Nanoparticles of plasmonic materials can sustain oscillations of their free electron density, called localized surface plasmon resonances (LSPRs), giving them a broad range of potential applications. Mg is an earth-abundant plasmonic material attracting growing attention owing to its ability to sustain LSPRs across the ultraviolet, visible, and near-infrared wavelength range. Tuning the LSPR frequency of plasmonic nanoparticles requires precise control over their size and shape; for Mg, this control has previously been achieved using top-down fabrication or gas-phase methods, but these are slow and expensive. Here, we systematically probe the effects of reaction parameters on the nucleation and growth of Mg nanoparticles using a facile and inexpensive colloidal synthesis. Small NPs of 80 nm were synthesized using a low reaction time of 1 min and ∼100 nm NPs were synthesized by decreasing the overall reaction concentration, replacing the naphthalene electron carrier with biphenyl or using metal salt additives of FeCl 3 or NiCl 2 at longer reaction times of 17 h. Intermediate sizes up to 400 nm were further selected via the overall reaction concentration or using other metal salt additives with different reduction potentials. Significantly larger particles of over a micrometer were produced by reducing the reaction temperature and, thus, the nucleation rate. We showed that increasing the solvent coordination reduced Mg NP sizes, while scaling up the reaction reduced the mixing efficiency and produced larger NPs. Surprisingly, varying the relative amounts of Mg precursor and electron carrier had little impact on the final NP sizes. These results pave the way for the large-scale use of Mg as a low-cost and sustainable plasmonic material.
In this work, we present a novel microfluidic-based approach for investigating the thermodynamics of multicomponent systems at high pressures and temperatures, such as determining miscibility diagrams and critical coordinates of complex mixtures. The developed method is primarily based on (i) bubble and dew point detection through optical characterization and (ii) the use of a so-called dynamic stop-flow measurement mode for fast screening of the diagram parameters, mainly P, T and composition. Our strategy was validated through the studies of model binary CO2-alkane mixtures. The obtained results were then compared to PREOS-calculated and literature data. We later applied this strategy for determining ternary and quaternary mixtures critical coordinates. This approach has equal accuracy compared to conventional high-pressure optical cell methods but allows for a much faster phase diagram determination, taking advantage of improved heat and mass transfers on the microscale and of the dynamic stop-flow approach.
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