Aqueous Synthesis of Plasmonic Gold-Tin Alloy Nanoparticles

Published: March 15, 2024

doi:

Ji Hyeon Cha, Samantha M. Silva, Anthony J. Branco, Michael B. Ross

¹Department of Chemistry,University of Massachusetts Lowell

Summary

Here, the synthesis of gold (Au) seeds is described using the Turkevich method. These seeds are then used to synthesize gold-tin alloy (Au-Sn) nanoparticles with tunable plasmonic properties.

Abstract

This protocol describes the synthesis of Au nanoparticle seeds and the subsequent formation of Au-Sn bimetallic nanoparticles. These nanoparticles have potential applications in catalysis, optoelectronics, imaging, and drug delivery. Previously, methods for producing alloy nanoparticles have been time-consuming, require complex reaction conditions, and can have inconsistent results. The outlined protocol first describes the synthesis of approximately 13 nm Au nanoparticle seeds using the Turkevich method. The protocol next describes the reduction of Sn and its incorporation into the Au seeds to generate Au-Sn alloy nanoparticles. The optical and structural characterization of these nanoparticles is described. Optically, prominent localized surface plasmon resonances (LSPRs) are apparent using UV-visible spectroscopy. Structurally, powder X-ray diffraction (XRD) reflects all particles to be less than 20 nm and shows patterns for Au, Sn, and multiple Au-Sn intermetallic phases. Spherical morphology and size distribution are obtained from transmission electron microscopy (TEM) imaging. TEM reveals that after Sn incorporation, the nanoparticles grow to approximately 15 nm in diameter.

Introduction

Plasmonic metal nanoparticles¹^,² have applications in catalysis, optoelectronics, sensing, and sustainability due to their ability to absorb light with great efficiency, concentrate light into sub-nanometer volumes, and enhance catalytic reactions³^,⁴^,⁵. Only a few metals display efficient localized surface plasmon resonances (LSPRs). Among them, one of the widely explored metals is Au³.

Au is an extensively studied noble metal known for its stable alloy formation with other metals. However, the Au LSPR is limited to the visible and infrared and cannot be tuned to higher energies⁶^,⁷^,⁸. Meanwhile, post-transition metals have a variety of interesting reactive and catalytic properties distinct from the noble metals⁶^,⁹^,¹⁰. By alloying Au with post-transition metals, the LSPR can be tuned toward higher energies toward the UV¹. This protocol focuses on Au-Sn alloying. Sn is known to alloy readily with many metals, can have UV LSPRs, and has interesting catalytic applications, such as formic acid formation via carbon dioxide reduction⁶^,⁷^,⁸. Au and Sn alloys were synthesized using a seeded process through chemical reduction and diffusion of Sn into the seeds.

The primary goal of this method is to synthesize aqueous metal nanoparticle alloys quickly (i.e., in a few hours) and reproducibly at the benchtop using aqueous chemistry. Initially, Au seeds are prepared using the Turkevich method¹¹, followed by seed-based diffusion synthesis, a common strategy when forming random alloy nanoparticles⁸. Notably, alloying of Sn requires a relatively short time (~30 min) in a mild environment with simple equipment compared to other methods⁷^,⁸ that require higher temperature, higher vacuum instrumentation, or hazardous solvents. This process can be performed in mild, aqueous conditions without the need for burdensome environmental controls. The resulting Au-Sn alloys have consistent morphology, size, shape, and optical properties that can be controlled by manipulating the Sn content.

Protocol

The equipment and reagents used in the study are listed in the Table of Materials. 1. Turkevich synthesis method of citrate-capped Au nanoparticle seeds Cleaning of the glassware Clean glassware and stir bars using aqua regia (1:3 mole ratio of HNO3:HCl). Rinse with ultrapure water until no odor remains and dry before use. Preparation of reagent solutions Measure 39.4 mg of HAuCl…

Representative Results

Figure 1 shows representative results for Au seeds and Au-Sn alloy nanoparticles. Following the Au seeds synthesis protocol, a distinct, asymmetric absorption peak around 517 nm with an extinction maximum of approximately 0.7 is observed, corresponding to the LSPR. The peak blue shifts with the addition of Sn, correlating with an apparent optical color change in the sample from burgundy to orange to tan-brown. Further blue-shifting and broadening of the peak are observed with an increased pe…

Discussion

In this study, Au seeds were prepared using the Turkevich method¹¹. Regarding procedural limitations of this method, it is necessary to perform the 480 µL injection of 100 mM trisodium citrate rapidly. If the citrate solution is injected slowly, polydisperse particles may form with a large size distribution. Additionally, the cleanliness of the glassware can significantly impact the quality and consistency of Au seeds. If glassware is not cleaned well before use with aqua regia, the Au seeds …

Divulgations

The authors have nothing to disclose.

