Rotating Disk Electrode Research Articles

Considerations for digitalisation of nickel electroforming

ABSTRACT This paper is a ‘follow-on’ from a paper previously published in this journal dealing with the laboratory to pilot scaling up approach using Industry 4.0 manufacturing methods. In particular, the paper reports a strategy for developing a model for the electroforming of nickel from a sulphamate electrolyte at laboratory scale which could subsequently provide an educated approach for transferring the process to a larger scale. At the laboratory scale, a rotating disc electrode assembly was used, which is a standard instrument to determine electrochemical parameters. Thereafter, small scale nickel discs were electroplated using this equipment, and a model of this process was developed and validated against those experimental results. These parameters were then used to actually produce electroforms in a prototype, 18 L tank system. Cross-validation between practical experiments and simulations followed which allowed for fine-tuning the model until it was consistently predicting the real process results within an acceptable error. Overall, it was found that a secondary current distribution model could be used for reasonably accurate description for the electroforming process, and could provide a quick virtual tool at a production facility.

Fluorine-Doped Carbon Support Enables Superfast Oxygen Reduction Kinetics by Breaking the Scaling Relationship.

It is well-established that Pt-based catalysts suffer from the unfavorable linear scaling relationship (LSR) between *OOH and *OH (ΔG(*OOH)=ΔG(*OH)+3.2±0.2 eV) for the oxygen reduction reaction (ORR), resulting in a great challenge to significantly reduced ORR overpotentials. Herein, we propose a universal and feasible strategy of fluorine-doped carbon supports, which optimize interfacial microenvironment of Pt-based catalysts and thus significantly enhance their reactive kinetics. The introduction of C-F bonds not only weakens the *OH binding energy, but also stabilizes the *OOH intermediate, resulting in a break of LSR. Furthermore, fluorine-doped carbon constructs a local super-hydrophobic interface that facilitates the diffusion of H2O and the mass transfer of O2. Electrochemical tests show that the F-doped carbon-supported Pt catalysts exhibit over 2-fold higher mass activities than those without F modification. More importantly, those catalysts also demonstrate excellent stability in both rotating disk electrode (RDE) and membrane electrode assembly (MEA) tests. This study not only validates the feasibility of tuning the electrocatalytic microenvironment to improve mass transport and to break the scaling relationship, but also provides a universal catalyst design paradigm for other gas-involving electrocatalytic reactions.

Fluorine‐Doped Carbon Support Enables Superfast Oxygen Reduction Kinetics by Breaking the Scaling Relationship

AbstractIt is well‐established that Pt‐based catalysts suffer from the unfavorable linear scaling relationship (LSR) between *OOH and *OH (ΔG(*OOH)=ΔG(*OH)+3.2±0.2 eV) for the oxygen reduction reaction (ORR), resulting in a great challenge to significantly reduced ORR overpotentials. Herein, we propose a universal and feasible strategy of fluorine‐doped carbon supports, which optimize interfacial microenvironment of Pt‐based catalysts and thus significantly enhance their reactive kinetics. The introduction of C−F bonds not only weakens the *OH binding energy, but also stabilizes the *OOH intermediate, resulting in a break of LSR. Furthermore, fluorine‐doped carbon constructs a local super‐hydrophobic interface that facilitates the diffusion of H2O and the mass transfer of O2. Electrochemical tests show that the F‐doped carbon‐supported Pt catalysts exhibit over 2‐fold higher mass activities than those without F modification. More importantly, those catalysts also demonstrate excellent stability in both rotating disk electrode (RDE) and membrane electrode assembly (MEA) tests. This study not only validates the feasibility of tuning the electrocatalytic microenvironment to improve mass transport and to break the scaling relationship, but also provides a universal catalyst design paradigm for other gas‐involving electrocatalytic reactions.

Electrodeposition and optimisation of amorphous NixSy catalyst for hydrogen evolution reaction in alkaline environment.

