『Abstract
The acidic, non-oxidative dissolution of galena (PbS) nanocrystals
has been studied in detail using transmission electron microscopy
(TEM) to follow the evolution of the size and shape of the nanocrystals
before and after dissolution experiments, X-ray photoelectron
spectroscopy (XPS) to follow particle chemistry, and dissolution
rate analysis to compare dissolution rates between nanocrystalline
and bulk galena. Dissolution characteristics were also studied
as a function of nanocrystal access to bulk vs. confined solution
due to the degree of proximity of next-nearest grains. Nearly
monodisperse galena nanocrystals with an average diameter of 14.4
nm were synthesized for this study, and samples were exposed to
pH 3, deoxygenated HCl solutions for up to 3 h at 25℃. Detailed
XPS analysis showed the nanocrystals to be free of unwanted contamination,
surface complexes, and oxidative artifacts, except for small amounts
of lead-containing oxidation species in both pre- and post-dissolution
samples which have been observed in fresh, natural bulk galena.
Depending on the calculation methods used, galena nanocrystals,
under the conditions of our experiments, dissolve at a surface
area normalized rate of one to two orders of magnitude faster
than bulk galena under similar conditions. We believe that this
reflects the higher percentage of reactive surface area on nanocrystalline
surfaces vs. surfaces on larger crystals. In addition, it was
shown that {111} and {110} faces dissolve faster than {100} faces
on nanocrystals, rationalized by the average coordination number
of ions on each of these faces. Finally, dissolution was greatly
inhibited for galena nanocrystal surfaces that were closely adjacent
(1-2 nm, or less) to other nanocrystals, a direct indication of
the properties of aqueous solutions and ion transport in extremely
confined spaces and relevant to dissolution variations that have
been suspected within aggregates.』
1. Introduction
2. Materials and methods
2.1. Galena synthesis and preparation for dissolution experiments
2.2. Dissolution experiments
2.3. characterization of galena nanocrystals
2.3.1. X-ray diffraction (XRD)
2.3.2. X-ray photoelectron spectroscopy (XPS)
2.3.3. Transmission electron microscopy (TEM)
3. Results and discussion
3.1. Pre-dissolution galena nanocrystals
3.1.1. XRD crystal structure and particle size
3.1.2. Chemical composition of nanocrystals
3.1.3. Pre-dissolution crystal structure and morphology observed
by HRTEM
3.2. Shape and size evolution of post-dissolution PbS nanocrystals
3.2.1. Shape evolution
3.2.2. Statistical analysis of size evolution
3.2.3. HRTEM observations of nanocrystal morphology evolution
3.2.3.1. Isolated nanocrystals
3.2.3.2. Particle clusters
4. Implications
Acknowledgments
Appendix A. Calculation of geometric surface area (AGEO)
and AGEO normalized dissolution rate (RGEO)
References