Here we quantify the electrochemical oxidation of Ag nanoparticles (NPs) as a function of size by electrostatically attaching Ag NPs synthesized by seed-mediated growth in the presence of citrate (diameter = 8 to 50 nm) to amine-functionalized indium-tin oxide coated glass electrodes (Glass/ITO), obtaining a linear sweep voltammogram from 0.1 V, where Ag(0) is stable, up to 1.0 V, and observing the peak potential (E(p)) for oxidation of Ag(0) to Ag(+). Electrostatic attachment to the organic linker presumably removes direct interactions between Ag and ITO and allows control over the total Ag coverage by altering the soaking time. This is important as both metal-electrode interactions and overall Ag coverage can affect E(p). E(p) shifts positive from an average of 275 to 382 mV as the Ag NP diameter increases for a constant Ag coverage and under conditions of planar diffusion, suggesting a shift in E(p) due to a thermodynamic shift in E(0) for the Ag/Ag(+) redox couple with size. The negative shift in E(p) with decreasing Ag NP radius follows the general trend predicted by theory and agrees with previous qualitative experimental observations. A better understanding of metal nanostructure oxidation is crucial considering their potential use in many different applications and the importance of metal corrosion processes at the nanoscale.

PurposeThis paper aims to provide a review of available published literature in which nanostructures are incorporated into AM printing media as an attempt to improve the properties of the final printed part. The purpose of this article is to summarize the research done to date, to highlight successes in the field, and to identify opportunities that the union of AM and nanotechnology could bring to science and technology.Design/methodology/approachResearch in which metal, ceramic, and carbon nanomaterials have been incorporated into AM technologies such as stereolithography, laser sintering, fused filament fabrication, and three‐dimensional printing is presented. The results of the addition of nanomaterials into these AM processes are reviewed.FindingsThe addition of nanostructured materials into the printing media for additive manufacturing affects significantly the properties of the final parts. Challenges in the application of nanomaterials to additive manufacturing are nevertheless numerous.Research limitations/implicationsEach of the AM methods described in this review has its own inherent limitations when nanoparticles are applied with the respective printing media. Overcoming these design boundaries may require the development of new instrumentation for successful AM with nanomaterials.Originality/valueThis review shows that there are many opportunities in the marriage of AM and nanotechnology. Promising results have been published in the application of nanomaterials and AM, yet significant work remains to fully harness their inherent potential. This paper serves the purpose to researchers to explore new nanomaterials‐based composites for additive manufacturing.

Here we describe the electrochemical oxidation of an assembly of gold nanoparticles (Au NPs) attached to glass/indium-tin-oxide (ITO) electrodes as a function of particle size. We synthesized Au NP arrays with NP diameters ranging from 8 to 250 nm by electrodeposition of Au from HAuCl(4) in H(2)SO(4) at potentials of -0.2 to 0.8 V versus Ag/AgCl using chronocoulometry to keep the amount of Au deposited constant. The average Au NP size increased with increasing deposition potential. The chemical reduction of HAuCl(4) by NaBH(4) in trisodium citrate solution led to 4 nm average diameter Au NPs, which we chemisorbed to the glass/ITO electrode. Linear sweep voltammograms (LSVs) obtained on the glass/ITO/Au NP (4 to 250 nm) electrodes (with a constant coverage of Au in terms of Au atoms per cm(2)) from 0.5 to 1.1 V in 0.01 M potassium bromide plus 0.1 M HClO(4) showed a positive shift in oxidation potential from 734 +/- 1 mV to 913 +/- 19 mV with increasing Au NP diameter. The shift agrees qualitatively with that predicted by a shift in the redox potential based on a difference in free energy associated with a change in surface energy as a function of particle size. On the basis of the charge during Au deposition versus the charge during oxidation, the oxidation process produces a mixture of Au(III)Br(4)(-) (25%) and Au(I)Br(2)(-) (75%). A glass/ITO electrode coated with a mixture of 4 and 250 nm Au NPs revealed 2 oxidation peaks, consistent with the two Au NP size populations present on the surface.

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