Cooperative Reorganization of Mineral and Template during Directed Nucleation of Calcium Carbonate
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Self-assembled monolayers (SAMs) prepared from organic thiol molecules on metal substrates are known to exert substantial influence over mineralization and, as such, provide model systems for investigating the mechanisms of templated crystallization by organic matrices. Characterizing the structural evolution at the organic/inorganic interface in SAM/crystal systems is of paramount importance in understanding these mechanisms. In this study, X-ray absorption spectroscopy is used to characterize the structural evolution of SAMs prepared from purpose-synthesized organic thiols, with similar yet subtly different structures and compositions, during the course of mineralization at their surfaces. The studies reveal that the structure of the thiol molecules strongly affects their ability to reorient within the SAM. Complementary scanning electron microscopy measurements demonstrate that the feature of the SAMs is strongly correlated with the capability of the monolayers to induce preferential ordering among the organic crystals. Consistent with recent modeling studies of SAM/crystal systems, these findings provide experimental evidence that structural flexibility within the SAMs is crucial for achieving templated crystallization and that templating is inherently a cooperative process that selects the most favorable combination of SAM and crystal orientations.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1212249
- Report Number(s):
- PNNL-SA-88837
- Journal Information:
- Journal of Physical Chemistry. C, Vol. 117, Issue 21; ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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