Rotating Ring Disk Electrode Research Articles

The Electrode/Electrolyte Interface Study during the Electrochemical CO2 Reduction in Acidic Electrolytes

AbstractElectrochemical CO2 Reduction (CO2R) in acidic electrolytes has gained significant attention owing to higher carbon efficiency and stability than in alkaline counterparts. However, the proton source and the role of alkali cations for CO2R are still under debate. By using rotating ring disk electrode and surface‐enhanced infrared absorption spectroscopy, we find that a neutral/alkaline environment at the interface is necessary for CO2R even in acidic electrolytes. We also confirm that water molecules, rather than protons serve as the proton source for CO2R. Alkali cations in the outer Helmholtz plane activate H2O and promote the desorption of adsorbed carbon monoxide. Additionally, the solvated CO2, or CO2(aq), is the actual reactant for CO2R. This study provides a deeper understanding of the electrode/electrolyte interface during CO2R in acidic electrolytes and sheds light on further performance improvement of this system.

Catalase‐Based Air‐Cathode for Biocompatible Zinc–Air Battery

AbstractThe use of catalase (CAT) from bovine liver as an electrocatalyst in the air electrode of a primary zinc–air battery (ZAB) with neutral electrolyte (pH 7.4) is reported. First, the use of Nafion for immobilizing CAT onto electrode surface allowed to obtain long‐term stability of the catalytic activity of CAT. Besides, analysis of the CAT and CAT‐Nafion as catalysts for oxygen reduction reaction (ORR) was carried out by linear sweep voltammetry (LSV) using a rotating ring‐disk electrode (RRDE), demonstrating a four‐electron ORR mechanism. Finally, CAT and CAT‐Nafion were tested as air electrodes in flooded ZAB and compared against human hemoglobin‐based ZAB. Our results demonstrated the significant influence of the protein coating of the heme groups on the ZAB performance, affecting greatly the discharge capacity and the power density.

Quantification of electrochemically accessible iridium oxide surface area with mercury underpotential deposition.

Research drives development of sustainable electrocatalytic technologies, but efforts are hindered by inconsistent reporting of advances in catalytic performance. Iridium-based oxide catalysts are widely studied for electrocatalytic technologies, particularly for the oxygen evolution reaction (OER) for proton exchange membrane water electrolysis, but insufficient techniques for quantifying electrochemically accessible iridium active sites impede accurate assessment of intrinsic activity improvements. We develop mercury underpotential deposition and stripping as a reversible electrochemical adsorption process to robustly quantify iridium sites and consistently normalize OER performance of benchmark IrOx electrodes to a single intrinsic activity curve, where other commonly used normalization methods cannot. Through rigorous deconvolution of mercury redox and reproportionation reactions, we extract net monolayer deposition and stripping of mercury on iridium sites throughout testing using a rotating ring disk electrode. This technique is a transformative method to standardize OER performance across a wide range of iridium-based materials and quantify electrochemical iridium active sites.

Alkali metal cations at work: Enhancing CO2 electroreduction to CO on ZnO nanorods

Oxide-derived zinc, an abundant and cost-effective electrode material alternative to gold and silver, has exhibited high activity for the electroreduction of CO2 to CO (CO2RR). However, the impact of cations on the CO2RR activity remains unexplored. In this study, we investigated the effect of three alkali metal cations (Cs+, K+, and Li+) on the CO2RR over a ZnO nanorod electrode, using a rotating ring disk electrode (RRDE) technique. Cyclic voltammetry of the Pt ring in the RRDE tip reveals a consistent trend in the buffering capacity of these cations (Cs+ > K+ > Li+), as evidenced by the availability of OH⁻ ions for CO electrooxidation and hydrogen oxidation reactions (HOR). Cs+ showed a pronounced effect on the activity of the CO2RR to CO since it can regulate OH⁻ concentration and maintain the local pH. This study addresses the ongoing debate concerning the effects of cations; interfacial electric field and buffering capacity; and elucidates the relationship among electrolyte/cation, local pH dynamics, and the CO2RR activity towards CO over the active oxide-derived Zn electrodes, all derived from the fast and facile RRDE technique.

