ACS Nano. 2014 Sep 23;8(9):9463-70. doi: 10.1021/nn503603e. Epub 2014 Aug 22.

Low capping group surface density on zinc oxide nanocrystals.

ACS nano

Carolyn N Valdez, Alina M Schimpf, Daniel R Gamelin, James M Mayer

PMID: 25131410 DOI: 10.1021/nn503603e

Abstract

The ligand shell of colloidal nanocrystals can dramatically affect their stability and reaction chemistry. We present a methodology to quantify the dodecylamine (DDA) capping shell of colloidal zinc oxide nanocrystals in a nonpolar solvent. Using NMR spectroscopy, three different binding regimes are observed: strongly bound, weakly associated, and free in solution. The surface density of bound DDA is constant over a range of nanocrystal sizes, and is low compared to both predictions of the number of surface cations and maximum coverages of self-assembled monolayers. The density of strongly bound DDA ligands on the as-prepared ZnO NCs is 25% of the most conservative estimate of the maximum surface DDA density. Thus, these NCs do not resemble the common picture of a densely capped surface ligand layer. Annealing the ZnO NCs in molten DDA for 12 h at 160 °C, which is thought to remove surface hydroxide groups, resulted in a decrease of the weakly associated DDA and an increase in the density of strongly bound DDA, to ca. 80% of the estimated density of a self-assembled monolayer on a flat ZnO surface. These findings suggest that as-prepared nanocrystal surfaces contain hydroxide groups (protons on the ZnO surfaces) that inhibit strong binding of DDA.

Keywords: NMR spectroscopy of nanocrystals; capping ligands; colloidal semiconductors; ligand shell; zinc oxide

Publication Types

• Journal Article
• Research Support, Non-U.S. Gov't
• Research Support, U.S. Gov't, Non-P.H.S.