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Method Article

Versatile Technique to Produce a Hierarchical Design in Nanoporous Gold

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DOI:

10.3791/65065

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February 10th, 2023

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In This Article

Erratum Notice

Important: There has been an erratum issued for this article. View Erratum Notice

Summary

Nanoporous gold with a hierarchical and bimodal pore size distribution can be produced by combining electrochemical and chemical dealloying. The composition of the alloy can be monitored via EDS-SEM examination as the dealloying process advances. The material's loading capacity can be determined by studying protein adsorption onto the material.

Abstract

The potential to generate variable pore sizes, simplistic surface modification, and a breadth of commercial uses in the fields of biosensors, actuators, drug loading and release, and the development of catalysts have unquestionably accelerated the usage of nanoporous gold (NPG)-based nanomaterials in research and development. This article describes the process of the generation of hierarchical bimodal nanoporous gold (hb-NPG) by employing a step-wise procedure involving electrochemical alloying, chemical dealloying techniques, and annealing to create both macro- and mesopores. This is done to improve the utility of NPG by creating a bicontinuous solid/void morphology. The area available for surface modification is enhanced by smaller pores, while molecular transport benefits from the network of larger pores. The bimodal architecture, which is the result of a series of fabrication steps, is visualized using scanning electron microscopy (SEM) as a network of pores that are less than 100 nm in size and connected by ligaments to larger pores that are several hundred nanometers in size. The electrochemically active surface area of the hb-NPG is assessed using cyclic voltammetry (CV), with a focus on the critical roles that both dealloying and annealing play in creating the necessary structure. The adsorption of different proteins is measured by solution depletion technique, revealing the better performance of hb-NPG in terms of protein loading. By changing the surface area to volume ratio, the created hb-NPG electrode offers tremendous potential for biosensor development. The manuscript discusses a scalable method to create hb-NPG surface structures, as they offer a large surface area for the immobilization of small molecules and improved transport pathways for faster reactions.

Introduction

Often seen in nature, hierarchical porous architectures have been imitated at the nanoscale to alter the physical characteristics of materials for improved performance1. Interconnected structural elements of various scales of length are a characteristic of the hierarchical architecture of porous materials2. Dealloyed nanoporous metals typically have unimodal pore size distributions; hence, multiple techniques have been devised to produce hierarchically bimodal porous structures with two separate pore size ranges3. The two fundamental objectives of the material design approach, namely the large spe....

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Protocol

1. Constructing a coating of nanoporous gold with hierarchical bimodal architecture on gold wires - Alloying

  1. Assemble an electrochemical cell in a 5 mL beaker. Use a Teflon-based lid with three holes to contain the three-electrode setup.
    NOTE: Teflon is a popular material for making lids, as it does not react with other chemicals.
  2. Place a platinum wire counter-electrode, an Ag/AgCl (saturated KCl) reference electrode, and a gold wire with a diameter of 0.2 mm and a length of 5.0 mm functioning as a working electrode (see Table of Materials) conveniently in each hole of the lid. Maintain a distance of 0.7 c....

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Results

The ligament size and inter-ligament gap adjustments are of utmost significance for the manufactured electrode. Creating a structure with dual-sized pores by optimizing the Au/Ag ratios is the first step in this study, along with the characterization utilizing surface morphology, roughness factor, and loading capacity. Compared to conventional NPG, the bimodal pore structure has demonstrated a higher electrochemical surface area, roughness factor, and protein loading capacity15.

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Discussion

Using a multistep procedure involving alloying, partial dealloying, thermal treatment, and acid etching, fabricating hierarchically NPG with dual-sized pores and a higher active electrochemical surface area is demonstrated.

In alloying, the standard potential of metal precursors influences how reactive they are during electrodeposition. Au and Ag ions from liquid solutions are reduced during electrodeposition16,17.

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Disclosures

The authors have nothing to disclose.

Acknowledgements

This work was supported by an award from the NIGMS (GM111835).

....