Boosting the bifunctional catalytic activity of Co3O4 on silver and nickel substrates for the alkaline oxygen evolution and reduction reactions

Developing an efficient bifunctional catalyst for oxygen reduction (ORR) and evolution reactions (OER) is a crucial step for the wide commercialization of alkaline water electrolyzers. However, a proper assessment and comparison of various catalysts is still challenging due to the different catalyst substrates and loadings. In this work, Co3O4 spinel nanoparticles (NPs) were investigated as a bifunctional catalyst at different substrates of glassy carbon or Ag bulk substrate or Ni particles and with different loadings. For Co3O4 (800 µg cm-2)/Ag electrode, not only the overpotential for ORR was 50 mV lower than the bare Ag electrode, but also the OER overpotential was 40 mV lower than the sole Co3O4. Besides, less than 1% peroxide intermediate was detected during ORR using the rotating ring disc electrode (RRDE) method, suggesting a 4-electron O2 reduction. Tafel slopes of 70 and 60 mV dec‑1 at Co3O4/Ag were obtained for ORR and OER, respectively. The improved bifunctional activity could be attributed to a synergistic effect between Co3O4 and the Ag support. For the loading effect, it is revealed that the number of accessible sites of Ag surface decreases with increasing the Co3O4 loading, as evaluated from lead-underpotential deposition measurements. Interestingly, after running ORR/OER cycles, the surface area increased by 4–6 times. This surface roughening was also confirmed by SEM and EDX. The study was extended to Co3O4+Ni mixed catalyst to validate the effect of the support on this induced synergism. Hence, this work provides a simple route for designing potential effective catalytic interfaces and contributes to unravelling the influence of the substrate and loading on the catalyst activity for water electrolyzers.

Unlocking OER potential: Tailoring layered double perovskites through self-reconstruction

The sluggish rate of the anode oxygen evolution reaction (OER) is a major bottleneck for green hydrogen production, making a room-temperature alkaline water electrolyser critical to unlocking the full potential of this technology. Using a perovskite oxide as an electrochemical matrix and forming a self-assembled oxyhydroxide (OOH) layer on the surface via a self-reconstruction activation process (SRAP) is a promising strategy to enhance OER catalytic activity. However, the mechanistic details and long-term impact of SRAP, especially its relationship to catalytic activity, oxygen collection efficiency, and catalyst dissolution, are not fully understood. To address this knowledge gap, we used layered double perovskite (LDP) PrBa0·75Ca0·25Co1·5Fe0·5O5+δ(PBCCF) and PrBa0·75Ca0·25Co1·5Fe0·4Ni0·1O5+δ (PBCCFN) as model electrochemical catalysts and then triggered SRAP. Subsequently, chronoamperometry (CA), rotating ring disk electrode (RRDE) and in-situ electrochemical quartz crystal microbalance (EQCM) were used to study the effect of the Ni-doping on PBCCF SRAP in terms of catalytic activity, oxygen collection efficiency and catalyst stability. The results showed that the OER catalytic current of the LDP PBCCF and PBCCFN was enhanced via SRAP and the oxygen collection efficiency can be maintained, suggesting that the increase in catalytic current is attributed to OER catalytic activity increase rather than electrochemical catalyst dissolution. Additionally, the effect of the catalytic activity enhancement was more significant in PBCCFN. More importantly, the stability of the LDP PBCCF and PBCCFN after SRAP are higher than simple perovskite Ba0·5Sr0·5Co0·8Fe0·2O3-δ (BSCF) because of the increase in the redeposition rate. The observations suggest that using LDP PBCCF and PBCCFN as matrices followed by triggering SRAP can provide valuable insights for designing LDP based OER electrocatalysts.

Coordination Structure Modulation in Group-VIB Metal Doped Ag3PO4 Augments Active Site Density for Electrocatalytic Conversion of N2 to NH3.

