Organic-to-Aqueous Phase Transfer of Alloyed AgInS2-ZnS Nanocrystals Using Simple Hydrophilic Ligands: Comparison of 11-Mercaptoundecanoic Acid, Dihydrolipoic Acid and Cysteine

Kowalik, Patrycja; Bujak, Piotr; Penkala, Mateusz; Proń, A.

doi:10.3390/nano11040843

Cited by 7 publications

(10 citation statements)

References 40 publications

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“…On the contrary, A-4 nanocrystals were enriched in Zn since precursors in the molar ratio Zn/Ag = 9.0 yielded nanocrystals of Zn/Ag = 12.4. Additional points in the plot B-1 ( Ag 1.0 In 2.8 Zn 1.3 S 4.0 (S 6.0 ) ) and B-2 ( Ag 1.0 In 1.5 Zn 7.8 S 17.0 (S 10.5 ) ) represent nanocrystals obtained with InCl 3 as a precursor, which were reported in ref . Elemental analyses of nanocrystals obtained with two different indium precursors (InCl 2 vs InCl 3 ) indicated distinct differences in their reactivities in the reaction medium.…”

Section: Resultssupporting

confidence: 54%

“…Comparison of nanocrystals prepared using the InCl 2 precursor with those synthesized applying InCl 3 in identical conditions, i.e ., B-1 in the same conditions as A-1 and B-2 in the same conditions as A-4 , clearly showed that the dissimilarity of their spectroscopic properties originated from significant differences in their chemical compositions caused by the use of indium precursors of different reactivities. B-1 ( Ag 1.0 In 2.8 Zn 1.3 S 4.0 (S 6.0 ) ) and B-2 ( Ag 1.0 In 1.5 Zn 7.8 S 17.0 (S 10.5 ) ) emitted red (720 nm) and green (543 nm) light, respectively, consistent with their different Zn/Ag ratios . It should be noted that A-4 and B-2 exhibit similar emission spectra with maxima at 528 and 542 nm, respectively, despite different shapes and sizes.…”

Section: Resultsmentioning

confidence: 74%

“…B-1 (Ag 1.0 In 2.8 Zn 1.3 S 4.0 (S 6.0 )) and B-2 (Ag 1.0 In 1.5 Zn 7.8 S 17.0 (S 10.5 )) emitted red (720 nm) and green (543 nm) light, respectively, consistent with their different Zn/Ag ratios. 54 It should be noted that A-4 and B-2 exhibit similar emission spectra with maxima at 528 and 542 nm, respectively, despite different shapes and sizes. In the case of ternary or quaternary nanocrystals of sizes inferior to their exciton Bohr radii, the luminescence band position is a complex product of their composition and the quantum confinement phenomenon.…”

Section: ■ Results and Discussionmentioning

confidence: 93%

“…Molar ratio of zinc stearate to AgNO 3 in the reaction mixture vs Zn/Ag ratio in the resulting AgInS 2 –ZnS nanocrystals (molar ratio of indium precursor to AgNO 3 = 3.0). Circles: this research (InCl 2 ) A-(1–4) , squares: experimental data (InCl 3 ) B-1 and B-2 from ref . The insets show photographs of UV-illuminated (365 nm) nanocrystals dispersed in toluene solutions.…”

Section: Resultsmentioning

confidence: 99%

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Indium(II) Chloride as a Precursor in the Synthesis of Ternary (Ag–In–S) and Quaternary (Ag–In–Zn–S) Nanocrystals

et al. 2022

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A new indium precursor, namely, indium(II) chloride, was tested as a precursor in the synthesis of ternary Ag−In−S and quaternary Ag−In−Zn−S nanocrystals. This new precursor, being in fact a dimer of Cl 2 In−InCl 2 chemical structure, is significantly more reactive than InCl 3 , typically used in the preparation of these types of nanocrystals. This was evidenced by carrying out comparative syntheses under the same reaction conditions using these two indium precursors in combination with the same silver (AgNO 3 ) and zinc (zinc stearate) precursors. In particular, the use of indium(II) chloride in combination with low concentrations of the zinc precursor yielded spherical-shaped (D = 3.7−6.2 nm) Ag−In−Zn−S nanocrystals, whereas for higher concentrations of this precursor, rodlike nanoparticles (L = 9−10 nm) were obtained. In all cases, the resulting nanocrystals were enriched in indium (In/Ag = 1.5−10.3). Enhanced indium precursor conversion and formation of anisotropic, longitudinal nanoparticles were closely related to the presence of thiocarboxylic acid type of ligands in the reaction mixture. These ligands were generated in situ and subsequently bound to surfacial In(III) cations in the growing nanocrystals. The use of the new precursor of enhanced reactivity facilitated precise tuning of the photoluminescence color of the resulting nanocrystals in the spectral range from ca. 730 to 530 nm with photoluminescence quantum yield (PLQY) varying from 20 to 40%. The fabricated Ag−In−S and Ag−In−Zn−S nanocrystals exhibited the longest, reported to date, photoluminescence lifetimes of ∼9.4 and ∼1.4 μs, respectively. It was also demonstrated for the first time that ternary (Ag−In− S) and quaternary (Ag−In−Zn−S) nanocrystals could be applied as efficient photocatalysts, active under visible light (green) illumination, in the reaction of aldehydes reduction to alcohols.

