Supported copper-copper oxide nanoparticles as active, stable and low-cost catalyst in the methanolysis of ammonia-borane for chemical hydrogen storage

YURDERI M., BULUT A., ERTAS I. E., Zahmakıran M., Kaya M.

APPLIED CATALYSIS B-ENVIRONMENTAL, vol.165, pp.169-175, 2015 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 165
  • Publication Date: 2015
  • Doi Number: 10.1016/j.apcatb.2014.10.011
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.169-175
  • Van Yüzüncü Yıl University Affiliated: Yes


The physical mixture of copper (Cu) copper(I) oxide (Cu2O) and copper(II) oxide (CuO) nanoparticles supported on activated carbon (Cu-Cu2O-CuO/C) were reproducibly prepared by a simple deposition-reduction technique without using any stabilizer in water at room temperature. The characterization of the resulting material by ICP-OES, P-XRD, XPS, DR-UV/vis, BFTEM and HRTEM techniques reveals that the formation of well-dispersed highly crystalline 3.8 +/- 1.7 nm nanoparticles on the surface of activated carbon. These carbon supported Cu-Cu2O-CuO nanoparticles were employed as heterogeneous catalyst in the methanolysis of ammonia-borane (NH3BH3), which has been considered as one of the attractive materials for the efficient storage of hydrogen, under mild conditions. We found that only 3.0 mol % Cu-Cu2O-CuO/C catalyst is enough to catalyze the methanolysis of ammonia-borane with high activity (TOF = 24 min(-1)) and conversion (>99%) at room temperature. More importantly, the exceptional stability of supported Cu-Cu2O-CuO nanoparticles against to sintering and leaching make Cu-Cu2O-CuO/C recyclable catalyst for the methanolysis of ammonia-borane. Cu-Cu2O-CuO/C catalyst retains >76% of its initial activity with 94% of conversion even at 8th recycle in the methanolysis of ammonia-borane at complete conversion. The study reported here also includes the collection of kinetic data for Cu-Cu2O-CuO/C catalyzed methanolysis of ammonia-borane depending on catalyst [Cu], substrate [NH3BH3] concentrations and temperature to determine the rate expression and the activation parameters (E-a, Delta H-#, and Delta S-#) of the catalytic reaction. (C) 2014 Published by Elsevier B.V.