Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Selective cation exchange in the core region of Cu2-xSe/Cu2-xS core/shell nanocrystals.

ABSTRACT: We studied cation exchange (CE) in core/shell Cu2-xSe/Cu2-xS nanorods with two cations, Ag(+) and Hg(2+), which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2-xS shell and reached the Cu2-xSe core, replacing first Cu(+) ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions.

SUBMITTER: Miszta K

PROVIDER: S-EPMC4591528 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Selective cation exchange in the core region of Cu2-xSe/Cu2-xS core/shell nanocrystals.

Miszta Karol K Gariano Graziella G Brescia Rosaria R Marras Sergio S De Donato Francesco F Ghosh Sandeep S De Trizio Luca L Manna Liberato L

Journal of the American Chemical Society 20150918 38

We studied cation exchange (CE) in core/shell Cu2-xSe/Cu2-xS nanorods with two cations, Ag(+) and Hg(2+), which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2-xS shell and reached the Cu2-xSe core, replacing first Cu(+) ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in ...[more]

PMID: 26360611

Similar Datasets

Tailoring Cu+ for Ga3+ Cation Exchange in Cu2-xS and CuInS2 Nanocrystals by Controlling the Ga Precursor Chemistry.

Project description:Nanoscale cation exchange (CE) has resulted in colloidal nanomaterials that are unattainable by direct synthesis methods. Aliovalent CE is complex and synthetically challenging because the exchange of an unequal number of host and guest cations is required to maintain charge balance. An approach to control aliovalent CE reactions is the use of a single reactant to both supply the guest cation and extract the host cation. Here, we study the application of GaCl3-L complexes [L = trioctylphosphine (TOP), triphenylphosphite (TPP), diphenylphosphine (DPP)] as reactants in the exchange of Cu+ for Ga3+ in Cu2-xS nanocrystals. We find that noncomplexed GaCl3 etches the nanocrystals by S2- extraction, whereas GaCl3-TOP is unreactive. Successful exchange of Cu+ for Ga3+ is only possible when GaCl3 is complexed with either TPP or DPP. This is attributed to the pivotal role of the Cu2-xS-GaCl3-L activated complex that forms at the surface of the nanocrystal at the onset of the CE reaction, which must be such that simultaneous Ga3+ insertion and Cu+ extraction can occur. This requisite is only met if GaCl3 is bound to a phosphine ligand, with a moderate bond strength, to allow facile dissociation of the complex at the nanocrystal surface. The general validity of this mechanism is demonstrated by using GaCl3-DPP to convert CuInS2 into (Cu,Ga,In)S2 nanocrystals, which increases the photoluminescence quantum yield 10-fold, while blue-shifting the photoluminescence into the NIR biological window. This highlights the general applicability of the mechanistic insights provided by our work.

| S-EPMC6890264 | biostudies-literature

Galvanic Exchange in Colloidal Metal/Metal-Oxide Core/Shell Nanocrystals.

Project description:While galvanic exchange is commonly applied to metallic nanoparticles, recently its applicability was expanded to metal-oxides. Here the galvanic exchange is studied in metal/metal-oxide core/shell nanocrystals. In particular Sn/SnO2 is treated by Ag(+), Pt(2+), Pt(4+), and Pd(2+). The conversion dynamics is monitored by in situ synchrotron X-ray diffraction. The Ag(+) treatment converts the Sn cores to the intermetallic Ag x Sn (x ? 4) phase, by changing the core's crystal structure. For the analogous treatment by Pt(2+), Pt(4+), and Pd(2+), such a galvanic exchange is not observed. This different behavior is caused by the semipermeability of the naturally formed SnO2 shell, which allows diffusion of Ag(+) but protects the nanocrystal cores from oxidation by Pt and Pd ions.

| S-EPMC5018861 | biostudies-literature

Nano-engineered electron-hole exchange interaction controls exciton dynamics in core-shell semiconductor nanocrystals.

