Thermochemical Measurements of Cation Exchange in CdSe Nanocrystals Using Isothermal Titration Calorimetry

Among the various reported post synthetic modifications of colloidal nanocrystals, cation exchange (CE) is one of the most promising and versatile approaches for the synthesis of nanostructures that cannot be directly synthesized from their constitutive precursors. Numerous studies have reported on the qualitative analysis of these reactions, but rigorous quantitative study of the thermodynamics of CE in colloidal nanoparticles is still lacking. We demonstrate using isothermal titration calorimetry (ITC), the thermodynamics of the CE between cadmium selenide (CdSe) nanocrystals and silver in solution can be quantified. We survey the influence of CdSe nanocrystal diameter, capping ligands and temperature on the thermodynamics of the exchange reaction. Results obtained from ITC provide a detailed description of overall thermodynamic parameters-equilibrium constant ( K _eq), enthalpy (Δ H), entropy (Δ S) and stoichiometry ( n)-of the exchange reaction. We compared the free energy change of reaction (Δ G) between CdSe and Ag⁺ obtained directly from ITC for both CdSe bulk and nanoparticles with values calculated from previously reported methods. While the calculated value is closer to the experimentally obtained Δ G _rxn for bulk particles, nanocrystals show an additional Gibbs free energy stabilization of ∼-14 kJ/mol Se. We discuss a thermochemical cycle elucidating the steps involved in the overall cation exchange process. This work demonstrates the application of ITC to probe the thermochemistry of nanoscale transformations under relevant solution conditions.