Effect of stabilizer type on the activity and stability of water-dispersible cobalt(0) nanocluster catalysts in hydrogen generation from the hydrolysis of sodium borohydride

Metin O., Kocak E., ÖZKAR S.

REACTION KINETICS MECHANISMS AND CATALYSIS, vol.103, no.2, pp.325-340, 2011 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 103 Issue: 2
  • Publication Date: 2011
  • Doi Number: 10.1007/s11144-011-0306-3
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.325-340
  • Keywords: Cobalt nanoclusters, Hydrogen phosphate, Poly(acrylic acid), Hydrogen generation, Hydrolysis of sodium borohydride, Kinetics, NICKEL(0) NANOCLUSTERS, PARTICLES
  • Middle East Technical University Affiliated: Yes


Hydrogen phosphate (HPO(4) (2-)) or poly(acrylic acid) (PAA) stabilized cobalt(0) nanoclusters were in situ generated from the reduction of cobalt(II) chloride during the catalytic hydrolysis of sodium borohydride (NaBH(4)) in the presence of stabilizers, HPO(4) (2-) or PAA. Cobalt(0) nanoclusters stabilized by HPO(4) (2-) or PAA were characterized by using UV-Visible spectroscopy, TEM, XPS and FT-IR techniques. They were employed as catalysts in the hydrolysis of NaBH(4) to examine the effect of stabilizer type on their catalytic activity and stability. Detailed reaction kinetics of the hydrolysis of NaBH(4) in the presence of both catalysts was studied depending on catalyst concentration, substrate concentration and temperature. PAA stabilized cobalt(0) nanoclusters provided higher total turnover number (TTON = 6,600) than that of HPO(4) (2-) stabilized cobalt(0) nanoclusters (1,285 turnovers). However, the HPO(4) (2-) stabilized cobalt(0) nanoclusters provided a lower activation energy (E (a) = 53 +/- A 2 kJ mol(-1)) than the PAA stabilized cobalt(0) nanoclusters (E (a) = 58 +/- A 2 kJ mol(-1)) for the hydrolysis of NaBH(4). The use of two types of stabilizers in the preparation of the same metal(0) nanoclusters following the same methodology enables us to compare the electrostatic and steric stabilization in terms of the catalytic activity and stability of metal(0) nanoclusters.