Doping is considered a promising material engineering strategy in electrochemical nitrogen reduction reaction (NRR), provided the role of the active site is rightly identified. This work concerns the doping of group VIB metal in Ag3PO4 to enhance the active site density, accompanied by d-p orbital mixing at the active site/N2 interface. Doping induces compressive strain in the Ag3PO4 lattice and inherently accompanies vacancy generation, the latter is quantified with positron annihilation lifetime studies (PALS). This eventually alters the metal d-electronic states relative to Fermi level and manipulate the active sites for NRR resulting into side-on N2 adsorption at the interface. The charge density deployment reveals Mo as the most efficient dopant, attaining a minimum NRR overpotential, as confirmed by the detailed kinetic study with the rotating ring disk electrode (RRDE) technique. In fact, the Pt ring of RRDE fails to detect N2H4, which is formed as a stable intermediate on the electrode surface, as identified from in-situ attenuated total reflectance-infrared (ATR-IR) spectroscopy. This advocates the complete conversion of N2 to NH3 on Mo/Ag3PO4-10 and the so-formed oxygen vacancies formed during doping act as proton scavengers suppressing hydrogen evolution reaction resulting into a Faradaic efficiency of 54.8% for NRR.

The Electrode/Electrolyte Interface Study during the Electrochemical CO2 Reduction in Acidic Electrolytes.

Electrochemical CO2 Reduction (CO2R) in acidic electrolytes has gained significant attention owing to higher carbon efficiency and stability than in alkaline counterparts. However, the proton source and the role of alkali cations for CO2R are still under debate. By using rotating ring disk electrode and surface-enhanced infrared absorption spectroscopy, we find that a neutral/alkaline environment at the interface is necessary for CO2R even in acidic electrolytes. We also confirm that water molecules, rather than protons serve as the proton source for CO2R. Alkali cations in the outer Helmholtz plane activate H2O and promote the desorption of adsorbed carbon monoxide. Additionally, the solvated CO2, or CO2(aq), is the actual reactant for CO2R. This study provides a deeper understanding of the electrode/electrolyte interface during CO2R in acidic electrolytes and sheds light on further performance improvement of this system.

Mechanochemically Synthesized RuO2‐Doped LaMnO3 Perovskites as Bifunctional Cathodes for Rechargeable Zn/Air Batteries

AbstractHerein, we have developed LaMnO3 (LMO) perovskite‐based electrocatalysts of oxygen reduction and oxygen evolution reactions (ORR and OER) in a basic aqueous solution. Mechanochemical grinding and thermal annealing leads to highly‐pure perovskites as shown by X‐ray diffraction. This methodology also allows doping the LMO perovskite with RuO2, thus improving its catalytic activity, especially the oxygen evolution reaction. ORR have been analyzed by rotating ring‐disk electrode (RRDE). Eventually, these catalysts are employed in Zn/air batteries resulting in specific capacity values of 12.76 Ahg−1 at 1 Ag−1, when LMO‐RuO2 (LMO−Ru) was used as catalyst in the positive electrodes. Besides, high operational stability of Zn/air batteries for over 100 cycles was obtained, saving 1.46 mWh per cycle when LMO−Ru was used with respect to pure LMO.

Selectivity Study of Direct Seawater Electrolyzer Anode Catalysts Using the Rotating Ring-Disc Electrode Method

Seawater electrolysis suffers from many issues that must be resolved before the technology can be scaled. The corrosive hypochlorite formation at the anode can damage the electrode and other electrolyzer components. Furthermore, hypochlorite is unstable and can decay, particularly when exposed to heat and metal ions, which could lead to erroneously high oxygen evolution reaction (OER) selectivity calculations in catalyst benchmarking experiments, resulting in poor catalyst and electrolyzer component selection. In this study, we used the rotating ring-disc electrode (RRDE) technique for the characterization of IrO2, NiO, Co3O4, RuO2, Pt/C, and PtRu electrocatalysts at near-neutral pH (8.4) in 0.5 M NaCl. The RRDE can overcome the challenge posed by thermocatalytic hypochlorite decay. IrO2 and PtRu were also studied over a range of chloride concentrations from 0.1 to 1 M. Our findings reveal that elevated temperatures (313 and 333 K) are conducive to higher OER selectivity, as the OER faradaic efficiency (FE) on IrO2 increased by 23% at 1.22 V vs SHE when the temperature was increased from 293 to 333 K. Increasing the chloride concentration from 0.1 to 1 M increased the OER current density by 40% and 200% on IrO2 and PtRu, respectively, indicating a synergistic relationship.

