Catalytic decomposition of acid hydrogen peroxide solutions on platinum, iridium, palladium and gold surfaces

Bianchi, Giuseppe; Mazza, F.; Mussini, T.

doi:10.1016/0013-4686(62)80034-6

Cited by 105 publications

(91 citation statements)

References 13 publications

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“…These experiments were performed in OER (green triangles), hydrogen peroxide oxidation (red squares, forming oxygen), and formic acid oxidation (blue circles, forming carbon dioxide, Figure 7). [40][41][42][43][44][45] These tests produced gas bubbles of various sizes on the electrode surface. At high gas generation rates, bubbles as large as 10 μl could periodically form and cover the electrode surface before diffusing away from the electrode.…”

Section: Resultsmentioning

confidence: 99%

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

Alia

Rasimick

Ngo

et al. 2016

J. Electrochem. Soc.

179

223

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Unsupported iridium (Ir) nanoparticles, that serve as standard oxygen evolution reaction (OER) catalysts in acidic electrolyzers, were investigated for electrochemical performance and durability in rotating disk electrode (RDE) half-cells. Fixed potential holds and potential cycling were applied to probe the durability of Ir nanoparticles, and performance losses were found to be driven by particle growth (coarsening) at moderate potential (1.4 to 1.6 V) and Ir dissolution at higher potential (≥1.8 V Hydrogen is a major commodity chemical with approximately 2% of U. S. used energy going through a hydrogen pathway, primarily for ammonia production (agriculture) and the upgrading of crude oil (transportation). The majority of hydrogen in the US is produced from natural gas by steam methane reformation.1 While electrochemical water splitting currently represents a small percentage of hydrogen production, it is expected to have a growing role as costs decrease. 2Although the commercial competitiveness of electrolysis is currently limited by feedstock costs, catalyst cost and durability will become increasingly important as electrolyzers move toward low cost, intermittent, renewable sources of electricity such as wind and solar. 3,4 Acidic electrolyzers typically use iridium (Ir) in the oxygen evolution reaction (OER) as this material exhibits both reasonable activity and stability.5 Platinum and ruthenium have also been investigated as alternatives. Platinum, however, requires a higher overpotential (lower efficiency) and ruthenium has durability (dissolution) concerns. [6][7][8] Efforts to develop improved OER catalysts for acidic electrolyzers typically focus on supporting Ir oxide on titania 9-13 or alloying Ir with platinum, ruthenium, or other transition metal oxides [14][15][16][17][18][19][20][21][22][23] to improve durability and performance. Density functional theory studies have correlated trends in the OER activity of metal oxides to the adsorption energies of surface oxygen species, suggesting future directions for improving OER catalysts.24 Strasser et al. also examined the intrinsic activity of Ir, platinum, and ruthenium polycrystalline metals and nanoparticles in rotating disk electrode (RDE) half-cells, using carbon monoxide to determine catalyst surface areas.6 Efforts exploring OER catalysts, however, pale in comparison to the efforts expended in the pursuit of fuel cell catalysts for the oxygen reduction reaction (ORR). Specifically, the fuel cell community has established baselines and protocols for the performance and durability of ORR catalysts. [25][26][27][28] No such protocols or baselines currently exist for OER catalysts.This study presents data from several different commercial suppliers of unsupported and supported Ir and Ir oxide catalysts, and investigates the intrinsic activity of Ir in RDE half-cells, evaluating both performance and durability while presenting the data under standardized conditions. The modes of losses for Ir nanoparticles under specific testing protocols are present...

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Section: Resultsmentioning

confidence: 99%

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

Alia

Rasimick

Ngo

et al. 2016

J. Electrochem. Soc.

179

223

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“…Here we do not model the saturation but focus on low concentrations of educts and products. Experiments with comparatively large (mm-sized) electrodes suggest that the decomposition of hydrogen-peroxide at metal surfaces in acidic medium happens via a formation of oxides at the surfaces 51 . As also discussed in App.…”

