The thermodynamic behaviour of small particles differs from that of the bulk material by the free energy term γA—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 size1,2. 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 configurations3,4. 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 biosphere6,7, will depend on both particle size and the nature of the surrounding molecules.
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We thank P. Alivisatos for access to equipment, and W. Smith, T. R. Forester and D. Fincham for providing MD codes. EXAFS data were acquired on the DCM beamline at the UW-Madison Synchrotron Radiation Center (SRC), and we thank A. Jürgensen. WAXS data were acquired on beamline 11-ID-C at the Advanced Photon Source (APS), and we thank Y. Ren and M. Beno. HRTEM was performed at the National Center for Electron Microscopy, Berkeley, California. We also thank J. Rustad and G. Waychunas for discussions. This work was supported by the US Department of Energy (DOE), the Lawrence Berkeley National Laboratory LDRD, and the US National Science Foundation (NSF). The SRC is supported by the Division of Materials Research of the US NSF. Use of the Advanced Photon Source is supported by the US DOE, Office of Science, Office of Basic Energy Sciences.
The authors declare that they have no competing financial interests.
Supplementary Figure 3 and Table 1: EXAFS analysis of the nanoparticle structure transition associated with methanol desorption. (DOC 201 kb)
Supplementary Figure 4: Pair distribution function (PDF) analysis of nanocrystalline ZnS before and after water binding. (DOC 121 kb)
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Zhang, H., Gilbert, B., Huang, F. et al. Water-driven structure transformation in nanoparticles at room temperature. Nature 424, 1025–1029 (2003). https://doi.org/10.1038/nature01845
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