Anion exchange membrane (AEM) water electrolyser has shown its potential in green hydrogen production. One of the crucial tasks is discover novel cost-effective and sustainable electrocatalyst materials. In this study, a low-cost Ni-S-based catalyst for hydrogen evolution reaction was prepared via a simple electrodeposition process from a modified Watts bath recipe. Physical characterisation methods suggest this deposit film to be amorphous. Optimisation of the electrodeposition parameters of the NixSy catalyst was carried out using a rotating disk electrode setup. The optimised catalyst exhibited excellent catalytical performance in 1 M KOH on a microelectrode, with overpotentials of 41 mV, 111 mV and 202 mV at 10, 100 and 1000 mA cm-2 with Tafel slope of 67.9 mV dec-1 recorded at 333 K. Long-term testing of the catalyst demonstrated steady performance over a 24 h period on microelectrode at 100 mA cm-2 with only 71 mV and 37 mV overpotential increase at 293 K and 333 K respectively. Full cell testing with the optimised NixSy as cathode and NiFe(OH-)2 as anode showed 1.88 V after 1 h electrolysis at 500 mA cm-2 in 1 M KOH under 333 K with FAA-3-30 membrane.

Toward more practical site density determination in Fe-N-C catalysts for oxygen reduction reaction: NO-stripping at gas diffusion electrode setup

Evaluation of the site density of single-site iron catalysts has always been a challenge due to the complexity of those materials, and the difficulty of finding selective and simple probing methodologies. Since iron coordinating nitrogen (FeN4) is recognized as the main active site for oxygen reduction reaction (ORR), it is fundamental to develop a method to assess the content in catalysts. Several bulk-probing and surface-probing methods have been developed in the last decade each one with its pros and cons. Among others, with certain limitations, NO stripping performed at a rotating disc electrode (RDE) has become a common characterization to evaluate site density and turnover frequency of Fe-N-C due to the relatively simple procedure. At the same time, gaining information on the activity on more practical devices has brought to the spreading of gas diffusion electrodes (GDE) in half-cell configuration to mimic the cathodic compartment of a fuel cell, a leading device for those materials applications. Here we proposed a transposition of NO-stripping from RDE to GDE to evaluate the site density under more practical devices. Several parameters have been considered (i.e., pH, loading, FeN4 selectiveness) and comparisons with RDE have been done to validate the methods. A homemade Fe-N-C catalyst has been used as a benchmark and compared to Pajarito Powder catalyst and others (including metal-free) showing the validity and selectivity of the method.

Achieving Highly Durable Intermetallic PtMn3N Electrocatalyst via the Strong Metal‐N Bonds toward Oxygen Reduction Reaction

AbstractPt‐based intermetallic compounds have been considered promising electrocatalysts in the practical applications of fuel cells; however, the development of Pt‐based catalysts that meet performance targets of high activity, maximized stability, and low cost remains a huge challenge. Herein, an atomically ordered and low‐Pt intermetallic nitride (PtMn3N) catalyst are synthesized consisting of a strained Pt shell and PtMn3N core on carbon support via the KCl‐matrix protection strategy. The PtMn3N catalyst represents a high mass activity of 0.70 A mgPt−1 at 0.9 V and a specific activity degradation of 4.2% after 5000 potential cycles for the oxygen reduction reaction (ORR) in rotating disk electrode (RDE) testing, which substantially outperformed commercial Pt/C (0.25 A mgPt−1 and 17.4%). Density functional theory calculations reveal that the introduction of Mn elements to the Pt lattice is beneficial to produce appropriate compressive strain to weaken the binding energy of oxygen species and the introduction of N elements to promote the strong metal‐N interactions is conducive to alleviating the dissolution of metal atoms, allowing for displaying the prominent durability. This work provides an effective strategy of N‐doped Pt‐based intermetallic compounds to enhance the corrosion resistance of 3d transition metals and to enhance the ORR performance.