Electroreduction of CO2 by Hybrid Cu‐TiO2/rGO Catalyst: Qualitative Detection of Products using Rotating Ring Disc Electrode

AbstractThe electrochemical reduction of CO2 (ERCO2) to valuable chemicals such as acetic acid/acetate offers a promising route to revolutionize chemical production and enhance sustainability. Here, we report the hydrothermal preparation of an electrocatalyst consisting of copper/titanium dioxide/reduced graphene oxide (Cu‐TiO2/rGO) for ERCO2 in aqueous medium. The metal‐support (TiO2/rGO) was pre‐synthesized by combining an aqueous solution of TiO2 and GO in an autoclave at 150 °C for 20 h. Then TiO2/rGO was added to synthesized Cu colloid formed through the reduction of copper (II) nitrate trihydrate resulting in the formation of Cu‐TiO2/rGO. The Cu‐TiO2/rGO hybrid nanocomposite was fully characterized using spectroscopic and microscopic techniques. This study explored the versatility of the rotating ring‐disc electrode (RRDE) as an in situ electroanalytical tool for the selective detection of products formed during ERCO2. The well‐designed hybrid electrocatalyst, containing Cu0/Cu+ active sites, facilitated the eight‐electron transfer for acetic acid (AA) formation at low potentials. AA formation was detected on the RRDE and validated by conventional NMR and HPLC techniques. This work highlights and expands the scope of selective hydrogenation of CO2 towards value‐added products.

Design and Impact: Navigating the Electrochemical Characterization Methods for Supported Catalysts.

This review will investigate the impact of electrochemical characterization method design choices on intrinsic catalyst activity measurements by predominantly using the oxygen reduction reaction (ORR) on supported catalysts as a model reaction. The wider use of hydrogen for transportation or electrical grid stabilization requires improvements in proton exchange membrane fuel cell (PEMFC) performance. One of the areas for improvement is the (ORR) catalyst efficiency and durability. Research and development of the traditional platinum-based catalysts have commonly been performed using rotating disk electrodes (RDE), rotating ring disk electrodes (RRDE), and membrane electrode assemblies (MEAs). However, the mass transport conditions of RDE and RRDE limit their usefulness in characterizing supported catalysts at high current densities, and MEA characterizations can be complex, lengthy, and costly. Ultramicroelectrode with a catalyst-filled cavity addresses some of these problems, but with limited success. Due to the properties discussed in this review, the recent floating electrode (FE) and the gas diffusion electrode (GDE) methods offer additional capabilities in the electrochemical characterization process. With the FE technique, the intrinsic activity of catalysts for ORR can be investigated, leading to a better understanding of the ORR mechanism through more reliable experimental data from application-relevant high-mass transport conditions. The GDEs are helpful bridging tools between RDE and MEA experiments, simplifying the fuel cell and electrolyzer manufacturing and operating optimization process.

Dynamic Oxygen Collection Efficiency: Unraveling the Effects of Perovskites on Carbon Corrosion As Composite Catalysts for Oxygen Electrode

