Thermodynamics of hydride formation and decomposition in supported sub-10 nm Pd nanoparticles of different sizes

May 22, 2014

Hydrogen storage properties of supported Pd nanoparticles with average sizes in the range 2.7–7.6 nm were studied using indirect nanoplasmonic sensing. For each particle size, a series of isotherms was measured and, through Van’t Hoff analysis, the changes in enthalpy upon hydride formation/decomposition were determined. Contrary to the expected decrease of the enthalpy, due to increasing importance of surface tension in smaller particles, we observe a very weak size dependence in the size range under consideration. We attribute this to a compensation effect due to an increased fraction of hydrogen atoms occupying energetically favorable subsurface sites in smaller nanoparticles.

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