Project description:A strong electron-hole exchange interaction (EI) in semiconductor nanocrystals (NCs) gives rise to a large (up to tens of meV) splitting between optically active ('bright') and optically passive ('dark') excitons. This dark-bright splitting has a significant effect on the optical properties of band-edge excitons and leads to a pronounced temperature and magnetic field dependence of radiative decay. Here we demonstrate a nanoengineering-based approach that provides control over EI while maintaining nearly constant emission energy. We show that the dark-bright splitting can be widely tuned by controlling the electron-hole spatial overlap in core-shell CdSe/CdS NCs with a variable shell width. In thick-shell samples, the EI energy reduces to <250 ?eV, which yields a material that emits with a nearly constant rate over temperatures from 1.5 to 300 K and magnetic fields up to 7 T. The EI-manipulation strategies demonstrated here are general and can be applied to other nanostructures with variable electron-hole overlap.

| S-EPMC3127490 | biostudies-literature

Near-Infrared Emitting CuInSe?/CuInS? Dot Core/Rod Shell Heteronanorods by Sequential Cation Exchange.

Project description:The direct synthesis of heteronanocrystals (HNCs) combining different ternary semiconductors is challenging and has not yet been successful. Here, we report a sequential topotactic cation exchange (CE) pathway that yields CuInSe2/CuInS2 dot core/rod shell nanorods with near-infrared luminescence. In our approach, the Cu(+) extraction rate is coupled to the In(3+) incorporation rate by the use of a stoichiometric trioctylphosphine-InCl3 complex, which fulfills the roles of both In-source and Cu-extracting agent. In this way, Cu(+) ions can be extracted by trioctylphosphine ligands only when the In-P bond is broken. This results in readily available In(3+) ions at the same surface site from which the Cu(+) is extracted, making the process a direct place exchange reaction and shifting the overall energy balance in favor of the CE. Consequently, controlled cation exchange can occur even in large and anisotropic heterostructured nanocrystals with preservation of the size, shape, and heterostructuring of the template NCs into the product NCs. The cation exchange is self-limited, stopping when the ternary core/shell CuInSe2/CuInS2 composition is reached. The method is very versatile, successfully yielding a variety of luminescent CuInX2 (X = S, Se, and Te) quantum dots, nanorods, and HNCs, by using Cd-chalcogenide NCs and HNCs as templates. The approach reported here thus opens up routes toward materials with unprecedented properties, which would otherwise remain inaccessible.

| S-EPMC4660388 | biostudies-literature

Core-shell Fe3O4@zeolite NaA as an Adsorbent for Cu2.

Project description:Here, using Fe3O4@SiO2 as a precursor, a novel core-shell structure magnetic Cu2+ adsorbent (Fe3O4@zeolite NaA) was successfully prepared. Several methods, namely X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), Transmission electron microscope (TEM), Brunauer Emmett Teller (BET) and vibrating sample magnetometry (VSM) were used to characterize the adsorbent. A batch experiment was conducted to study the Cu2+ adsorption capacity of Fe3O4@zeolite NaA at different pH values, contact time, initial Cu2+ concentration and adsorbent does. It is found that the saturated adsorption capacity of Fe3O4@zeolite NaA on Cu2+ is 86.54 mg/g. The adsorption isotherm analysis shows that the adsorption process of Fe3O4@zeolite NaA to Cu2+ is more consistent with the Langmuir model, suggesting that it is a monolayer adsorption. Adsorption kinetics study found that the adsorption process of Fe3O4@zeolite NaA to Cu2+ follows the pseudo-second kinetics model, which means that the combination of Fe3O4@zeolite NaA and Cu2+ is the chemical chelating reaction. Thermodynamic analysis shows that the adsorption process of Fe3O4@zeolite NaA to Cu2+ is endothermic, with increasing entropy and spontaneous in nature. The above results show that Fe3O4@zeolite NaA is a promising Cu2+ adsorbent.

| S-EPMC7665120 | biostudies-literature

Hydrothermal Cation Exchange Enabled Gradual Evolution of Au@ZnS-AgAuS Yolk-Shell Nanocrystals and Their Visible Light Photocatalytic Applications.