Introduction The composite catalyst comprising perovskite and carbon has been extensively studied as a catalyst for the oxygen evolution reaction (OER) at the oxygen electrode in alkaline media. However, the competitive corrosion of carbon under harsh OER potential necessitates additional caution when determining OER activity from the overall oxidation current. The use of a rotating ring-disk electrode (RRDE) is acknowledged for its ability to quantitatively determine the faradaic efficiency of the OER. [1] However, for practical applications, the generation of oxygen bubbles can cause unpredictable disturbance, leading to the erroneous collection efficiency. In this study, we aim to establish a dynamic current-response collection efficiency during the generation of oxygen bubbles. This was achieved by modelling with an Au/Au RRDE, well-known for its electrochemical stability under harsh conditions. In addition, using this calibrated collection efficiency, we investigate the influence of perovskite catalysts on the degradation behaviors of carbon materials at OER potentials in alkaline media. Materials and electrochemical measurements Measurements of oxygen gas collection efficiency were conducted using a modeled RRDE comprising an Au disk electrode and an Au ring electrode. The RRDE served as the working electrode, with a Pt wire as the counter electrode, a reversible hydrogen electrode (RHE) as the reference electrode, and a solution of Ar-saturated 1 mol dm-3 KOH as the electrolyte. The disk electrode underwent a 5-minute chronopotentiometry with varied oxidation currents, while the ring electrode underwent chronoamperometry at 0.3 V (vs. RHE). The collection efficiency was calculated from the ring current attributed to the oxygen 2-electron reduction reaction.Two kinds of perovskite catalysts, namely Sr2Co0.8Fe0.2O3Cl[2] (hereafter SCFOC) and LaCoO3 (hereafter LCO), and two carbonaceous materials, namely graphitized carbon black (TOKABLACK#3845, hereafter TB) and ketjen black (EC-600JD, hereafter KB), were used to evaluate the influence of perovskite on the carbon degradation behavior. Four composite catalysts, each comprising perovskite and carbon with a weight ratio of 5:1, were loaded on a disk electrode of the glassy carbon disk/Au ring RRDE. A cell analogous to the aforementioned design was assembled. Electrochemical measurements were conducted through chronoamperometry, employing various potentials at the disk electrode, and maintaining a potential of 0.3 V vs. RHE at the ring electrode, for a duration of 5 minutes. Results and discussion Figure 1 illustrates a three-dimensional representation of the oxygen gas collection efficiency of the Au/Au RRDE as two functions of disk current density and measurement time. It was evident that the oxygen gas collection efficiency varied significantly from the theoretical value (25.6 %) and was dependent on the disk current density and measurement time. The constrained solubility of oxygen in aqueous solution and the hydrophobic nature of the PTFE between the ring and the disk might cause a decrease in the collection efficiency due to the partial retention of oxygen bubbles on the electrode as the oxygen generation current increased and the measurement time elapsed. This suggests that, unlike typical solution reactions, the dynamic determination of the oxygen gas collection efficiency is essential, considering current density and measurement time.Figure 2 illustrates the computation of faradaic oxygen efficiency, utilizing dynamic oxygen collection efficiency. The composite catalyst composed of TB and SCFOC was taken as an illustrative example. The variation in collection efficiency, synchronized with the shape of disk current density, was employed in determining the faradaic oxygen efficiency. This dynamic collection efficiency yielded a comparatively smooth faradaic oxygen efficiency.Utilizing the calibrated faradaic oxygen efficiency, we proceeded to assess the capacity of carbon degradation by integrating the current density of the carbon oxidation reaction (COR) calculated by subtracting the OER current from the overall current. As depicted in Figure 3, the COR capacity as a function of the potential suggested that the components of the composite catalysts had distinct impacts on carbon degradation. Specifically, SCFOC appears to enhance degradation, whereas LCO exhibits a comparatively less pronounced effect.A more comprehensive discussion of these findings will be presented at the upcoming meeting.[1] I.S. Filimonenkov et al., Electrochim. Acta 321, 134657 (2019).[2] Y. Miyahara et al., Chem. Mater. 32, 8195 (2020). Figure 1

Benchmarking Local pH of Electrocatalysts for Water Electrolysis Using the Rotating Ring-Disk Electrode Technique