Glucose oxidation on gold in alkaline solution: A DEMS and microkinetic modelling study

The mechanism and kinetics of the electrochemical oxidation of glucose on gold surfaces in 0.1 M NaOH solution are investigated by rotating disc electrode and differential electrochemical mass spectrometry coupled to microkinetic modelling. For this purpose, the glucose mass-transport parameters (solution viscosity and density, glucose diffusion coefficient) were determined in the relevant conditions. Koutecký-Levich analysis of rotating disc electrode current-potential curves revealed that the glucose oxidation reaction (GOR) follows a one-electron mechanism at 0.6 V vs RHE, while H2 production could be evidenced by DEMS in this potential range. This suggests that the glucose oxidation selectively produces gluconate at 0.6 V vs RHE through an electrochemical oxidative dehydrogenation (EOD) mechanism. A microkinetic model of the current-potential curves was developed, taking into account the hydrogen electrode reactions kinetics, the dissociative adsorption/desorption of glucose, and the glucose electrooxidation on gold surfaces. The dissociative adsorption of glucose was found to be the rate-determining step of the reaction. It is also revealed that the release of anodic H2 through the Tafel step is triggered by the consumption of the adsorbed reaction intermediates. The gluconate electrooxidation into further products has to be considered for potential above 0.7 V vs RHE.

Stability of supported Pd-based ethanol oxidation reaction electrocatalysts in alkaline media

This study evaluates the dissolution of the supported electrocatalysts Pd/C, PdSn/C, PdNb/C, and PdFe3O4/C during ethanol oxidation reaction for Alkaline Direct Liquid Fuel Cells (ADLFC) applications. A scanning flow cell (SFC) combined to an inductively coupled plasma mass spectrometry (online ICP-MS) is used to assess the dissolution stability in a broad potential window. Accelerated stress tests with and without ethanol are developed using a rotating disk electrode (RDE) with dissolution products analysis by ex-situ ICP-MS. Potential profiles simulating those experienced by the catalyst during regular fuel cell operation were used. Sn and Fe catalysts demonstrate improved activity and stability compared with the material with Pd alone. For these reasons, PdSn/C and PdFe3O4/C are suitable for ADLFC applications. Severe Nb dissolution destabilizes Pd, increasing its leaching. This work demonstrates that while additional metals and oxides can improve the alcohol oxidation kinetics of Pd, these additives’ dissolution stability must already be considered at the catalyst design stage.

Designer Electrocatalysts for the Oxygen Reduction Reaction with Controlled Platinum Nanoparticle Locality

AbstractFor global deployment of proton exchange membrane fuel cells, achieving optimal interaction between the components of the cathode active layer remains challenging. Studies addressing the effect of nanoparticle location (inside vs outside of pores) on performance and durability mostly compare porous and nonporous carbon supports, thus coming short of decoupling nanoparticle locality from carbon support effects. To address the influence of nanoparticle locality on performance and durability, new carbon‐supported electrocatalysts with designed and distinct nanoparticle localities are presented. The developed methodology allows to place Pt nanoparticles preferentially inside or outside of the mesopores of conductive carbon supports from materials under development at Cabot Corporation. Synthesis protocols are tuned to control nanoparticle size, crystallinity, and loading; this way the effect of Pt locality can be studied for two experimental carbon supports in isolation from all other parameters. For one carbon support, Pt active surface area and activity are significantly lower when nanoparticles are placed inside the pores. In contrast, for another, more graphitic carbon support, placing nanoparticles inside or outside of the carbon pores produces no appreciable difference in active surface area and performance rotating disk electrode measurements. Given their carefully tailored structure, these catalysts provide a framework for evaluating locality‐performance‐durability relationships.

Oxygen reduction reaction on Ag nanocatalysts prepared by the microemulsion method

The microemulsion (water-in-oil) method is used to prepare novel silver catalysts onto three different carbon supports (multi-walled carbon nanotubes (MWCNT), mesoporous carbon (MC) and Vulcan carbon (C)). It allows to control the Ag particle growth and produces particles that range between 2 and 3 nm. The Ag-based catalysts are characterised by scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS). The electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M KOH is studied using the rotating disc electrode method. High-angle annular dark-field (HAADF) STEM images reveal the Ag particle size range between 1.8 and 2.4 nm, and the EDS mapping shows uniform Ag distribution on the substrates used. Ag1/MC (two-step synthesis) and Ag2/MC (one-step synthesis) catalysts prepared onto the MC support show the highest mass activity of 30–37 A g−1. The two-step synthesis method is preferred to prepare Ag/MWCNT and Ag/C catalysts. The mass activity of the Ag1/MWCNT catalyst is more than two times higher than that of Ag2/MWCNT. Ag1/MWCNT shows the highest electrochemical stability after the accelerated durability test, with only a 6 mV shift in half-wave potential. The microemulsion method is very promising for the production of highly stable Ag-based catalysts with Ag particles smaller than 3 nm in size.

