Key role of anions in the 2D–3D electrochemical deposition of Rh on Ag electrodes

Schulz, Eduardo Nicolás; Ruderman, Andrés; Soldano, Germán; García, Sara Mallén; Santos, Elizabeth

doi:10.1016/j.electacta.2015.08.071

Cited by 6 publications

(2 citation statements)

References 42 publications

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“…The successful realization of galvanic reaction strategy can be attributed to the higher Nernst equilibrium potential for Pt 2+ /Pt redox couple ( ϕ θ = 1.19 V) and Rh 3+ /Rh redox couple ( ϕ θ = 0.76 V) than Cu 2+ /Cu 2 O redox couple ( ϕ θ = 0.16 V) . According to the actual reaction kinetics, the controlled experimental results indicate that galvanic reaction between K 2 PtCl 4 and Cu 2 O can occur easily (120 °C for 4 h), but galvanic reaction between RhCl 3 and Cu 2 O cannot occur under same experimental conditions.…”

Section: Resultsmentioning

confidence: 99%

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Han

Liu

Chen

et al. 2018

Advanced Energy Materials

250

134

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CC bond cleavage, resulting in the low fuel utilization and less than theoretical 12 elections transfer. [12,13] Thus, improving the ability of electrocatalysts for splitting CC bond is critical for the development and application of DEFCs. [14][15][16] At present, Pt is the most effective monometallic electrocatalyst for the EOR. However, expensive price and weak ability of splitting CC bond seriously hamper its commercial applications. [10,17] Recently, alloying Pt with other metal is generally considered as an efficient strategy for decreasing the cost of electrocatalyst and simultaneously improving electrocatalytic activity for the EOR. [18][19][20][21] For example, the addition of Ru and Rh elements can obviously promote the CC bond cleavage, which is beneficial to the C 1 reaction pathway of the EOR. The introduction of highly oxophilic metals (such as Ni and Cu) can decrease the CO poisoning of electrocatalyst due to the bifunctional mechanism. [17,22,23] Considering that CC bond cleavage and CO poisoning, trimetallic Pt-based electrocatalysts have been designed to simultaneously improve their CC bond cleavage capability and antipoisoning capability. For example, PtPdRh [24] and PtRhNi [22] alloys nanoparticles displayed the excellent electrocatalytic activity for the EOR.Apart from chemical composition, the morphology of nanostructures also strongly affects their electrocatalytic performance. [25][26][27][28][29][30] For example, hollow nanostructures generally show enhanced activity and stability due to their unique advantages, including large surface area, abundant active sites, high atomic utilization, rich holes, fast mass transfer, stable 3D structure, and slow Ostwald ripening. [31][32][33][34][35] Given the effect of chemical composition and morphology on the EOR performance, herein, we designed and synthesized the porous trimetallic PtRhCu cubic nanoboxes (CNBs) by the galvanic reaction between K 2 PtCl 4 , RhCl 3 , and Cu 2 O nanocubes template. The shell thickness and chemical composition of PtRhCu CNBs could be easily regulated by controlling the amount and proportion of noble metal precursors. Due to geometric effect and alloy effect, the composition optimized PtRhCu CNBs exhibited a significantly enhanced C 1 pathway selectivity for the EOR, resulting in super electrocatalytic activity and stability. Additionally, the template method could also be used to synthesize other trimetallic cubic nanoboxes (such as PtIrCu and PtAuCu CNBs), showing its universality.Direct ethanol fuel cells (DEFCs) have great activity as a green energy conversion device. However, the weak activity of most anode electrocatalysts for the CC bond cleavage is an obstacle to the DEFCs development. Herein, a simple galvanic replacement reaction strategy to synthesize hollow and porous PtRhCu trimetallic nanoboxes (CNBs) with a tunable Pt/Rh atomic ratio is developed. For the ethanol oxidation reaction (EOR), PtRhCu CNBs show morphology and composition-dependent electrocatalytic activity. The composition optimized Pt...

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Section: Resultsmentioning

confidence: 99%

Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation

Han

Liu

Chen

et al. 2018

Advanced Energy Materials

250

134

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“…The subsequent gradual decrease in the current at t ≥ t M follows the Cottrell equation (Eq. 1) [26] giving diffusion coefficient values for each curve (plots presented in Figure S3). These values can be found in Table 1.

true - j = \frac{z F c D^{1 / 2}}{π^{1 / 2}} t^{- 1 / 2}

…”

Section: Resultsmentioning

confidence: 99%

Zinc Electrodeposition in Acetate‐based Water‐in‐Salt Electrolyte: Experimental and Theoretical Studies

Amiri

Bélanger

2021

ChemElectroChem

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Zinc electroplating has found applications in many fields. The chemical composition of the electrodeposition bath can have a great impact on the final coating quality and the economics of the process. In traditional aqueous electrolytes, zinc deposition competes with the hydrogen evolution and oxygen reduction reactions, which can lead to hydrogen embrittlement of the substrate as well as decrease in efficiency. Highly concentrated water-in-salt electrolytes can suppress these reactions significantly. Here, we show that electrodeposition of zinc with high efficiencies can be achieved using an acetate-based water-in-salt electrolyte at room temperature. Nucleation studies confirm that at potentials more negative than À 1.30 V vs. Ag/AgCl, the three-dimensional (3D) nucleation process becomes instantaneous, while at more positive potentials it is progressive. Using two of the most common nucleation and growth models, Scharifker-Mostany and Mirkin-Nilov-Heerman-Tarallo, nucleation parameters such as the nucleation rate constant and nuclei density are found, showing a good agreement between the two models.

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