1. Department of Earth and Planetary Sciences, University of California, Berkeley, California 94720, USA
2. These authors contributed equally to this work

Correspondence to: Jillian F. Banfield Correspondence and requests for materials should be addressed to J.F.B. (Email: jill@eps.berkeley.edu).

Abstract

The thermodynamic behaviour of small particles differs from that of the bulk material by the free energy term A—the product of the surface (or interfacial) free energy and the surface (or interfacial) area. When the surfaces of polymorphs of the same material possess different interfacial free energies, a change in phase stability can occur with decreasing particle size^{1, 2}. Here we describe a nanoparticle system that undergoes structural changes in response to changes in the surface environment rather than particle size. ZnS nanoparticles (average diameter 3 nm) were synthesized in methanol and found to exhibit a reversible structural transformation accompanying methanol desorption, indicating that the particles readily adopt minimum energy structural configurations^{3, 4}. The binding of water to the as-formed particles at room temperature leads to a dramatic structural modification, significantly reducing distortions of the surface and interior to generate a structure close to that of sphalerite (tetrahedrally coordinated cubic ZnS). These findings suggest a route for post-synthesis control of nanoparticle structure and the potential use of the nanoparticle structural state as an environmental sensor. Furthermore, the results imply that the structure and reactivity of nanoparticles at planetary surfaces, in interplanetary dust⁵ and in the biosphere^{6, 7}, will depend on both particle size and the nature of the surrounding molecules.