Oleylamine-Stabilized Copper(0) Nanoparticles: An Efficient and Low-Cost Catalyst for the Dehydrogenation of Dimethylamine Borane

DUMAN S., ÖZKAR S.

CHEMCATCHEM, vol.9, no.13, pp.2588-2598, 2017 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 9 Issue: 13
  • Publication Date: 2017
  • Doi Number: 10.1002/cctc.201700367
  • Journal Name: CHEMCATCHEM
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.2588-2598
  • Keywords: copper, dehydrogenation, dimethylamine borane, nanocatalysis, nanoparticles, METAL-ORGANIC FRAMEWORK, BORON-NITROGEN BONDS, AMMONIA-BORANE, RUTHENIUM(III) ACETYLACETONATE, HYDROLYTIC DEHYDROGENATION, HETEROGENEOUS CATALYSIS, REUSABLE NANOCATALYST, HOMOGENEOUS CATALYST, HYDROGEN-PRODUCTION, ALCOHOL OXIDATION
  • Middle East Technical University Affiliated: Yes

Abstract

Copper(0) nanoparticles, in situ generated from the reduction of copper(II) 2-ethylhexanoate during the dehydrogenation of dimethylamine borane (DMAB) at 50.0 +/- 0.1 degrees C in toluene solution, are active catalysts in hydrogen generation from DMAB, but not very stable against agglomeration. Addition of 5.0 equivalents of oleylamine (OAm) was found to stabilize copper(0) nanoparticles noticeably, while maintaining high catalytic activity. Oleylamine-stabilized copper(0) nanoparticles could be isolated from the solution and characterized by XRD, TEM, UV/Vis, attenuated total reflectance (ATR)-FTIR, and B-11 NMR spectroscopies. Our report also includes (i) comparative catalytic activities of copper(0) nanoparticles in the absence and presence of OAm depending on the initial [OAm]/[Cu] ratio, catalyst concentration, substrate concentration, and temperature, (ii) the catalytic lifetime of copper(0) nanoparticles in the absence and presence of OAm in the dehydrogenation of DMAB at 50.0 +/- 0.1 degrees C, (iii) testing the ease of isolation and reusability of copper(0) nanoparticles in the absence and presence of OAm in the dehydrogenation of DMAB, (iv) the results of quantitative kinetic poisoning experiments by using 1,10-phenanthroline, showing that copper(0) nanoparticles are kinetically competent catalysts in the dehydrogenation of DMAB.