Kinetics and Mechanism of Metal Nanoparticle Growth via Optical Extinction Spectroscopy and Computational Modeling: The Curious Case of Colloidal Gold
An overarching computational framework unifying several optical theories to describe the temporal volution of gold nanoparticles (GNPs) during a seeded growth process is presented. To achieve this, we sed the inexpensive and widely available optical extinction spectroscopy, to obtain quantitative kinetic data. In situ spectra collected over a wide set of experimental conditions were regressed using the hysical model, calculating light extinction by ensembles of GNPs during the growth process. This model rovides temporal information on the size, shape, and concentration of the particles, and any electromagnetic interactions between them. Consequently, we were able to describe the mechanism of GNP growth and divide the process into distinct genesis periods. We provide explanations for several longstanding mysteries, e.g., the phenomena responsible for the purple-greyish hue during the early stages of GNP growth, the complex interactions between nucleation, growth and aggregation events, and a clear distinction between agglomeration and electromagnetic interactions. The presented theoretical formalism has been developed in a generic fashion so that it can readily be adapted to other nanoparticulate formation scenarios such as the genesis of various metal nanoparticles.
Forschende des PSI haben einen neuen Katalysator für die Reinigung von Abgasen aus Erdgasmotoren entwickelt. Er ist auch bei niedrigen Temperaturen sehr aktiv und bleibt es über lange Zeit. So lässt sich Erdgas sauberer und klimaschonender verbrennen. Erd- und Biogas werden dadurch noch attraktiver als Ersatz für Erdölprodukte – zum Beispiel als Treibstoff für Autos.
Supported gold as catalyst for the decomposition of ammonia precursors in the selective catalytic reduction of NOx
Titaniumdioxide supported gold was found to catalyze the hydrolysis of formate-based ammonia precursor compounds which are proposed for the selective catalytic reduction of nitrogen oxides (NOx) in combustion exhaust gas. In contrast to other noble metals, the supported gold does not oxidize the released NH3, while it maintains decomposition of intermediate formic acid.
Gold particles supported on carbon when subjected to a flow of methyl iodide or bromide redisperse from large ensembles to single atoms and/or dimers of gold. Methyl halide oxidizes gold leading to gradual particle dissolution. The process could be carried out at temperatures as low as 50 °C. The excess of halide could be removed by a post-treatment of the material with 1%H2O/H2, which does not influence the metal dispersion. This remarkable transformation opens the possibility of re-activating gold catalysts that lost their performance due to metal particles sintering.
The hydrolysis of isocyanic acid was studied experimentally and theoretically and a reaction mechanism on different catalysts was established. The decreasing NOx emission limits for diesel vehicles impel the further development of the existing NOx deactivation technologies, particularly the selective catalytic reduction (SCR) of nitrogen oxides with urea. In the urea-SCR process, urea is injected into the hot exhaust gas, where it thermally decomposes into isocyanic acid (HNCO) and ammonia.