N2 - Potentiometric sensors, such as polymeric membrane, ion-selective electrodes (ISEs), have been used in the past to monitor a variety of chemical processes. However, the use of these sensors has traditionally been limited to aqueous solutions and moderate temperatures. Here we present an ISE with a high-capacity ion-exchange sensing membrane for measurements of nitrate and nitrite in the organic solvent propylene glycol at 150°C. It is capable of continuously measuring under these conditions for over 180 h. We demonstrate the usefulness of this sensor by in situ monitoring of anion concentrations during the synthesis of copper and silver nanoparticles in propylene glycol using the polyol method. Ion chromatography and a colorimetric method were used to independently confirm anion concentrations measured in situ. In doing so, it was shown that in this reaction the co-ion nitrate is reduced to nitrite.
This paper discusses the relationship between synthesis conditions, crystal morphology, and theoretical modeling of copper and nickel nanoparticles prepared by a modified polyol process. The polyol serves as a solvent, a reducing agent, and a capping agent, and we investigate the role several polyol types play in the nucleation and growth of metallic nanoparticles. The nanoparticles are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Our results demonstrate that changing the solvent system from a short chain polyol (ethylene glycol) to a long chain polyol (tetraethylene glycol) greatly affects the resulting morphology of copper nanoparticles. These results suggest that the polyol is playing a major role as an in situ capping agent and that the various polyol chain lengths in-turn result in various particle morphologies by directly altering the nucleation and growth steps. We were also able to use theoretical modeling to investigate the mechanism for growth to better understand the intermediate structure stability. This work presents an alternative approach in investigating the polyol mechanism by using both theoretical and experimental results and opens new insight for the synthesis of metals and alloys by the polyol process.
30/12/2014 · J Am Oil Chem Soc (2015) 92:243–255
Highly monodisperse sodium citrate-coated spherical silver nanoparticles (Ag NPs) with controlled sizes ranging from 10 to 200 nm have been synthesized by following a kinetically controlled seeded-growth approach via the reduction of silver nitrate by the combination of two chemical reducing agents: sodium citrate and tannic acid. The use of traces of tannic acid is fundamental in the synthesis of silver seeds, with an unprecedented (nanometric resolution) narrow size distribution that becomes even narrower, by size focusing, during the growth process. The homogeneous growth of Ag seeds is kinetically controlled by adjusting reaction parameters: concentrations of reducing agents, temperature, silver precursor to seed ratio, and pH. This method produces long-term stable aqueous colloidal dispersions of Ag NPs with narrow size distributions, relatively high concentrations (up to 6 × 1012 NPs/mL), and, more important, readily accessible surfaces. This was proved by studying the catalytic properties of as-synthesized Ag NPs using the reduction of Rhodamine B (RhB) by sodium borohydride as a model reaction system. As a result, we show the ability of citrate-stabilized Ag NPs to act as very efficient catalysts for the degradation of RhB while the coating with a polyvinylpyrrolidone (PVP) layer dramatically decreased the reaction rate.
The mechanochemical method was proposed by Ao et al
A convergent total synthesis of (−)-nahuoic acid Ci(Bii) (3), a novel -decalin polyketide, has been achieved. Key synthetic transformations include Type II Anion Relay Chemistry (ARC) to construct the polyol chain, a Ti-catalyzed asymmetric Diels–Alder reaction to generate the -decalin skeleton, and a late-stage large fragment union exploiting a Micalizio alkoxide-directed alkyne–alkene coupling tactic.
, they synthesized ZnO with an average crystallite size of 21 nm
This article reports a robust method based upon polyol reduction for the deterministic synthesis of Pd decahedra or icosahedra with tunable sizes and a purity approaching 100%. The success of such a selective synthesis relies on an ability to fine-tune the reaction kinetics through the addition of Na 2SO4 and HCl for decahedra and icosahedra, respectively. In the absence of any additive, the product of a similar synthesis in diethylene glycol contained 10% decahedra and 90% icosahedra. By optimizing the amount of Na2SO4 (or HCl) added into the reaction solution, the percent of decahedra (or icosahedra) in the product could be increased up to 100%. The roles of Na2SO4 and HCl were also investigated in great detail, and two plausible mechanisms were proposed and validated through a set of experiments. In general, a faster reduction rate is needed for the synthesis of Pd decahedra when compared with what is needed for Pd icosahedra. This work not only offers a simple approach to the deterministic syntheses of Pd decahedra and icosahedra but also provides an in-depth understanding of the mechanisms involved in shape-controlled syntheses of noble-metal nanocrystals from the perspective of reaction kinetics. On the basis of the mechanistic understanding, we have also achieved successful synthesis of Pd decahedra as pure samples by adding a proper amount of NaOH into the system to speed up the reduction kinetics.