Mathematical modeling of hydrogen evolution by $${{{H}}}^{+}$$ and $${{{H}}}_{2}{{O}}$$ reduction at a rotating disk electrode: theoretical and numerical aspects

Mathematical modeling of hydrogen evolution by $${{{H}}}^{+}$$ and $${{{H}}}_{2}{{O}}$$ reduction at a rotating disk electrode: theoretical and numerical aspects

Be aware of the effect of electrode activation and morphology on its performance in gas diffusion electrode setups

The superior performance enhancement in catalyst research for proton exchange membrane fuel cells (PEMFC) revealed in the model rotating disc electrode (RDE) environment is rarely demonstrated in membrane electrode assemblies (MEA). The discrepancy is typically attributed to the difference in the chemical structure and morphology of the catalyst layer (CL), affecting the transport of reactants of the oxygen reduction reaction (ORR). In this study, the gas diffusion electrode (GDE) half-cell setup is used to focus on crucial aspects of CL development, especially on the activation and morphology of CLs, to gain a fundamental understanding of the development of PEMFCs. Adjusting the CL porosity by using different solvent compositions of water and isopropyl alcohol and implementing an activation method for low platinum content catalysts, we focus on understanding the contributions of macro-porosity and hydrophobicity in a liquid electrolyte-based system. We show that macro-porosity significantly influences the O2 mass transport in the CL, demonstrating increased performance with higher porosities. Coupling inductively coupled plasma mass spectrometry (ICP-MS) with the GDE half-cell setup, we propose a method for qualitative estimation of water content in the CL. Lower macro-porosity shows higher platinum dissolution, attributed to improved mass transport of dissolved ions in aqueous media.

Electrochemistry Beyond Solutions: Modeling Particle Self-Crowding of Nanoparticle Suspensions.

Nanoparticle suspensions hold promise to transform functionality of next-generation electrochemical systems including batteries, capacitors, wastewater treatment, and sensors, challenging the limits of existing electrochemical models. Classical solution-based electrochemistry assumes that charge is transported and transferred by point-like carriers. Herein, we examine the electrochemistry of a model aqueous suspension of nondissolvable electroactive nanoparticles over a wide concentration range using a rotating disk electrode. Past a concentration and rotation rate threshold, the electrochemistry deviates from solution theory with a maximum attainable current due to particle "self-crowding" where reacted particles on the electrode surface reduce the area accessible for charge transfer by unreacted particles. The observed response is rationalized with an analytical model considering the physical adsorption/desorption kinetics and interfacial transport of nondissolvable finite-size charge carriers. Experimental validation shows the model to be applicable across a range of electrode sizes and thus suitable for engineering electrochemical systems employing nondissolvable nanoparticle suspensions.

Impact of Nickel on Iridium-Ruthenium Structure and Activity for the Oxygen Evolution Reaction under Acidic Conditions.