Project description:Yolk-shell hybrid nanoparticles with noble metal core and programmed semiconductor shell composition may exhibit synergistic effects and tunable catalytic properties. In this work, the hydrothermal cation exchange synthesis of Au@ZnS-AgAuS yolk-shell nanocrystals (Y-S NCs) with well-fabricated void size, grain-boundary-architectured ZnS-AgAuS shell and in situ generated Au cocatalyst are demonstrated. Starting from the novel cavity-free Au@AgAuS core-shell NCs, via aqueous cation exchange reaction with Zn2+, the gradual evolution with produced Au@ZnS-AgAuS Y-S NCs can be achieved successfully. This unprecedented evolution can be reasonably explained by cation exchange initialized chemical etching of Au core, followed by the diffusion through the shell to be AgAuS and then ZnS. By hydrothermal treatment provided optimal redox environment, Au ions in shell were partially reduced to be Au NCs on the surface. The UV-vis absorption spectra evolution and visible light photocatalytic performances, including improved photodegradation behavior and photocatalytic hydrogen evolution activity, have demonstrated their potential applications. This new one-pot way to get diverse heterointerfaces for better photoinduced electron/hole separation synergistically can be anticipated for more kinds of photocatalytic organic synthesis.

| S-EPMC5770678 | biostudies-literature

Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

Project description:We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature.

| S-EPMC4521286 | biostudies-literature

Sn cation valency dependence in cation exchange reactions involving Cu(2-x)Se nanocrystals.

Project description:We studied cation exchange reactions in colloidal Cu(2-x)Se nanocrystals (NCs) involving the replacement of Cu(+) cations with either Sn(2+) or Sn(4+) cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu(2-x)Se NCs remains cubic regardless of the degree of copper deficiency (that is, "x") in the NC lattice. Also, Sn(4+) ions are comparable in size to the Cu(+) ions, while Sn(2+) ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn(4+) cations are used, alloyed Cu(2-4y)Sn(y)Se NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu(+) cations with Sn(4+) cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn(2+) cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu(2-x)Se/SnSe heterostructures, with no Cu-Sn-Se alloys.

| S-EPMC4244862 | biostudies-literature

Metastable CdTe@HgTe Core@Shell Nanostructures Obtained by Partial Cation Exchange Evolve into Sintered CdTe Films Upon Annealing.

Project description:Partial Hg2+ → Cd2+ cation exchange (CE) reactions were exploited to transform colloidal CdTe nanocrystals (NCs, 4-6 nm in size) into CdTe@HgTe core@shell nanostructures. This was achieved by working under a slow CE rate, which limited the exchange to the surface of the CdTe NCs. In such nanostructures, when annealed at mild temperatures (as low as 200 °C), the HgTe shell sublimated or melted and the NCs sintered together, with the concomitant desorption of their surface ligands. At the end of this process, the annealed samples consisted of ligand-free CdTe sintered films containing an amount of Hg2+ that was much lower than that of the starting CdTe@HgTe NCs. For example, the CdTe@HgTe NCs that initially contained 10% of Hg2+, after being annealed at 200 °C were transformed to CdTe sintered films containing only traces of Hg2+ (less than 1%). This procedure was then used to fabricate a proof-of-concept CdTe-based photodetector exhibiting a photoresponse of up to 0.5 A/W and a detectivity of ca. 9 × 104 Jones under blue light illumination. Our strategy suggests that CE protocols might be exploited to lower the overall costs of production of CdTe thin films employed in photovoltaic technology, which are currently fabricated at high temperatures (above 350 °C), using post-process ligand-stripping steps.

| S-EPMC8016170 | biostudies-literature

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water.

Project description:Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

| S-EPMC5059460 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data