Filtern
Erscheinungsjahr
Dokumenttyp
Schlagworte
- Mechanochemistry (13)
- Polymorphism (6)
- Crystallization (5)
- SAXS (5)
- In situ (4)
- Synchrotron radiation (4)
- XRD (4)
- Cocrystal (3)
- Nanoparticle (3)
- Nifedipine (3)
Organisationseinheit der BAM
- 6 Materialchemie (3)
- 6.3 Strukturanalytik (3)
An unusually fast crystallization of the organic glass former nifedipine has been observed. The crystallization process, starting from an amorphous film to crystalline material, was investigated by time resolved Raman microspectroscopy. The crystallization rates of the initially crystallizing metastable β-form are four orders of magnitude higher than those of previous studies.
The formation mechanisms of silver nanoparticles using aqueous silver perchlorate solutions as precursors and sodium borohydride as reducing agent were investigated based on time-resolved in situ experiments. This contribution addresses two important issues in colloidal science: (i) differences and analogies between growth processes of different metals such as gold and silver and (ii) the influence of a steric stabilizing agent on the growth process. The results reveal that a growth due to coalescence is a fundamental growth principle if the monomer-supplying chemical reaction is faster than the actual particle formation.
In any given matrix control over the final particle size distribution requires a constitutive understanding of the mechanisms and kinetics of the particle evolution. In this contribution we report on the formation mechanism of silver nanoparticles embedded in a soda-lime silicate glass matrix. For the silver ion-exchanged glass it is shown that at temperatures below 410 °C only molecular clusters (diameter <1 nm) are forming which are most likely silver dimers. These clusters grow to nanoparticles (diameter >1 nm) by annealing above this threshold temperature of 410 °C. It is evidenced that the growth and thus the final silver nanoparticle size are determined by matrix-assisted reduction mechanisms. As a consequence, particle growth proceeds after the initial formation of stable clusters by addition of silver monomers which diffuse from the glass matrix. This is in contrast to the widely accepted concept of particle growth in metal–glass systems, in which it is assumed that the nanoparticle formation is predominantly governed by Ostwald ripening processes.
A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.
The cocrystal formation of pyrazinamide (PZA) with malonic acid (MA) was studied in situ. The mechanochemical reaction proceeds via conversion of a crystalline intermediate (PZA:MA II) into the thermodynamically more stable form (PZA:MA I) upon further grinding. The information derived from in situ powder X-ray diffraction (PXRD) enabled the isolation of this new metastable polymorph. On the basis of the PXRD data, the crystal structure of the 1:1 cocrystal PZA:MA II was solved. The polymorphs were further characterized and compared by Raman spectroscopy, solid-state NMR spectroscopy, differential thermal analysis/thermogravimetric analysis, and scanning electron microscopy. Our study demonstrates how monitoring mechanochemical reactions by in situ PXRD can direct the discovery and isolation of even short-lived intermediates not yet accessed by conventional methods.
We report on the formation of silver subsurface ion-exchanged metal oxide (silver SIMO) glasses and their surface-enhanced Raman scattering (SERS) activity. The samples were prepared by a combined thermal and chemical three-step methodology and characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), environmental electron scanning microscopy (ESEM), and UV/Vis spectroscopy. This unique method provides SERS substrates with protection against contamination and strong, reliable and reproducible SERS enhancement. The Raman enhancement factors of the long-term stable SIMO glasses were estimated to approximately 107.
The syntheses and crystal structures of two cerium(IV) phosphonates are presented. Cerium(IV) bis(phenylphosphonate) Ce(O3PC6H5)2 1 can be formed from precipitation and mechanochemical reaction, whereas cerium(IV) bis(carboxymethylphosphonate) monohydrate Ce(O3PCH2COOH)2 H2O 2 is only accessible via ball milling. All reactions proceed very fast and are completed within a short time span. In situ measurements for the syntheses of 1 show that the product occurs within seconds or a few minutes, respectively. The structures were solved from powder X-ray diffraction data.
The strategy of utilizing mechanochemical synthesis to obtain metal–organic frameworks (MOFs) with high surface areas is demonstrated for two model systems. The compounds HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) and MOF-14 (Cu3(BTB)2, BTB = 4,4',4''-benzenetribenzoate) were synthesized by ball milling and characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and thermal analysis (DTA/DTG/MS). The specific surface area (SSA) of both compounds was characterized by nitrogen adsorption. To verify these results and to understand how the synthetic conditions influence the pore structure and the surface area, additional small-angle X-ray scattering (SAXS) experiments were carried out. Our investigations confirm that this synthesis approach is a promising alternative method for distinct MOFs. This facile method leads to materials with surface areas of 1713 m²/g, which is comparable to the highest given values in the literature for the respective compounds.