Electrodeposition of Two-Dimensional Pt Nanostructures on Highly Oriented Pyrolytic Graphite (HOPG): The Effect of Evolved Hydrogen and Chloride Ions

Alpuche-Avilés, Mario A.; Farina, Filippo; Ercolano, Giorgio; Subedi, Pradeep; Cavaliere, Sara; Jones, Deborah J.; Rozière, Jacqués

doi:10.3390/nano8090668

Cited by 11 publications

(8 citation statements)

References 43 publications

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“…Having taken these steps, the noise in the data may be due to droplet restructuring on the UME surface or differences in ion-transfer potential between droplets. From these data, an average apparent rate constant of 0.003 ± 0.001 cm•s −1 was extracted, which is consistent with bulk values extracted from electrokinetic growth experiments, 49 and is similar to previously reported rate constants for platinum 50 (0.006 cm•s −1 ) and silver 51 (0.05 ± 0.02 cm•s −1 ) electrodeposition. Furthermore, values for the rate constant of single platinum NP growth on platinum substrates have not been reported.…”

Section: Resultssupporting

confidence: 88%

Quantifying Growth Kinetics of Single Nanoparticles in Sub-Femtoliter Reactors

2020

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The progression of nanoscience necessitates quantitative tools to understand reactivity at the nanoscale. Here, we report a quantitative model that describes both the electrokinetic and diffusion-limited growth of a single nanoparticle (NP) within sub-femtoliter reactors and apply the model to quantify growth kinetics of platinum NPs within single aqueous nanodroplets (r drop ≈ 500 nm). The time-resolved growth mechanism of the platinum NPs can be observed by studying the collisions of chloroplatinate-filled aqueous nanodroplets with ultramicroelectrodes (UMEs). If the potential of the UME is biased sufficiently negative to drive the reduction of chloroplatinate to platinum metal, transients in the amperometric trace can be observed for individual nanodroplet collision events. At low overpotentials, a parabolic increase in current following t 2, indicative of electrokinetic growth, is observed, and at high overpotentials, an instantaneous rise in current following t 1/2, indicative of diffusion-controlled growth, is observed. Each transient is followed by a rounded peak and a slow decay to baseline, which can be explained by the competition between the rate of NP growth and the rate of metal precursor consumption (electrolysis). We demonstrate that the model couples electrocrystallization and nanodroplet electrolysis to quantitatively predict the collision transient shape, amplitude, and duration. Importantly, the only adjustable parameter in the developed model for electrokinetic growth is the heterogeneous rate constant, k, allowing the growth kinetics of single NPs to be directly evaluated. We measured k for 100 single platinum NPs and found k = 0.003 ± 0.001 cm·s–1 for the growth of platinum NPs on a platinum UME. This platform permits rapid data acquisition for the high-throughput study of the growth kinetics of single NPs, and the model can be generalized to elucidate kinetic and mass-transfer rates under nanoscale conditions of high spatial confinement.

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Section: Resultssupporting

confidence: 88%

Quantifying Growth Kinetics of Single Nanoparticles in Sub-Femtoliter Reactors

2020

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“…[ 39 ] Since the physically dissolved O 2 can be easily integrated into the electrochemically deposited material, [ 40 ] its replacement by N 2 helps to improve the electrical transport properties. [ 41 ] The electrolytes were hence bubbled with N 2 for 20 min so that the physically dissolved O 2 gas within the electrolytes would be replaced by N 2 gas. The EDX data of the electrochemically deposited BiTeSe showed reduction in the atomic percent of oxygen from 6.9 at% to 2.8 at% after N 2 bubbling (Section III, Figure S3, and Table S1, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Dutt

