K W Hipps - Predicting the Size Distribution in Crystallization of TSPP:TMPyP Binary Porphyrin Nanostructures in a Batch Desupersaturation Experiment

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  Adinehnia, Morteza, Mazur, Ursula, Hipps, K. W. Crystal   Growth & Design 2014 14 (12)   6599-6606

  Abstract: Crystallization of a binary porphyrin   nanostructure (BPN) of TSPP   (meso-tetra(4-sulfonatophenyl)porphyrin) and TMPyP   (meso-tetra(N-methyl-4-pyridyl)porphyrin) was studied. The   morphology and crystallinity of the BPN was investigated using   transmission electron (TEM) and atomic force microscopies (AFM).   The composition of the BPN was analyzed using X-ray photoelectron   spectroscopy (XPS), elemental analysis, and UV–visible   spectroscopy. These techniques revealed a 1:1 composition of   anionic to cationic porphyrins in the structure. Our initial   studies on the synthesis of these materials revealed that the   average size of these crystals increases monotonically with   synthesis temperature and decreasing monotonically with initial   concentration (supersaturation) of the mother solution. In this   work we have developed a model to simulate the growth of these   organic monocrystalline materials for the first time. This model   encompasses all the major kinetic and thermodynamic steps of   crystallization including homogeneous nucleation, growth, and   Ostwald ripening. The model is then validated by comparing the   simulation results with experimental crystallization histograms.   The unknown parameters are extracted by fitting the simulation to   the experimental data. This investigation will help in better   understanding of crystallization and size control in this class   of photoactive organic materials. The integration rate constant   pre-exponential is found to be (2.9 ± 1.3) × 106 m4/(mol s), and   the activation energy for the integration rate is determined as   44 ± 2 kJ/mol.

  Address (URL): http://dx.doi.org/10.1021/cg501506s