bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of the EMIM Cation on the CO2 Reduction Reaction on Gold
Authors: Richards Danielle , Percival Stephen J. 
Published: August 2024

The electrochemical CO2 reduction reaction (CO2RR) is emerging as a promising method to produce carbon neutral chemical feedstocks. Additives or co-catalysts in the electrolyte can lower the activation barrier for CO2RR, yielding faster conversion rates at lower voltages. Recently, electrocatalytic CO2 reduction mediated by ionic liquids (IL) has been reported but with conflicting accounts to whether the ILs benefit CO2RR or adversely, the competing hydrogen evolution reaction (HER).
We report the effect of added IL EMIM-Cl, specifically EMIM+, in aqueous solutions on the electrochemical CO2RR and competing HER on gold. We show the CO2 reduction current increases by ~1.5x with the highest amount of added EMIM+ relative to the pure electrolyte. Differential pulse voltammetry reveals an additional large change in the reduction current that only appears with both CO2 and EMIM+ present. Lastly, we use advanced electrochemical analysis methods to determine the reaction kinetics and preliminary evidence shows that the standard heterogeneous rate constant increases for the reaction at large overpotentials while the HER is suppressed at low overpotentials with EMIM+ present.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Investigating the Role of Mixed Oxides for Oxygen Evolution Reaction on Iridium Oxide Electrocatalysts
Authors: Tseng Cindy , Benetti Daniele , Yang Guangmeimei , Rao Reshma R , West Norton , Durrant James , Moore Katie , Stephens Ifan 
Published: August 2024

Ongoing concerns over anthropogenic emissions, fossil fuel sustainability, and related geopolitical aspects point to an increasing need for cost-effective renewable fuel sources. A promising solution is the generation of hydrogen via the catalytic splitting of water, which can be achieved with the aid of proton exchange membrane (PEM) electrolyzers. Notably, the anode material in current commercially available PEM electrolyzers is typically iridium oxide. Despite its effectiveness in facilitating the oxygen evolution reaction (OER), the use of iridium oxide poses challenges due to the scarcity and high cost associated with this precious metal. As the quest for sustainable energy intensifies, ongoing research explores innovative approaches, such as the incorporation of alternative materials and catalysts, to enhance efficiency while addressing the economic and environmental concerns associated with iridium oxide. Studies have shown that incorporating mixed oxides and switching the supports for iridium oxide catalysts help lower the iridium loading while enhancing the OER performance.1,2

In this study, we investigate a series of different sputtered, mixed iridium oxides (Ta, Ti, Ir). We use a rotating disk electrode system to benchmark the catalytic activity of different loadings of mixed oxides. To measure the intrinsic activity of each catalytic active site, we use a home-built operando UV-Vis system to quantify the populations of surface species as well as track the kinetics of different redox transitions during OER. We incorporate nanoscale secondary ion mass spectrometry to probe the migration of different mixed oxide species before and after electrochemical cycling and use kelvin probe force microscopy to estimate the conductivity through the different films. In this study, we show the importance of cooperative effects between neighboring iridium oxide species and the coordination of iridium that are responsible for enhanced OER performance. These results indicate that doping modulates coverage dependent interactions at the surface, which affects both the binding energetics and populations of rate limiting intermediates. We believe this study will serve as a steppingstone for future designs of more cost-efficient PEM electrolyzers.
(1) Oh, Hyung-Suk, et al. "Electrochemical catalyst–support effects and their stabilizing role for IrO x nanoparticle catalysts during the oxygen evolution reaction." Journal of the American Chemical Society 138.38 (2016): 12552-12563.
(2) Zheng, Ya-Rong, et al. "Monitoring oxygen production on mass-selected iridium–tantalum oxide electrocatalysts." Nature Energy 7.1 (2022): 55-64.
Simulation Studies of Interfacial Kinetics of Dye-Sensitized Solar Cells Photoanodes in Scanning Electrochemical Microscopy
Authors: Hamzat Wasiu abidemi , Momontenko Dmitry , Wittstock Gunther 
Published: August 2024

Approach curves in the feedback mode of scanning electrochemical microscopy (SECM) were simulated for photoanodes in dye-sensitized solar cells by finite element simulation using COMSOL Multiphysics and compared to experimental data for the sample set with varying the photoanode film thickness (ZnO, cobalt mediator, organic dye). This reveals quantitatively the effect of the mass transport limitation of the mediator diffusion and organic dye regeneration kinetics in the mesoporous photoanode. The simulation of the mesoporous material was made with a pseudo-homogeneous approach in two space dimensions.
The simulation allows to extract the maximum information content from the experimental data. The light adsorption was treated as exponential decay of intensity within the photoanode (Lambert-Beer law), electron injection in the conduction band of ZnO photoanode and loss mechanism was explicitly considered. The light illumination is homogeneous over the entire simulation domain of 1 mm in diameter. Just like in the experiment, the built geometry used for the simulation has a conducting blocking layer (0.6 µm in thickness) to prevent the recombination of electrons with the back contact. The porous dye-sensitized layer has a porosity of 50 - 60% and a thickness of 1- 10 µm. The inner surface holds the dye for absorbing light. The mediator diffuses in the pore of the photoanode (internal solution) and in the bulk of the electrolyte (external diffusion). The transparent conducting glass makes the boundary of the simulation domain. The electrolyte-platinum contact is not modelled. The selected boundary conditions are equivalent to the short-circuit operation of the cell.
Interestingly, the simulation suggests that built meshes which had earlier been used for porous electrode simulation could not adequately describe the electron concentration profile for thinner electrodes despite providing a correct ME electrode current for limiting cases. The mesh convergence analysis studies were made to optimize the mesh to reduce computation time and memory size. The electrons in the conduction band were quantitatively determined because transport in the semiconducting photoanode is primarily driven by a thermally activated trapping-untrapping mechanism that can be described by transport equations similar to Fick's laws.
The unknown parameters (dye absorption coefficient and recombination rate constant) were adjusted to ensure various light intensities in the simulation correspond to the experiment. An accurate description of the electrons within the semiconductor is critical for explaining the time-dependent behavior of the dye-sensitized photoanode in SECM approach curves. After obtaining agreement with experimental approach curves under steady-state conditions, the same parameters are used to study the current transient obtained under intermittent illumination.
Kinetics of Charge Reversal in the Double Layer Studied with an Electrochemical Quartz Crystal Microbalance (EQCM-D)
Authors: Langhoff Arne , Leppin Christian , Johannsmann Diethelm 
Published: August 2024