Deng

et al. 2022

Adv Elect Materials

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any moving parts and are thus maintenance free, and also environmentfriendly. [1][2][3][4] They are used for the thermal management of parts of electric circuits [5] or optoelectronic devices, [6] cooling of power electronics, [7] powering devices for the internet-of-things, [8] and body-powered wearable electronics. [9][10][11] With increased reliability and accurate temperature control, they could also be effective replacements for macroscopic thermoelectric devices (TEDs) in medical applications, [12][13][14] for example DNA replication [15] or heating and cooling experiments for treating lowgrade tissue injuries. [16] Early μTEDs were fabricated by J.-P. Fleurial and co-workers. [17] During the past two decades, as the approaches to fabrication have evolved continuously, so has the performance of μTEDs. [1,2,[18][19][20] In 2003, Snyder et al. fabricated a cross plane μTED using electrochemical deposition, which showed a maximum cooling of 2 K at 110 mA. [2] μTEDs based on superlattice materials were later fabricated but were not characterized as coolers. [21] In 2007, Huang et al. fabricated a device using MEMS technology in combination with electroplating and reported a maximum cooling of Micro-thermoelectric devices (μTEDs) are used for bio-medical applications, powering internet-of-things devices, and thermal management. For such applications, μTEDs need to have a robust packaging so that the devices can be brought in direct thermal contact with the target heat sink and source. The packaging technology developed for macroscopic modules needs improvement as it cannot be applied to μTEDs due to a large thermal resistance between the capping material and the device which deteriorates its performance. In this work, μTEDs with high net cooling temperature are fabricated by optimizing the contact resistance and device design combined with a novel packaging technique that is fully compatible with on-chip integration. The simulations and experiments demonstrate that the additional thermal loss caused by the packaging leads to an only marginal decrease in the net cooling temperature. The devices achieve a high net cooling temperature of 10.8 K without packaging and 9.6 K with packaging at room temperature. The packaging only slightly increases the thermal response time of the devices, which also shows an extremely high reliability of over 85 million cooling cycles. This simple packaging technique together with robust device performance is a step toward wide-spread application of μTEDs.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/aelm.202101042.

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“…Therefore, as suggested in most of the investigations described above, the surface chemistry plays a major role for the initiation of the spontaneous redox process. Studies on spontaneous noble metal deposition mention various sources for the coupled surface oxidation reaction, e.g., stepedge functional groups of HOPG, 1,7 incompletely oxidized functionalities of HOPG, 5 oxygen-based surface functional groups in porous carbon, 12,15 and defects in intentionally produced defective graphene. 21 Apart from surface functional groups, there is still another, yet underestimated, factor that may play an important role in the spontaneous metal deposition process.…”

Section: ■ General Conceptmentioning

confidence: 99%

“…This process is a result of a direct redox reaction between the solute metal species and the carbon materials and differs from typical electroless deposition that requires additional reducing agents or catalysts to drive the reduction reaction. A series of papers were devoted to the spontaneous metal deposition on highly oriented pyrolytic graphite (HOPG) of Pt, − Ag, and Au. , Nanostructured carbons such as single-walled CNTs (SWCNTs), nanodots, and nanosheets were used for spontaneous deposition of Au, Pt, , Ag, , Pd, , Ir, Rh, and Ru . Spontaneous metal reduction was observed also for Ag, Au, and Pd on graphene oxide (GO), − for Pt on graphene, and for Pd on graphdyine and oxidized graphdyine .…”

Section: Introductionmentioning

confidence: 99%

Spontaneous Carbon-Support-Induced Metal Deposition

Tsakova

2022

ACS Omega

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Recent investigations have demonstrated the possibility for spontaneous deposition of noble metal nanoparticles from corresponding metal ion solutions on carbon supports, in the absence of additional reductants in the experimental systems. This process is a result of a direct redox reaction between the solute metal species and the carbon materials and differs from the typical electroless plating, the latter requiring additional reducing agents or catalysts to drive the reduction reaction. Due to the diversity of the used carbon materials including both dispersed nanostructured carbons and supported electrode-like carbon materials and the different approaches to follow the process and characterize the products, these studies are scattered in the scientific literature. The aim of the present review is to put these diverse investigations in a common context and focus on the existing experimental findings, the ways to monitor and control the process, and the general concept. Some aspects that need to be further corroborated are outlined in view of the involvement of the spontaneous redox process as a practical tool for the development of new catalysts.

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Electrodeposition of Two-Dimensional Pt Nanostructures on Highly Oriented Pyrolytic Graphite (HOPG): The Effect of Evolved Hydrogen and Chloride Ions

Cited by 11 publications

References 43 publications

Quantifying Growth Kinetics of Single Nanoparticles in Sub-Femtoliter Reactors

Quantifying Growth Kinetics of Single Nanoparticles in Sub-Femtoliter Reactors

Geometric Study of Polymer Embedded Micro Thermoelectric Cooler with Optimized Contact Resistance

Spontaneous Carbon-Support-Induced Metal Deposition

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