Water electrolysis is an important route for production of green hydrogen and remains a field of active research in pursuit of improved electrocatalytic activity and durability. Operating with a near-neutral feed is critical for this technology to be more widely adapted, because it allows the direct use of various water sources and imposes less stringent requirements on the components of the electrochemical cell.During water electrolysis, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) involving protons and hydroxides can experience a significant change in local pH at the surface of the catalyst, especially in near-neutral bulk conditions. This change in local pH is usually dictated by the reaction conditions such as electrolyte composition and mass transport within the system. Notably, there has been an increase in development of catalysts for water electrolysis with the ability to modulate their local pH in recent years. 1–6 However, comparing and quantifying the local pH modulation effects of these catalysts is challenging due to varying experimental techniques and protocols. The rotating ring-disk electrode (RRDE) with a potentiometric pH sensing ring has been presented as a promising and facile tool for in-situ local pH detection. 3,4,7,8 The local pH at the disk is estimated from the ring pH through solving the convective-diffusion equation under the well-defined mass transport conditions of an RRDE system. 8 In this study, we have investigated the local pH of iridium oxide during OER in both unbuffered and buffered electrolytes under near-neutral to alkaline bulk conditions using the RRDE technique. Our results provide benchmarks for future studies on the local pH modulation effects of catalysts and insights into the impact of electrolyte composition on local pH. In combination with mass transport modelling, we further examined the limitations of this technique and provide suggestions for best practices. References X. Liu et al., Appl. Catal. B Environ., 331, 122715 (2023).Z. Li et al., Angew. Chemie Int. Ed., 62, e202217815 (2023).J. Guo et al., Nat. Energy, 8, 264–272 (2023).X. Zheng et al., Nat. Commun. 2023 141, 14, 1–13 (2023).X. Wang, C. Xu, M. Jaroniec, Y. Zheng, and S. Z. Qiao, Nat. Commun. 2019 101, 10, 1–8 (2019).H. Tan et al., Nat. Commun. 2022 131, 13, 1–9 (2022).Y. Yokoyama et al., Chem. Lett., 49, 195–198 (2020).W. J. Albery and E. J. Calvo, J. Chem. SOC., Faraday Trans. 1, 79, 2583–2596 (1983). Figure 1

Selectivity Study of Anodic Seawater Electrolysis Catalysts Using the Rotating Ring-Disc Electrode Method

Water electrolysis generating green hydrogen will play a vital role in achieving the net-zero 2050 goal; however, freshwater electrolysis will further strain an already strained supply of clean freshwater.1 If seawater electrolysis can be scaled successfully, it would provide an important source of green hydrogen. Current research on untreated, direct seawater electrolysis is limited, and only recently have studies emerged analyzing catalyst performance at near-neutral pH.2 At industrially-relevant current densities, the formation of corrosive hypochlorite must be considered as a secondary reaction.3 Hypochlorite forms through the chloride oxidation reaction (ClOR), which competes with the oxygen evolution reaction (OER) in seawater electrolysis.2 In this work, we discuss the limitations of the current methods for determining anodic catalyst selectivity between OER and ClOR. The short lifetime of hypochlorite can cause faradaic efficiency measurement methods such as titration or oxygen gas capture to become unreliable, as these tests require that the hypochlorite remain stable. Using a rotating ring-disc electrode (RRDE), we measure the selectivity of common OER catalysts in-situ (Figure 1a). Real-time hypochlorite sensing overcomes the challenge of measuring catalyst selectivity posed by the short lifetime of hypochlorite. Remarkably, a PtRu catalyst outperformed more common OER catalysts with the best in OER selectivity and low overpotential, a novel development in the field of near-neutral water electrolysis. We also determine that elevated heat and low chlorine concentration are conducive to improved OER selectivity on an IrO2 catalyst (Figure 1b). We hope this work will set the standard in catalyst benchmarking for seawater electrolysis catalysts and could lead to the development of catalysts for efficient, scalable, and sustainable hydrogen production from seawater. H. Jin et al., Sci Adv, 9, eadi7755 (2023) https://www.science.org/doi/10.1126/sciadv.adi7755.F. Dionigi, T. Reier, Z. Pawolek, M. Gliech, and P. Strasser, ChemSusChem, 9, 962–972 (2016) https://onlinelibrary.wiley.com/doi/full/10.1002/cssc.201501581.J. Guo et al., Nature Energy 2023, 1–9 (2023) https://www.nature.com/articles/s41560-023-01195-x. Figure 1. a) LSV profiles of common OER catalysts (solid line) and the corresponding faradaic efficiency (dashed line) for the OER, measured using the ring current of the rotating ring-disc electrode. Catalysts were tested in 0.5 M NaCl and buffered with KHCO3 to pH 8.5. b) A ternary plot depicting the effect of varying Cl concentrations and temperatures on the selectivity of an IrO2 catalyst at pH 8.5. Figure 1