Section: Hydrodynamic Equationsmentioning

confidence: 99%

Nonlinear, electrocatalytic swimming in the presence of salt

Sabass

Seifert

2012

The Journal of Chemical Physics

112

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A small, bimetallic particle in a hydrogen peroxide solution can propel itself by means of an electrocatalytic reaction. The swimming is driven by a flux of ions around the particle. We model this process for the presence of a monovalent salt, where reaction-driven proton currents induce salt ion currents. A theory for thin diffuse layers is employed, which yields nonlinear, coupled transport equations. The boundary conditions include a compact Stern layer of adsorbed ions. Electrochemical processes on the particle surface are modeled with a first order reaction of the Butler-Volmer type. The equations are solved numerically for the swimming speed. An analytical approximation is derived under the assumption that the decomposition of hydrogen peroxide occurs mainly without inducing an electric current. We find that the swimming speed increases linearly with hydrogen peroxide concentration for small concentrations. The influence of ion diffusion on the reaction rate can lead to a concave shape of the function of speed vs. hydrogen peroxide concentration. The compact layer of ions on the particle diminishes the reaction rate and consequently reduces the speed. Our results are consistent with published experimental data.

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“…The previous literature also suggests that a mechanism similar to mechanism #2 explains the reduction of peroxide on Pt in alkaline solutions [63][64][65][66] and mechanism #4 is the proposed reduction pathway on mercury, graphite, and gallium phosphide. 63 Mechanism #4 suggests the Tafel slope of 0.19, which is in agreement with the experiment (Table IV) and mechanism #2 suggests that the current is chemically controlled and so is independent of potential.…”

Section: Resultsmentioning

confidence: 90%

Corrosion Characteristics of Alloy 800 in Aqueous Solutions up to 200°C

Nickchi

Alfantazi

2012

J. Electrochem. Soc.

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The corrosion behavior of Alloy 800 in sulfate solutions containing hydrogen peroxide in the temperature range of 100-200 • C was studied. Electrochemical techniques were used to study both the cathodic and anodic processes. The reduction of hydrogen peroxide showed an increase in the steady state current density and the H 2 O 2 diffusion coefficient by increasing the temperature from 100 to 200 • C. The electrochemical corrosion of Alloy 800 showed a decrease in corrosion potential and a decrease in transpassive potential in accordance with calculations for CrO 4 −2 /Cr 2 O 3 and HCrO 4 − /Cr 2 O 3 couples. The increase in corrosion current density was compared with a predictive model based on both reaction kinetics and water property changes. The findings were compared with weight loss measurements and surface characterization studies.The next generation of power plants aims to approach more efficient and safer designs. One of the candidate designs is the supercritical water cooled reactor (SCWR). Two major advantages are identified for this new design. The first is the higher thermal efficiency because of higher maximum water temperature. 1 The most recent models have proposed that the efficiency of SCWR will be nearly 45% compared to the current reactors' typical efficiency of 33%. The second is the simpler plant design. It is partly because the supercritical water has an appreciably higher heat capacity compared to liquid water and, as a consequence, lower cooling water flow rates would be sufficient at a fixed production rate. The lower flow rate translates into simpler parts in the cooling system loop. 2 However, there are uncertainties regarding the SCWR development due to corrosion characteristics of the environment. The water is exposed to radiation, and the consequent water radiolysis generates radicals such as O .. , H . , HO . and H 2 O 2 which are considered corrosive. 3,4 Therefore, predicting the water chemistry and its interaction with materials at high temperature and pressure should first be fully understood. The corrosion behavior of materials in such an environment is determined by two factors: 1) the operating temperature: the thermodynamic stability of species changes and the reaction rates acceleration which translates into higher corrosion rate. 2) The concentration of radicals such as O .. , H . , H 2 O 2 : the higher the concentration, the more corrosive the solution.The generation of these radicals and their interactions with various metals have been studied. [4][5][6][7][8][9] The maximum transient concentration of hydrogen peroxide in a typical radiation flux is 10 −4 M. 7 Therefore, the corrosion of metals could be simulated by adding hydrogen peroxide up to 10 −4 M. The high-temperature, high-pressure corrosion of 1018 carbon steel, 10 304 stainless steel, 11 316 stainless steel, 12,13 Alloy 182, 14 Alloy 690, 15 and duplex stainless steel 16 in the presence of hydrogen peroxide have been studied.One of the candidate materials of construction is Alloy 800, which has acceptable high...

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Catalytic decomposition of acid hydrogen peroxide solutions on platinum, iridium, palladium and gold surfaces

Cited by 105 publications

References 13 publications

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction

Nonlinear, electrocatalytic swimming in the presence of salt

Corrosion Characteristics of Alloy 800 in Aqueous Solutions up to 200°C

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