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Materials

List of materials used in this article
NameCompanyCatalog NumberComments
Argon gas compressedFisher Scientific Compay
Bovine serum albumin (BSA)Sigma-Aldrich (St.Louis, MO)A9418> 98% purity
Counter electrode (Platinum wire)Alfa Aesar43288-BU0.5 mm diameter
Digital Lab furnaceBarnstead Thermolyne 47,900F47915used for annealing at high temperatures
Digital Potentiostat/galvanostatEG&G Princeton Applied Research273APowerPULSE software
EthanolSigma-Aldrich (St.Louis, MO)CAS-64-17-5HPLC/spectrophotometric grade
Fetuin from fetal calf serumSigma-Aldrich (St.Louis, MO)F2379lyophilized powder
Gold wire rollElectron Microscopy Sciences (Fort Washington, PA)731000.2 mm diameter, 10 ft, 99.9%
Hydrochloric acidFisher ChemicalA144C-21236.5-38%
Hydrogen peroxideFisher Scientific (Pittsburg, PA)CAS-7732-18-530%
KimwipesKIMTECH Science brand, Kimberly-Clark professional341204.4 x 8.2 in
Nitric acidFisher Scientific (Pittsburg, PA)A2008-212trace metal grade
ParafilmBemis PM99613-374-104 IN. x 125 FT.
Peroxidase from horseradish (HRP)Sigma-Aldrich (St.Louis, MO)9003-99-0
PharMed silicone tubingNortonAY242606 1/32" Inner Diameter, 5/32" Outer Diameter, 1/16" Wall Thickness, 25' Length
Potassium dicyanoargentateSigma-Aldrich (St.Louis, MO)37916699.96%, 10 G
Potassium dicyanoaurateSigma-Aldrich (St.Louis, MO)38986799.98%, 1 G
PowerSuite softwareEG&G Princeton Applied Researchcomes with the instrument
PTFE tapeFisherbrand15-078-2611" wide 600" long
Reference electrode (Ag/AgCl)Princeton Applied Research K0265
Scanning Electron Microscopy (SEM) Apreo 2CThermoFisher scientificAPREO 2 SEMequipped with Color SEM technology
Simplicity UV systemMillipore corporation, Boston, MA, USASIMSV00WWfor generating Milli-Q water(18.2 MΩ cm at 25 °C) 
Sodium BorohydrideSigma-Aldrich (St.Louis, MO)213462100 G
Sodium CarbonateSigma-Aldrich (St.Louis, MO)452882enzyme grade, >99%, 100 G
Stir barFisherbrand14-512-1535 x 2 mm
Sulphuric acidFisher Scientific (Pittsburg, PA)A300C-212certified ACS plus
Supracil quartz cuvetteFisher Scientific (Pittsburg, PA)14-385-902C10 mm light path, volume capacity 1 mL
UV-Visible SpectrophotometerVarian Cary 50

References

  1. Fang, M., Dong, G., Wei, R., Ho, J. C. Hierarchical nanostructures: design for sustainable water splitting. Advanced Energy Materials. 7 (23), 1700559(2017).
  2. Inayat, A., Reinhardt, B., Uhlig, H., Einicke, W. -D., Enke, D. Silica monoliths with hierarc....

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Reprints and Permissions

Erratum


Formal Correction: Erratum: Versatile Technique to Produce a Hierarchical Design in Nanoporous Gold
Posted by JoVE Editors on 3/10/2023. Citeable Link.

An erratum was issued for: Versatile Technique to Produce a Hierarchical Design in Nanoporous Gold. The Authors section was updated from:

Palak Sondhi1
Dharmendra Neupane2
Jay K. Bhattarai3
Hafsah Ali1
Alexei V. Demchenko4
Keith J. Stine1
1Department of Chemistry and Biochemistry, University of Missouri-Saint Louis
2Food and Drug Administration
3Mallinckrodt Pharmaceuticals Company
4Department of Chemistry, Saint Louis University

to:

Palak Sondhi1
Dharmendra Neupane1
Jay K. Bhattarai2
Hafsah Ali1
Alexei V. Demchenko3
Keith J. Stine1
1Department of Chemistry and Biochemistry, University of Missouri-Saint Louis
2Mallinckrodt Pharmaceuticals Company
3Department of Chemistry, Saint Louis University

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