at the end of the 10th recycle.