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Section: Resultssupporting

confidence: 54%

Section: Resultsmentioning

confidence: 74%

Section: ■ Results and Discussionmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Indium(II) Chloride as a Precursor in the Synthesis of Ternary (Ag–In–S) and Quaternary (Ag–In–Zn–S) Nanocrystals

et al. 2022

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“…Also, Z-type ligands such as metal halides like ZnCl 2 can effectively passivate dangling bonds on AgIn x Ga 1– x S 2 QDs, leading to a 3-fold increase of PL QY . Recently, also the organic-to-aqueous phase transfer of ZAIS QDs was assessed by NMR spectroscopy for the hydrophilic ligands 11-mercaptoundecanoic acid, DHLA, and cysteine, and the efficiency of the ligand exchange and its influence on the PL QY were determined . Other studies of ligand exchange procedures for ternary or quaternary QDs focus on the impact of this exchange on QD performance in applications such as hydrogen production, optoelectronic devices, ,, and bioimaging. ,,− However, life sciences application-dedicated studies of the effect of biocompatible surface ligands are still scarce, especially the systematic exploration of the influence of ligand denticity on the colloidal stability and optoelectronic properties of ternary and quaternary QDs.…”

Section: Introductionmentioning

confidence: 99%

Influence of Hydrophilic Thiol Ligands of Varying Denticity on the Luminescence Properties and Colloidal Stability of Quaternary Semiconductor Nanocrystals

et al. 2022

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Binary photoluminescent semiconductor nanocrystals (quantum dots, QDs) are one of the best studied fluorescent nanomaterials, and their unique optoelectronic properties paved the road to many applications in (bio)nanophotonics, optoelectronics, and photovoltaics. However, concerns related to their toxic constituents like cadmium or lead and the emerging interest in greener chemistry synthesis approaches hamper their future applicability. Interesting alternatives for some applications like biosensing or bioimaging are heavy-metal-free ternary QDs like AgInS2 (AIS), CuInS2 (CIS), and quaternary QDs such as AIS-ZnS (ZAIS). In this context, we explored the effect of ligand denticity on the organic-to-aqueous phase transfer of oleylamine-stabilized ZAIS QDs with the hydrophilic ligands mercaptopropionic acid (MPA), dihydrolipoic acid (DHLA), and 3-mercapto-2,2-bis(mercaptomethyl)propanoic acid (3MPA), bearing mono-, bi-, and trialkyl thiol groups. Spectroscopic studies of the resulting water-dispersible ZAIS QDs revealed a considerable influence of ligand denticity and ligand-to-QD ratio on the spectral position and width (FWHM; full width at half-maximum) of the photoluminescence (PL) bands, the PL quantum yields (PL QY), and the PL decay kinetics. Thiol capping and phase transfer resulted in a loss in PL by at least a factor of 2. The ligand-induced PL quenching observed particularly for ligands bearing two or three thiol groups was attributed to the facilitated formation of surface-bound disulfides. The best colloidal stability under high dilution conditions was observed for 3MPA.

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Enhancement of the alloyed CdZnSeS/ZnS quantum dots photoluminescence by thiol ligands capping

Drozd,

Strokin,

Kornilov

et al. 2024

Chemical Engineering Journal

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Organic-to-Aqueous Phase Transfer of Alloyed AgInS2-ZnS Nanocrystals Using Simple Hydrophilic Ligands: Comparison of 11-Mercaptoundecanoic Acid, Dihydrolipoic Acid and Cysteine

Cited by 7 publications

References 40 publications

Indium(II) Chloride as a Precursor in the Synthesis of Ternary (Ag–In–S) and Quaternary (Ag–In–Zn–S) Nanocrystals

Indium(II) Chloride as a Precursor in the Synthesis of Ternary (Ag–In–S) and Quaternary (Ag–In–Zn–S) Nanocrystals

Influence of Hydrophilic Thiol Ligands of Varying Denticity on the Luminescence Properties and Colloidal Stability of Quaternary Semiconductor Nanocrystals

Enhancement of the alloyed CdZnSeS/ZnS quantum dots photoluminescence by thiol ligands capping

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