Rotating Disk Electrode Studies of Benzaldehyde Oxidation on Group Ib Metals

Water electrolysis is a green means of producing hydrogen gas to be used as a fuel or reactant in key industrial processes such as ammonia production. The conventional system of oxygen evolution (OER) and hydrogen evolution (HER) suffers from slow kinetics at the anode and a high cell voltage limited by thermodynamics. One solution is to replace OER with another reaction such as an organic oxidation reaction that has a lower equilibrium potential and produces a valuable organic byproduct at the anode. Recent work has demonstrated that biomass-derived aldehydes such as furfural and 5-hydroxymethylfurfural can be selectively oxidized to their corresponding carboxylates and H2 on Cu-based anodes at low potentials (~0.1 VRHE) in alkaline media. In alkaline media, a hydroxide ion adds to the carbonyl carbon of an aldehyde molecule forming a gem diolate in solution phase. It is argued that dehydrogenation becomes more facile due to the weaker C-H bond of the gem diolate compared to the aldehyde form of the molecule. This may enable oxidation without the need for coadsorbed-OH. Additionally, aldehyde oxidation is only active on Au, Ag, and Cu electrodes at higher pHs.The aim of this work is to identify the conditions under which low potential oxidation of aldehydes and high anodic Faradaic efficiency to H2 occurs, namely, electrode material and applied potential. To avoid polymerization side reactions of furans in alkaline media, we studied benzaldehyde as a model compound which has also been shown to exhibit low potential oxidation and anodic H2. The activity (rate of aldehyde consumption) and selectivity (to anodic H2 versus H2O) were compared for the group Ib metals (Au, Ag, Cu), each of which demonstrates a relatively early onset potential (<0.4 VRHE) and generates anodic H2 at certain potentials. Rotating disk electrode studies with Koutecky-Levich analysis were conducted to separate mass transfer effects from kinetic current to compare the intrinsic activity of each electrode. Additionally, the average number electrons transferred per aldehyde molecule consumed was estimated from Koutecky-Levich analysis; the one-electron pathway combines the aldehyde hydrogens to H2 while the two-electron pathway requires an additional electron per aldehyde molecule to oxidize the hydrogen from the surface to form H2O. Rotating ring disk electrode studies were used to further validate the anodic H2 generation as a Pt ring was still able to oxidize H2 despite the presence of benzaldehyde. This was used as an additional means of estimating the selectivity to H2 as a function of potential.CVs for benzaldehyde oxidation on each metal are shown in Figure a. Peak current followed the order of Au > Ag >> Cu. Au reached a mass transfer limiting current, and Ag also showed an RPM dependence but did not reach full mass transfer limitations. Cu was the least active and did not show any mass transfer dependence. On the other hand, Cu has the earliest onset potential followed by Ag then Au. The average number of electrons transferred per aldehyde molecule according to RRDE measurements is shown in Figure b, where one electron represents H2 and two electrons represents H-oxidation to H2O. Cu had 100% selectivity to H2 over its entire potential window of activity (up to 0.45 VRHE). Au and Ag have high selectivity to H2 at low potentials but decreases to near zero H2 production in the range of 0.6-0.8 VRHE; the decrease in selectivity to H2 on Ag occurs slightly earlier than Au (~0.1 V). H2 selectivity is related to the inability of each metal to oxidize H to H2O at low potentials. Figure 1

FeMnO3/CNT as a synergistic bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions in alkaline medium

The development of highly effective and low-cost electrocatalysts for energy conversion and storage devices is triggered by the sluggish kinetics of oxygen reduction and evolution reactions. Perovskite-based oxides are identified as potential ORR and OER electrocatalysts in an alkaline medium. Thus, the present study discusses the synthesis and characterization of FeMnO3/CNT as a bifunctional catalyst with a low potential gap of 0.89 V. The FeMnO3/CNT composite was synthesized by the solution combustion method and characterized using spectroscopic and electron microscopic techniques. The increase in the ID/IG ratio obtained from the Raman spectra of the FeMnO3/CNT composite with respect to bare CNT indicates the functionalization of CNT. The ORR and OER characteristics of the FeMnO3/CNT composite were analyzed with rotating ring disc electrode and rotating disc electrode measurements. The LSV curve of the FeMnO3/CNT composite synthesized with 0.3g of CNT show better ORR and OER activity. The ORR activity measurements of the composite done in 0.1 M KOH electrolyte show a good onset potential of 0.95 V vs. RHE and a half-wave potential of 0.74 V. The HPRR studies show that the ORR reaction mechanism follows a 2e− + 2e− reduction pathway. The OER measurements in an alkaline medium show an onset potential of 1.63 V vs. RHE with a Tafel slope of 115.3 mV dec−1. Also, this work gives an insight into the fundamental understanding of the synergy between the perovskite and CNT, leading to an enhanced ORR and OER catalytic activity. In addition, the material exhibits good stability for ORR and OER stability studies.

