Colloidal Synthesis of Cu–M–S (M = V, Cr, Mn) Nanocrystals by Tuning the Copper Precursor Reactivity

Mantella, Valeria; Varandili, Seyedeh Behnaz; Pankhurst, James R.; Buonsanti, Raffaella

doi:10.1021/acs.chemmater.0c03788

Cited by 19 publications

(19 citation statements)

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“…More recently, we extended this approach to CuCrS 2 and Cu 2 MnS 2 . Taking CuCrS 2 as an example, Cu x S ( x = 1, 2) and Cr y S z ( y = 2, 3 and z = 3, 4) were isolated as the reaction intermediates when CuI and chromium acetylacetonate (Cr(acac) 3 ) were used as the Cu and Cr precursors, respectively (Figure ).…”

Section: In-situ Forming Nanocrystals As Reaction Intermediates In Co...mentioning

confidence: 99%

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Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Polyelemental compounds with dimensions in the nanosized regime are desirable in a large variety of applications, yet their synthesis remains a general challenge in chemistry. One of the major bottlenecks to obtaining multinary systems is the complexity of the synthesis itself. As the number of elements to include in one single nano-object increases, different chemical interactions arise during nucleation and growth, thus challenging the formation of the targeted product. Choosing the reaction conditions and identifying the parameters which ensure the desired reaction pathway are of the uttermost importance. When, in addition to composition, the simultaneous control of size and shape is sought after, the development of new synthetic strategies guided by the fundamental understanding of the formation mechanisms becomes crucial.In this Account we discuss the use of colloidal chemistry to target multinary oxide nanomaterials, with focus on light absorbers which can drive chemical reactions. We propose the combination of soft and solid-state chemistries as one successful strategy to target this family of polyelemental compounds with control on composition and morphological features. To start with, we highlight studies where in situ forming nanoparticles act as reaction intermediates, which we found in both oxide (i.e., Bi−V−O) and sulfide (Cu−M−S, with M = V, Cr, Mn) nanocrystals (NCs). Examples of ternary sulfides are mentioned only with the purpose of showing that similar mechanisms can apply to different families of multinary nanomaterials. Using this new knowledge, we demonstrate that reacting pre-synthesized NCs with well-defined composition and size with molecular precursors allows significant control of these same property-dictating features (i.e., composition and grain size) in the resulting ternary and quaternary compounds. For example, nanostructured BiV 1−x Sb x O 4 thin films with tunable composition and nanostructured β-Cu 2 V 2 O 7 with tunable grain size were accessed from colloidally synthesized Bi 1−x Sb x NCs (0 < x < 1) and sizecontrolled Cu NCs reacted with a vanadium molecular precursor, respectively. The analysis of reaction aliquots revealed that the formation of these materials occurs via a solid-state reaction between the NC precursors and V-containing amorphous nanoparticles, which form in situ from the molecular precursors. With the aim to achieve better control on the reaction product, we finally propose the use of colloidally synthesized NCs as reactants in solid state reactions. As the first proof of concept, ternary metal oxide NCs, including CuFe 2 O 4 , CuMn 2 O 4 , and CuGa 2 O 4 with defined size and shape regulated by the NC precursors were obtained.Considering the huge library of single component and binary NCs accessible by colloidal chemistry, the extension of this synthetic concept, which combines soft and solid-state chemistries, to a larger variety of polyelemental nanomaterials is foreseen. Such an approach will contribute to...