Proton exchange membrane water electrolysis (PEMWE) is a promising technology to produce hydrogen directly from renewable electricity sources due to its high power density and potential for dynamic operation. Widespread application of PEMWE is, however, currently limited due to high cost and low efficiency, for which high loading of expensive iridium catalyst and high OER overpotential, respectively, are important reasons. In this study, we synthesize highly dispersed IrRu nanoparticles (NPs) supported on antimony-doped tin oxide (ATO) to maximize catalyst utilization. Furthermore, we study the effect of adding various amounts of Ni to the synthesis, both in terms of catalyst structure and OER activity. Through characterization using various X-ray techniques, we determine that the presence of Ni during synthesis yields significant changes in the structure of the IrRu NPs. With no Ni present, metallic IrRu NPs were synthesized with Ir-like structure, while the presence of Ni leads to the formation of IrRu oxide particles with rutile/hollandite structure. There are also clear indications that the presence of Ni yields smaller particles, which can result in better catalyst dispersion. The effect of these differences on OER activity was also studied through rotating disc electrode measurements. The IrRu-supported catalyst synthesized with Ni exhibited OER activity of up to 360 mA mgPGM -1 at 1.5 V vs RHE. This is ∼7 times higher OER activity than the best-performing IrO x benchmark reported in the literature and more than twice the activity of IrRu-supported catalyst synthesized without Ni. Finally, density functional theory (DFT) calculations were performed to further elucidate the origin of the observed activity enhancement, showing no improvement in intrinsic OER activity for hollandite Ir and Ru compared to the rutile structures. We, therefore, hypothesize that the increased activity measured for the IrRu supported catalyst synthesized with Ni present is instead due to increased electrochemical surface area.

Electrocatalytic oxidation of glycerol performed by nickel/cobalt alloys: Adding value to a common subproduct of chemical industry

The present work shows the electrocatalytical performance of nickel/cobalt alloys towards the conversion of glycerol into higher value molecules, such as glycolic acid, oxalic acid, maleic acid, diethylene glycol and ethylene glycol, identified by chromatographic technique. To do so, the alloy was directly electrodeposited on graphite electrodes, which is a simple, readily available and cheap material, the modified electrodes were characterized by scanning electron microscopy, infrared spectroscopy and electrochemical analysis. Kinetic parameters were obtained using by both Galus methodology and rotating disc electrode (RDE), obtaining the better electrocatalytic modified electrode and the total number of electrons transferred per mol of glycerol. The modified electrode labeled as Ni0.8Co0.2(OH)2 proportion has achieved the highest glycerol conversion after 4 h of reaction, approximately 99.8%, with an energy consumption of 36.38 W/mol.

Rotating Disk Electrode Study of Sm(III)/Sm(II) in LiCl-KCl Eutectic Molten Salt

Understanding the redox reactions of fission products in molten salts is crucial for developing pyroprocessing techniques for used nuclear fuel. A rotating disk electrode is useful for investigating the electrochemical reactions with controlled mass transfer conditions, but its application has been limited in high-temperature corrosive molten salts. This study employs a tungsten (W) rotating disk electrode (RDE) to measure the electrochemical and kinetic properties of the Sm(III)/Sm(II) redox reaction in a LiCl-KCl eutectic molten salt. The properties of the Sm(III)/Sm(II) redox reaction, including diffusion coefficients, exchange current densities, charge transfer coefficients, activation energies, and Tafel slopes, were determined over a temperature range of 723–803 K using limiting currents in linear sweep voltammetry at various rotating speeds and mass transfer-corrected Tafel plots. The kinetic parameters obtained using the rotating disk electrode system can be useful for optimizing the design of pyroprocessing techniques.

Study on Attenuation Mechanism and Durability Improvement of Platinum-Carbon Catalysts for Proton Exchange Membrane Fuel Cells

The relationship between Pt particle size and activity and durability of Pt/C electrocatalysts on rotating disk electrodes is established and the results show that Pt/C electrocatalysts with particle size over 3.5 nm have excellent resistance to Pt particle decay and carbon corrosion. Further, the research results on the mechanism of Pt particle decay and carbon corrosion show that the Pt particle attenuation is composed of 80% Ostwald ripening and 20% particle agglomeration, and the carbon corrosion is affected by the catalytic action of Pt particles. Therefore, the above results show that regulating the Pt particle size to 3.5–4.0 nm can improve the durability of Pt/C electrocatalysts on RDE. To verify the accuracy of this conclusion and determine the optimal particle size range in practical application, single cells with 5 × 5 cm2 is assembled to evaluate the performance and durability of cathode Pt/C electrocatalysts under H2/air. The results show that cathode Pt/C electrocatalysts with particle size between 3.5 nm and 3.8 nm have high single cell performance (2.3 A cm−2@0.65 V) and durability (A loss of 15 mV@0.8 A cm−2 after 30000 cycles). These findings reveal the attenuation mechanism of Pt/C electrocatalysts and provide ideas for the development of high-durability Pt-based electrocatalysts for practical applications.

