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. 2022 Jan 25;34(2):809-825.
doi: 10.1021/acs.chemmater.1c03800. Epub 2022 Jan 3.

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

Patrycja Kowalik  1   2 , Piotr Bujak  1 , Mateusz Penkala  3 , Anna M Maroń  3 , Andrzej Ostrowski  1 , Angelika Kmita  4 , Marta Gajewska  4 , Wojciech Lisowski  5 , Janusz W Sobczak  5 , Adam Pron  1
Affiliations

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

Patrycja Kowalik et al. Chem Mater. .

Abstract

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 Cl2In-InCl2 chemical structure, is significantly more reactive than InCl3, 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 (AgNO3) 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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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Mechanism of Indium(II) Chloride Disproportionation
Figure 1
Figure 1
(a) X-ray diffraction (XRD) patterns of Ag1.0In1.4S2.5(S2.6) (AIS) nanocrystals; (b) HR-TEM image and selected area electron diffraction (SAED) patterns of Ag1.0In1.4S2.5(S2.6) (AIS); and (c) TEM image and the corresponding histogram of Ag1.0In1.4S2.5(S2.6) (AIS) nanocrystals.
Figure 2
Figure 2
Molar ratio of zinc stearate to AgNO3 in the reaction mixture vs Zn/Ag ratio in the resulting AgInS2–ZnS nanocrystals (molar ratio of indium precursor to AgNO3 = 3.0). Circles: this research (InCl2) A-(1–4), squares: experimental data (InCl3) B-1 and B-2 from ref (54). The insets show photographs of UV-illuminated (365 nm) nanocrystals dispersed in toluene solutions.
Figure 3
Figure 3
X-ray powder diffractograms of Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1), Ag1.0In1.5Zn1.9S3.6(S4.6) (A-2), Ag1.0In1.5Zn4.4S6.8(S7.1) (A-3), and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) nanocrystals (a), HR-TEM (b, d), and TEM (c, e) images of Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1) and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) alloyed nanocrystals and their corresponding histograms.
Figure 4
Figure 4
Absorbance, photoluminescence excitation, and emission spectra of toluene dispersion of Ag1.0In1.4S2.5(S2.6) (AIS) (a) and alloyed Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1) (b), Ag1.0In1.5Zn1.9S3.6(S4.6) (A-2) (c), Ag1.0In1.5Zn4.4S6.8(S7.1) (A-3) (d), and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) (e) nanocrystals. For comparison, the emission spectra (dot lines) of toluene dispersions of Ag1.0In2.8Zn1.3S4.0(S6.0) (B-1) and Ag1.0In1.5Zn7.8S17.0(S10.5) (B-2) alloyed nanocrystals are presented.
Figure 5
Figure 5
Photoluminescence decay curves of Ag1.0In1.4S2.5(S2.6) (AIS) (a) and alloyed Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1) (a, c) and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) (c) nanocrystals and the corresponding bi (AIS and A4) and three (A-1)-exponential fitting curves. Schematic of the relaxation dynamics proposed for AIS, A-1, and A-4 nanocrystals (b).
Figure 6
Figure 6
In 3d (a) and Cl 2p (b) high-resolution XPS spectra in the surface region of indium(II) chloride and Ag1.0In1.4S2.5(S2.6) (AIS) nanocrystals. Binding energy of the reference substances: InCl3, InCl, and In2O3 are also shown.
Figure 7
Figure 7
Comparison of the valence bands XPS spectra of Ag1.0In1.4S2.5(S2.6) (AIS), Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1), and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) nanocrystals.
Figure 8
Figure 8
(a) 1H NMR spectra of the organic residue from Ag1.0In1.4S2.5(S2.6) (AIS), Ag1.0In1.5Zn0.3S3.3(S3.0) (A-1), and Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) nanocrystals, 1-octadecene (ODE), stearic acid (SA), 1-dodecanethiol (DDT), and oleylamine (OLA) recorded in C6D6, (b) 1H–1H COSY NMR spectrum of the organic residue (in C6D6) from Ag1.0In10.3Zn12.4S11.8(S28.3) (A-4) nanocrystals.
Scheme 2
Scheme 2. Proposed Reaction Pathways in the Reaction Mixtures Used for the Preparation of Ag–In–S and Ag–In–Zn–S Nanocrystals
Figure 9
Figure 9
(a) Setup for investigation of photocatalytic reactions under 10 W green LED (λ = 528 nm) irradiation, (b) photocatalytic reduction of aldehydes to alcohols, (c) 1H NMR spectra of the photocatalytic reduction reaction mixture used for photocatalytic reduction of 4-chlorobenzaldehyde or 4-methoxybenzaldehyde with AIS (Ag1.0In1.4S2.5(S2.0)) or A-1 (Ag1.0In1.5Zn0.3S3.3(S3.0)) nanocrystals as photocatalysts (in C6D6). All four processes were carried out under the same conditions.
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References

    1. Derfus A. M.; Chan W. C. W.; Bhatia S. N. Probing the Cytotoxicity of Semiconductor Quantum Dots. Nano Lett. 2004, 4, 11–18. 10.1021/nl0347334. - DOI - PMC - PubMed
    1. Kirchner C.; Liedl T.; Kudera S.; Pellegrino T.; Javier A. M.; Gaub H. E.; Stölzle S.; Fertig N.; Parak W. J. Cytotoxicity of Colloidal CdSe and CdSe/ZnS Nanoparticles. Nano Lett. 2005, 5, 331–338. 10.1021/nl047996m. - DOI - PubMed
    1. Ye L.; Yong K.-T.; Liu L.; Roy I.; Hu R.; Zhu J.; Cai H.; Law W.-C.; Liu J.; Wang K.; Liu J.; Liu Y.; Hu Y.; Zhang X.; Swihart M. T.; Prasad P. N. A Pilot Study in Non-Human Primates Shows No Adverse Response to Interavenous Injection of Quantum Dots. Nat. Nanotechnol. 2012, 7, 453–458. 10.1038/nnano.2012.74. - DOI - PubMed
    1. Reiss P.; Carrière M.; Lincheneau C.; Vaure L.; Tamang S. Synthesis of Semiconductor Nanocrystals, Focusing on Nontoxic and Earth-Abundant Materials. Chem. Rev. 2016, 116, 10731–10819. 10.1021/acs.chemrev.6b00116. - DOI - PubMed
    1. Coughlan C.; Ibáñez M.; Dobrozhan O.; Singh A.; Cabot A.; Ryan K. M. Compound Copper Chalcogenide Nanocrystals. Chem. Rev. 2017, 117, 5865–6109. 10.1021/acs.chemrev.6b00376. - DOI - PubMed