Acknowledgements

This work relates to Department of Navy awards N00014-20-1-2858 and N00014-22-1-2654 issued by the Office of Naval Research. Characterization was supported in part by the National Science Foundation Major Research Instrumentation program under Grant 2216240. This work was also partially supported by the University of Massachusetts Lowell and the Commonwealth of Massachusetts. We are grateful to the UMass Lowell Core Research Facilities.

Materials

Basix Microcentrifuge Tubes	Fisher Scientific	Cat#02-682-004
Cary 100 UV-visible Spectrophotometer	Agilent Technologies	Cat#G9821A; RRID:SCR_019481
Cary WinUV	Agilent Technologies		https://www.agilent.com/en/product/molecular-spectroscopy/uv-vis-uv-visnir-spectroscopy/uv-vis-uv-vis-nirsoftware/cary-winuv-softwar
Crystallography Open Database	CrystalEye	RRID: SCR_005874	http://www.crystallography.net/
Cu Carbon Type-B Grids (200 mesh, 97 µm grid holes)	Ted Pella	Cat#01811
Direct-Q 3 UV-R Water Purification System	MilliporeSigma	Cat#ZRQSVR300
Entris Analytical Balance	Sartorius	Cat#ENTRIS64I-1SUS
Glass round-bottom flask (250 mL)	Fisher Scientific	Cat#FB201250
Glass scintillation vials	Wheaton	Cat#986548
Hydrochloric acid (HCl, NF/FCC)	Fisher Scientific	CAS: 7647-01-0, 7732-18-5
Hydrogen tetrachloroaurate (III) trihydrate (HAuCl₄·3H₂O, 99.99%)	Alfa Aesar	CAS: 16961-25-4	kept in a desiccator for consistency of purity and stability
ImageJ	National Institute of Health	RRID: SCR_003070	https://imagej.nih.gov/ij/download.html
Isotemp GPD 10 Hot Water Bath	Fisher Scientific	Cat#FSGPD10
Isotemp Hot Plate Stirrer	Fisher Scientific	Cat#SP88857200
Mili-Q Ultrapure Water (18.2 MΩ-cm)	Water purification system
Miniflex X-Ray Diffractometer	Rigaku	RRID:SCR_020451	https://www.rigaku.com/products/xrd/miniflex
Model 5418 Microcentrifuge	Eppendorf	Cat#022620304
Nitric acid (HNO₃, Certified ACS Plus)	Fisher Scientific	CAS: 7697-37-2, 7732-18-5
On/Off Temperature Controller for Heating Mantle	Fisher Scientific	Cat#11476289
Optifit Racked Pipette Tips (0.5-200 µL)	Sartorius	Cat#790200
Optifit Racked Pipette Tips (10-1000 µL)	Sartorius	Cat#791000
Philips CM12 120 kV Transmission Electron Microscope	Philips	RRID:SCR_020411
Pipette Tups (1-10 mL)	USA Scientific	Cat#1051-0000
Poly(vinylpyrrolidone) (PVP; molecular weight [MW] = 40,000)	Alfa Aesar	CAS: 9003-39-8	kept in a desiccator for consistency of purity and stability
Practum Precision Balance	Sartorius	Cat# PRACTUM1102-1S
PTFE Magnetic Stir Bar (12.7 mm)	Fisher Scientific	Cat#14-513-93
PTFE Magnetic Stir Bar (25.4 mm)	Fisher Scientific	Cat#14-513-94
Quartz Cuvette (length × width × height: 10 mm × 12.5 mm × 45 mm)	Fisher Scientific	Cat#14-958-126
Round Bottom Heating Mantle 120 V 250 mL	Fisher Scientific	Cat#11-476-004
SmartLab Studio II	Rigaku		https://www.rigaku.com/products/xrd/studio
Sodium borohydride (NaBH₄, 97+%)	Alfa Aesar	CAS: 16940-66-2	kept in a desiccator for consistency of purity and stability
SureOne Pipette Tips (0.1-10 µL)	Fisher Scientific	Cat#02-707-437
Tacta Mechanical Pipette (P10)	Sartorius	Cat#LH-729020
Tacta Mechanical Pipette (P1000)	Sartorius	Cat#LH-729070
Tacta Mechanical Pipette (P10000)	Sartorius	Cat#LH-729090
Tacta Mechanical Pipette (P20)	Sartorius	Cat#LH-729030
Tacta Mechanical Pipette (P200)	Sartorius	Cat#LH-729060
Tin (IV) chloride (SnCl₄, 99.99%)	Alfa Aesar	CAS: 7646-78-8	kept in the fume hood and sealed with Parafilm between uses to avoid exposure to ambient conditions
Trisodium citrate dihydrate (C₆H₅Na₃O₇·2H₂O, 99%)	Alfa Aesar	CAS: 6132-04-3	kept in a desiccator for consistency of purity and stability
Zero-Background Si Sample Holder	Rigaku

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