Electrochemical CO2 Reduction at Surface Modified Silver Nanoparticles

CO2 capture and transformation into chemical fuels presents a useful carbon-neutral energy source to curb the effects of global warming if the electrocatalyst used is highly active, exhibits sufficient product selectivity, and is energetically efficient. Metal nanoparticles (NPs) have emerged as a promising class of catalysts for the electrochemical CO2 reduction reaction (CO2RR) and their product selectivity are expected to be further improved through surface modification with different ligands. The primary objective of this work is to compare the use of Scanning Electrochemical Microscopy (SECM) and Rotating Ring Disk Electrode (RRDE) to study CO2 reduction at silver nanoparticles (Ag NPs) modified with amino acids (cysteine and tryptophan) and Ag NPs synthesized by a citrate reduction method. RRDE studies showed the onset potential for CO2RR was earlier for both the Ag NPs with cysteine and Ag NPs with tryptophan than those with citrate. SECM showed earlier onset potentials for CO2RR than the RRDE experiment for every type of Ag NP as well as higher sensitivity in detecting the major CO2RR products such as formate and CO. SECM also showed less hydrogen formation for the Ag NPs with cysteine and Ag NPs with tryptophan.

The Influence of Alkali Cations on the Performance of Pt Electrodes in Kolbe Electrolysis of Acetic Acid

AbstractElectrochemical decarboxylation of carboxylic acids is considered a sustainable method to improve the quality of pyrolysis oil. In this study, we assess the effect of monovalent alkali cations (of the acetates) on the performance of Pt electrodes in acid decarboxylation and the competing OER, using various electrochemical methods. We reveal a strong cation dependence generally following the trend Li+&lt;Na+&lt;K+~Cs+ within a large pH range. Using rotating ring disc electrode measurements, we highlight the strong contribution of the oxygen evolution reaction particularly for electrolytes containing Li+ and Na+ which decreases the selectivity for Kolbe oxidation. In addition, the faradaic efficiency (FE) towards methanol ranges between 16 % (for Li+) and 29 % (for Cs+) at high solution pH (9 or 12). The observed trends are generally explained by a cation‐dependent interfacial pH and surface coverage of acetate, both lowest for Li. This is evident from differences in charge transfer resistance determined by impedance measurements and local pH measurements. Additionally, enhanced dissolution of Pt by Li+ is also proposed. This work highlights that K+ and Cs+ cations favor FE for electrochemical Kolbe oxidation, at relatively low current densities.

Removing 65 Years of Approximation in Rotating Ring Disk Electrode Theory with Physics-Informed Neural Networks.

The rotating Ring Disk Electrode (RRDE), since its introduction in 1959 by Frumkin and Nekrasov, has become indispensable with diverse applications in electrochemistry, catalysis, and material science. The collection efficiency () is an important parameter extracted from the ring and disk currents of the RRDE, providing valuable information about reaction mechanism, kinetics, and pathways. The theoretical prediction of is a challenging task: requiring solution of the complete convective diffusion mass transport equation with complex velocity profiles. Previous efforts, including by Albery and Bruckenstein who developed the most widely used analytical equations, heavily relied on approximations by removing radial diffusion and using approximate velocity profiles. 65 years after the introduction of RRDE, we employ a physics-informed neural network to solve the complete convective diffusion mass transport equation, to reveal the formerly neglected edge effects and velocity corrections on , and to provide a guideline where conventional approximation is applicable.