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Section: In-situ Forming Nanocrystals As Reaction Intermediates In Co...mentioning

confidence: 99%

“…(B) HAADF-STEM image elemental mapping performed on the aliquot extracted after 3 min of reaction between CuI and Cr(acac) 3 . Additional details on the mechanistic studies are reported in ref . The scale bars are 20 nm.…”

Section: In-situ Forming Nanocrystals As Reaction Intermediates In Co...mentioning

confidence: 99%

Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

2021

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“…[6,9,[22][23][24][25] Commonly, the micro and nanostructured Cu-based materials with controlled particle size, chemical composition, and surface morphology are synthesized by solid-state or solution-based techniques. [26][27][28] Most of these methods involve organic surfactants as structure-directing agents which can modify, even mask, the surface chemistry of the micro and nanostructures. Moreover, electrodes of these materials can be fabricated by deposition onto suitable support in the presence of polymeric binders (e.g., Nafion or polytetrafluoroethylene).…”

Section: Introductionmentioning

confidence: 99%

In‐Liquid Plasma for Surface Engineering of Cu Electrodes with Incorporated SiO₂ Nanoparticles: From Micro to Nano

Menezes

Elnagar

Al-Shakran

et al. 2021

Adv Funct Materials

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A robust and efficient route to modify the chemical and physical properties of polycrystalline copper (Cu) wires via versatile plasma electrolysis is presented. Silica (SiO 2 ) nanoparticles (11 nm) are introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these SiO 2 nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral-like microstructures are observed by scanning electron microscopy on the Cu surface after the in-liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of CuO as a thin outer layer and a significant amount of inner Cu 2 O. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral-like microstructures by a simple electrochemical treatment.

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“…For this purpose, micro and nanostructured Cu catalysts are of special consideration owing to their superior selectivity and performance for several electrocatalytic reactions [6,9,[22][23][24] . Commonly, the micro and nanostructured Cu-based materials with controlled particle size, chemical composition, and surface morphology are synthesized by solid-state or solution-based techniques [25][26][27] . Most of these methods involve organic surfactants as structure-directing agents which can modify, even mask, the surface chemistry of the micro and nanostructures.…”

Section: Introductionmentioning

confidence: 99%

In-liquid plasma for surface engineering of Cu electrodes with incorporated SiO2 nanoparticles: From micro to nano

Menezes

Elnagar

Al-Shakran

et al. 2021

Preprint

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A robust and efficient route to modify the chemical and physical properties of polycrystalline Cu wires via versatile plasma electrolysis is presented. Silica nanoparticles (11 nm) have been introduced during the electrolysis to tailor the surface structure of the Cu electrode. The influence of these silica nanoparticles on the structure of the Cu electrodes during plasma electrolysis over a wide array of applied voltages and processing time is investigated systematically. Homogeneously distributed 3D coral-like microstructures are observed by scanning electron microscopy on the Cu surface after the in-liquid plasma treatment. These 3D microstructures grow with increasing plasma processing time. Interestingly, the microstructured copper electrode is composed of Cu(II) oxide as a thin outer shell and a significant amount of inner Cu(I) oxide. Furthermore, the oxide film thickness (between 1 and 70 µm), the surface morphology, and the chemical composition can be tuned by controlling the plasma parameters. Remarkably, the fabricated microstructures can be transformed to nanospheres assembled in coral-like microstructures by a simple electrochemical treatment.

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Colloidal Synthesis of Cu–M–S (M = V, Cr, Mn) Nanocrystals by Tuning the Copper Precursor Reactivity

Cited by 19 publications

References 28 publications

Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

In‐Liquid Plasma for Surface Engineering of Cu Electrodes with Incorporated SiO₂ Nanoparticles: From Micro to Nano

In-liquid plasma for surface engineering of Cu electrodes with incorporated SiO2 nanoparticles: From micro to nano

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Colloidal Synthesis of Cu–M–S (M = V, Cr, Mn) Nanocrystals by Tuning the Copper Precursor Reactivity

Cited by 19 publications

References 28 publications

Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

Colloidal Nanocrystals as Precursors and Intermediates in Solid State Reactions for Multinary Oxide Nanomaterials

In‐Liquid Plasma for Surface Engineering of Cu Electrodes with Incorporated SiO2 Nanoparticles: From Micro to Nano

In-liquid plasma for surface engineering of Cu electrodes with incorporated SiO2 nanoparticles: From micro to nano

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In‐Liquid Plasma for Surface Engineering of Cu Electrodes with Incorporated SiO₂ Nanoparticles: From Micro to Nano