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It is expected that atomic vacancies or nanometric cavities reduce the numberof chemical bonds of nearby atoms and hence the strength of a voided solid.However, the hardness of a porous specimen does not always follow this simplepicture of coordination counting. An introduction of a certain amount of atomicvacancies or nanocavities could, instead, enhance the mechanical strength ofthe porous specimen. Understanding the mechanism behind the intriguingobservations remains yet a high challenge. Here we show with analyticalexpressions that the shortened and strengthened bonds between theunder-coordinated atoms and the associated local strain and energy trapping[Sun, Prog Solid State Chem 35, 1-159 (2007)] in the negatively curved surfaceskins dominate the observed nanocavity hardening. Agreement between predictionsand the experimentally observed size-dependence of mechanical strength of somenanoporous materials evidences for the proposed mechanism.

Nanocavity hardening: impact of broken bonds at the negatively curved surfaces