Hypochlorous acid electrosynthesis and service life assessment of a Ti|Ti–Ru–Ir-oxides anode assembled in a flow electrolyzer: Understanding the influence of the concurrent O2 bubbling flow

This paper addresses the influence of bubbling flow and service life of the Ti|Ti–Ru–Ir-oxides anode during the electrosynthesis of HClO in a laboratory-scale filter-press-type electrolyzer. The electrolyzer was assembled in a flow plant in recirculation mode. Polarization curves in rotating disk electrode (RDE) revealed the coexistence of the oxygen evolution reaction (OER) during HClO electrosynthesis in diluted chloride solutions (containing 35 mM NaCl at pH 3). CFD simulations of the two-phase (O2–H2O) flow were obtained by solving simultaneously the Navier-Stokes and charge conservation equations using a finite element method code. The O2–H2O simulations show the efficient gas release in the electrolyzer provoked by the continuous phase (H2O) inertia and the well-engineered cell design. The moderated O2 dispersion caused a quasi-homogeneous current distribution along the anode. However, the current efficiency during HClO electrosynthesis gave values of ∼32% provoked by the OER on the anode. The HClO accumulations (from 3.02 to 6.64 mM) showed excellent agreement with CFD simulations. The accelerated life tests revealed that the Ti | Ti–Ru–Ir-oxides anode has a lifetime of at least 26 years during the HClO electrosynthesis in diluted chloride solutions.

Experiments and Calculation on New N,N-bis-Tetrahydroacridines.

Tetrahydroacridines arouse particular interest due to the potential possibilities of application in the medical field and protection against corrosion. Bis-tetrahydroacridines were newly synthesized by Pfitzinger condensation of 5,5'-(ethane-1,2-diyl) diindoline-2,3-dione with several cyclanones. NMR, MS, and FT-IR were used to prove their molecular structure. In addition, a computer-aided study was performed for the lowest energy conformers of each structure, in vacuum conditions, at ground state using DFT models to assess their electronic properties. UV-Vis and voltammetric methods (cyclic voltammetry, differential pulse voltammetry, and rotating disk electrode voltammetry) were used to investigate their optical and electrochemical properties. The results obtained for these π-conjugated heteroaromatic compounds lead to the conclusion that they have real potential in applications in different fields such as pharmaceuticals and especially as corrosion inhibitors.

Modelling and verification of the nickel electroforming process of a mechanical vane fit for Industry 4.0

In previous studies, the comprehensive scaling-up of nickel electroforming on a lab-scale rotating disk electrode (RDE) suggested that secondary current distribution could adequately simulate such a forming process. In this work, the use of a 3-D, time-dependent, secondary current distribution model, developed in COMSOL Multiphysics®, was examined to validate the nickel electroforming of an industrial mechanical vane, a low-tolerance part with a demanding thickness profile of great interest to the aerospace industry. A set of experiments were carried out in an industrial pilot tank with computations showing that the model can satisfactorily predict the experimental findings. In addition, these experiments revealed that the local applied current density was related to the surface appearance (shiny vs matt) of the electroform.Simulations of the process at applied current densities ≤5A/dm2 satisfactorily predicted the experimentally observed thickness distribution while, simulations of the process at applied current densities ≥5A/dm2 underpredicted the experimentally achieved thicknesses. Nevertheless, it is proposed that the model can be used for either quantitative or qualitative studies, respectively, depending on the required operating current density on a case-by-case basis. Scanning electron microscopy was used to determine the microstructure of the electroforms and determine the purity of nickel (i.e., if nickel oxide is formed), with imaging suggesting that pyramid-shaped nickel particles evolve during deposition. Another interesting observation revealed a periodicity in the deposit's growth mechanism which leads to “necklace”-like deposit layers at the areas where the electroforms presented the highest thickness.