Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica

The controlled formation and stabilization of nanoparticles is of fundamental relevance for materials science and key to many modern technologies. Common synthetic strategies to arrest growth at small sizes and prevent undesired particle agglomeration often rely on the use of organic additives and r...

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Main Authors: Bastian Rödig, Diana Funkner, Thomas Frank, Ulrich Schürmann, Julian Rieder, Lorenz Kienle, Werner Kunz, Matthias Kellermeier
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Nanomaterials
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Online Access:https://www.mdpi.com/2079-4991/14/24/2054
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author Bastian Rödig
Diana Funkner
Thomas Frank
Ulrich Schürmann
Julian Rieder
Lorenz Kienle
Werner Kunz
Matthias Kellermeier
author_facet Bastian Rödig
Diana Funkner
Thomas Frank
Ulrich Schürmann
Julian Rieder
Lorenz Kienle
Werner Kunz
Matthias Kellermeier
author_sort Bastian Rödig
collection DOAJ
description The controlled formation and stabilization of nanoparticles is of fundamental relevance for materials science and key to many modern technologies. Common synthetic strategies to arrest growth at small sizes and prevent undesired particle agglomeration often rely on the use of organic additives and require non-aqueous media and/or high temperatures, all of which appear critical with respect to production costs, safety, and sustainability. In the present work, we demonstrate a simple one-pot process in water under ambient conditions that can produce particles of various transition metal carbonates and sulfides with sizes of only a few nanometers embedded in a silica shell, similar to particles derived from more elaborate synthesis routes, like the sol–gel process. To this end, solutions of soluble salts of metal cations (e.g., chlorides) and the respective anions (e.g., sodium carbonate or sulfide) are mixed in the presence of different amounts of sodium silicate at elevated pH levels. Upon mixing, metal carbonate/sulfide particles nucleate, and their subsequent growth causes a sensible decrease of pH in the vicinity. Dissolved silicate species respond to this local acidification by condensation reactions, which eventually lead to the formation of amorphous silica layers that encapsulate the metal carbonate/sulfide cores and, thus, effectively inhibit any further growth. The as-obtained carbonate nanodots can readily be converted into the corresponding metal oxides by secondary thermal treatment, during which their nanometric size is maintained. Although the described method clearly requires optimization towards actual applications, the results of this study highlight the potential of bottom-up self-assembly for the synthesis of functional nanoparticles at mild conditions.
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spelling doaj-art-4cf5def84f894ecbb6a6ad42a5b67ba52024-12-27T14:43:37ZengMDPI AGNanomaterials2079-49912024-12-011424205410.3390/nano14242054Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with SilicaBastian Rödig0Diana Funkner1Thomas Frank2Ulrich Schürmann3Julian Rieder4Lorenz Kienle5Werner Kunz6Matthias Kellermeier7Institute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, GermanyInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, GermanyInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, GermanyFaculty of Engineering, Kiel University, Kaiserstr. 2, D-24143 Kiel, GermanyInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, GermanyFaculty of Engineering, Kiel University, Kaiserstr. 2, D-24143 Kiel, GermanyInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, GermanyMaterial Science, BASF SE, RGA/BM–B007, Carl-Bosch-Str. 38, D-67056 Ludwigshafen, GermanyThe controlled formation and stabilization of nanoparticles is of fundamental relevance for materials science and key to many modern technologies. Common synthetic strategies to arrest growth at small sizes and prevent undesired particle agglomeration often rely on the use of organic additives and require non-aqueous media and/or high temperatures, all of which appear critical with respect to production costs, safety, and sustainability. In the present work, we demonstrate a simple one-pot process in water under ambient conditions that can produce particles of various transition metal carbonates and sulfides with sizes of only a few nanometers embedded in a silica shell, similar to particles derived from more elaborate synthesis routes, like the sol–gel process. To this end, solutions of soluble salts of metal cations (e.g., chlorides) and the respective anions (e.g., sodium carbonate or sulfide) are mixed in the presence of different amounts of sodium silicate at elevated pH levels. Upon mixing, metal carbonate/sulfide particles nucleate, and their subsequent growth causes a sensible decrease of pH in the vicinity. Dissolved silicate species respond to this local acidification by condensation reactions, which eventually lead to the formation of amorphous silica layers that encapsulate the metal carbonate/sulfide cores and, thus, effectively inhibit any further growth. The as-obtained carbonate nanodots can readily be converted into the corresponding metal oxides by secondary thermal treatment, during which their nanometric size is maintained. Although the described method clearly requires optimization towards actual applications, the results of this study highlight the potential of bottom-up self-assembly for the synthesis of functional nanoparticles at mild conditions.https://www.mdpi.com/2079-4991/14/24/2054nanodotstransition metal oxidestransition metal sulfidessilicaco-precipitationcore–shell particles
spellingShingle Bastian Rödig
Diana Funkner
Thomas Frank
Ulrich Schürmann
Julian Rieder
Lorenz Kienle
Werner Kunz
Matthias Kellermeier
Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
Nanomaterials
nanodots
transition metal oxides
transition metal sulfides
silica
co-precipitation
core–shell particles
title Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
title_full Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
title_fullStr Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
title_full_unstemmed Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
title_short Nanodots of Transition Metal Sulfides, Carbonates, and Oxides Obtained Through Spontaneous Co-Precipitation with Silica
title_sort nanodots of transition metal sulfides carbonates and oxides obtained through spontaneous co precipitation with silica
topic nanodots
transition metal oxides
transition metal sulfides
silica
co-precipitation
core–shell particles
url https://www.mdpi.com/2079-4991/14/24/2054
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