Model for adsorption of ligands to colloidal quantum dots with concentration-dependent surface structure

Adam J. Morris-Cohen, Vladislav Vasilenko, Victor A. Amin, Matthew G. Reuter, Emily Allyn Weiss*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

90 Scopus citations


Figure Persented: A study of the adsorption equilibrium of solution-phase CdS quantum dots (QDs) and acid-derivatized viologen ligands (N-[1-heptyl],N'-[3-carboxypropyl]-4,4′-bipyridinium dihexafluorophosphate, V 2+) reveals that the structure of the surfaces of the QDs depends on their concentration. This adsorption equilibrium is monitored through quenching of the photoluminescence of the QDs by V 2+ upon photoinduced electron transfer. When modeled with a simple Langmuir isotherm, the equilibrium constant for QD-V 2+ adsorption, K a, increases from 6.7 × 10 5 to 8.6 × 10 6 M -1 upon decreasing the absolute concentration of the QDs from 1.4 × 10 -6 to 5.1 × 10 -8 M. The apparent increase in K a upon dilution results from an increase in the mean number of available adsorption sites per QD from 1.1 (for [QD] = 1.4 × 10 -6 M) to 37 (for [QD] = 5.1 × 10 -8 M) through desorption of native ligands from the surfaces of the QDs and through disaggregation of soluble QD clusters. A new model based on the Langmuir isotherm that treats both the number of adsorbed ligands per QD and the number of available binding sites per QD as binomially distributed quantities is described. This model yields a concentration-independent value for K a of 8.7 × 10 5 M -1 for the QD-V 2+ system and provides a convenient means for quantitative analysis of QD-ligand adsorption in the presence of competing surface processes.

Original languageEnglish (US)
Pages (from-to)557-565
Number of pages9
JournalACS Nano
Issue number1
StatePublished - Jan 24 2012


  • binomial distribution
  • equilibrium constant
  • ligand adsorption
  • photoluminescence
  • quantum dot

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)


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