Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape.
Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Svetlana
S
Syrenova
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Carl
C
Wadell
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Ferry A A
FA
Nugroho
Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Tina A
TA
Gschneidtner
Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Yuri A
YA
Diaz Fernandez
Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Giammarco
G
Nalin
Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warsaw, Poland.
Dominika
D
Świtlik
Biology and Biological Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Fredrik
F
Westerlund
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.|Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warsaw, Poland.
Tomasz J
TJ
Antosiewicz
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.|Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk 630090, Russia.
Vladimir P
VP
Zhdanov
Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Kasper
K
Moth-Poulsen
Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.
Christoph
C
Langhammer
D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D053758:Nanoparticles; D010165:Palladium / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D013816:Thermodynamics
D010165:Palladium; D006859:Hydrogen