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Synthesis of gold nanoparticles under highly oxidizing conditions

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Abstract

Gold nanoparticles (AuNPs) were synthesized in a microemulsion water/Triton X-100/1-pentanol/cyclohexane using various reducing agents. Basically, three microemulsion syntheses of AuNPs were studied: (i) one using a strong chemical reducing agent (NaBH4), (ii) another using γ-irradiation under moderately strong reducing/oxidizing conditions, and (iii) yet another under highly oxidizing conditions (with the addition of NaOH aqueous solution). All the three were performed at room temperature. When a strong chemical reducing agent NaBH4 was used in the microemulsion, gold crystallites 11.7 nm in size were obtained, as determined on the basis of X-ray powder diffraction line broadening. The γ-irradiation of nitrogen-saturated microemulsion at the acidic pH produced AuNPs about 12 nm in size, which under the isolation by centrifugation aggregated into large preconcentrated AuNPs about 150 nm in size. These AuNPs possess thixotropic properties. The microemulsion stirred at room temperature and at the pH < 7 under oxidizing conditions did not produce gold nanoparticles. Under the identical experimental conditions and at the pH > 7 (stronger oxidizing conditions), well-dispersed AuNPs 12 nm in size were formed. The microemulsion synthesis of AuNPs in the alkaline range but not at an acidic pH was explained by the oxidation of alcohol groups (–OH) into carbonyl groups (>C=O) due to the catalytic action of hydroxyl ions and gold. In parallel with the catalytic oxidation of alcohol groups in microemulsion, the Au(III) were reduced with the subsequent formation of gold nanoparticles. The synthesis of AuNPs in 1-pentanol by adding the aqueous NaOH solution at room temperature without using microemulsions confirmed the role of the base-catalyzed oxidation of alcohols in the formation of AuNPs. Based on the findings in this study, we propose the base-catalyzed alcohol oxidation at room temperature as a new, simple, and versatile synthesis route for obtaining gold nanoparticles. The results of this study suggest that the classical approach of using a reducing agent for the synthesis of AuNPs is not a determining factor, since a diametrically opposite approach to the synthesis of AuNPs can be used, namely, stimulating the oxidation of the functional organic groups in close proximity to gold ions.

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Acknowledgments

The financial support of the Centre of Excellence for Advanced Materials and Sensors, “Ruđer Bošković” Institute, Croatia, is gratefully acknowledged. Goran Dražić acknowledges the financial support of the Slovenian Research Agency (ARRS) through Program No. P2-0393 and Project J2-6754. We thank Mr. Igor Sajko for the technical assistance on γ-irradiation.

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Authors and Affiliations

  1. Division of Materials Chemistry, Ruđer Bošković Institute, Bijenička 54, Zagreb, Croatia

    Tanja Jurkin & Marijan Gotić

  2. Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 19, 10000, Zagreb, Croatia

    Martina Guliš

  3. Laboratory for Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1001, Ljubljana, Slovenia

    Goran Dražić

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  1. Tanja Jurkin
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Correspondence to Marijan Gotić.

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Scheme S1

Experimental procedure for the preparation of samples MAu-1 through MAu-7 and sample Au-8. (DOC 125 kb)

Table S1

UV-Vis, TEM and SEM characterization of samples. The gold nanoparticle size was determined from the UV-Vis spectra using a procedure presented by Haiss et al. [S1]. The method is based on the relative A SPR/A 450 ratio. For samples MAu-1 and MAu-3 the nanoparticle size was determined using a procedure presented by Khlebtsov [S2]. The mean particle size was calculated from TEM images using the normal function. (DOCX 15.5 kb)

Fig. S1

UV-Vis spectra of samples MAu-1 and MAu-3. Sample MAu-1 was diluted with “pure” microemulsion at a ratio of 1 : 2 (33 % dilution), whereas sample MAu-3 was recorded as synthesized. (DOCX 209 kb)

Fig. S2

SEM images of samples MAu-2 (A) and MAu-3 (B) isolated by centrifugation and recorded on a carbon support. Below the images are corresponding particle size distributions. For sample MAu-2 two size distributions are given, for small (14.9 nm) and large (153.2 nm) nanoparticles. The mean particle size was calculated using the normal function, where \( \overline{D} \) and σ stand for the mean particle diameter and standard deviation, respectively. (DOCX 5074 kb)

Fig. S3

SEM images and corresponding EDS analyses of samples MAu-2 (A) and MAu-3 (B) upon centrifugation. (DOCX 374 kb)

Fig. S4

SEM images and corresponding EDS analyses of sample MAu-3 before (A) and after centrifugation (B). The relative concentration of gold rises and the size of nanoparticles increases upon centrifugation. (DOCX 655 kb)

Fig. S5

SEM images and corresponding EDS analyses of sample MAu-2 before (A) and after the addition of acetone (B). Both samples were analyzed as microemulsion (there was no centrifugation). The size of nanoparticles did not change before or after the addition of acetone. The relative concentration of gold was higher on addition of acetone, which suggests that the samples contained an amount of Au(I) ions that were reduced upon adding acetone. Generally, acetone is added to the microemulsion prior to centrifugation in order to impair its stability and facilitate the isolation of gold nanoparticles in the form of the precipitate (powder). (DOCX 258 kb)

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Jurkin, T., Guliš, M., Dražić, G. et al. Synthesis of gold nanoparticles under highly oxidizing conditions. Gold Bull 49, 21–33 (2016). https://doi.org/10.1007/s13404-016-0179-3

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