Normal pulse voltammetry on inert electrolytes was combined with a new electrochemical quartz crystal microbalance (EQCM) with millisecond time resolution, which allows to probe the kinetics of charge reversal in the diffuse double layer (DL) after a step in electrode potential. The QCM responds to the charge reversal because the local viscosity-density product depends on the type and the concentration of the ions. The time resolution was improved to 1 ms using multifrequency lockin amplification, which allows to study kinetic effects in dynamic electrochemistry, which were previously not accessible with gravimetry. The noise was lowered to less than 10 mHz by modulating the electrode potential and averaging Δf and ΔΓ over many modulation cycles.
The overtone scaling was found to be the same as in gravimetry (-Δf/n » const. and ΔΓ/n < -Δf/n with n the overtone order), which, however, is not caused by a deposition of a rigid film in the Sauerbrey sense. A Sauerbrey-type QCM response is also caused by changes in Newtonian viscosity inside a layer with a thickness far below the penetration depth of the shear wave (such as the double layer).
The frequency response in the electrolytes studied correlated well with the viscosity B-coefficients of the respective ions as employed in the Dole-Jones equation. The time constants inferred from gravimetry were similar to the time constants (the RC-times) from electrochemical impedance spectroscopy (EIS). There were small differences, which presumably go back to slow rearrangements inside the Helmholtz layer, which are not seen in EIS.
The QCM response to double layer recharging in inert electrolytes is of great importance for the interpretation of QCM results on processes involving Faradayic charge transfer. Such a response is omnipresent as a background and might be misinterpreted as a gravimetric signal.[1]

References
[1] Leppin, C.; Peschel, A.; Meyer, F. S.; Langhoff, A.; Johannsmann, D. Kinetics of Viscoelasticity in the Electric Double Layer Following Steps in the Electrode Potential Studied by a Fast Electrochemical Quartz Crystal Microbalance (EQCM). Analyst
2021, 146 (7), 2160–2171.
Caption: Shifts in frequency and bandwidth in response to potential steps (left). The gravimetric signal followed the steps with a delay of a few milliseconds. The amplitude and the response time depend on cation type (right). The counter ion was NO3
-. Both the amplitude and the response time correlate well with the viscosity B-coefficient.

Figure 1
Protic Ionic Liquids as Electrolytes for Metal-Hydride Batteries
Authors: Kurchavova Ekaterina , Chan Julie , Zhang Junxian , Cuevas Fermin , Mateos Mickael , Monnier Judith , Vivier Vincent , Turmine Mireille 
Published: August 2024

Nowadays, the most popular and effective energy storage systems are Li-ion batteries, despite some limitations such as high cost, flammability, temperature restrictions, and use of critical raw material (e.g. Co) [1]. This raises the challenge of the demand for alternative systems. One potential alternative is the Ni-MH battery, which are recognized for their good cyclability, competitive energy density, low memory effect, wide range of operating temperatures, low cost, and environmental friendliness [1]. Their practical use, however, is constrained due to their low specific energy density, high self-discharge rate, and electrode ageing [2,3].
This work is focused on the study of the negative electrode of the Ni-MH battery and its interaction with the electrolyte. The objective aims to improve the performance of the negative electrode of Ni-MH batteries by substituting the conventional water-based KOH 8.7 M electrolyte by a Protic Ionic Liquid (PIL) to overcome aforementioned drawbacks [4]. PILs can exchange a labile proton, thereby supporting the main redox reaction, hydrogenation, at the negative electrode of Ni-MH battery.
Thus, a series of twelve PILs or their combinations were synthesized and tested in a half-cell configuration. The charge/discharge cycle tests were carried out. Results showed that Pyrrolidinium Acetate (PyrrAc), Ethanolammonium Acetate (EOAAc) mixed with g-butyrolactone (GBL), and Diethanolammonium Acetate (DEOAAc) exhibited promising performance in half-cell configuration (Table 1).
PyrrAc was shown to be an optimal electrolyte and has been further studied in terms of long-term performance and system degradation. The morphology of the aged negative electrodes was observed by Scanning Electron Microscopy (SEM) (Fig. 1). For instance, after 7 cycles of charge/discharge, formation of cracks was observed in the electrode (Fig. 1 (right)) due to hydrogen ab/desorption.
The utilization of PyrrAc as electrolyte resulted in no initial capacity loss and, moreover, exhibited an increase in capacity during the first cycles, which can be recognized as an activation of the electrode (similar to the one observed in aqueous electrolytes). In order to obtain a complete understanding of the electrode stability, the electrolytes after cycling as well as calendar corrosion were studied using Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES).
[1] M.A. Hannan, M.M. Hoque, A. Mohamed, and A. Ayob, Renewable and Sustainable Energy Reviews, 69 (2017) 771–789.
[2] B. Puga et al., ChemElectroChem, 2 (2015) 1321–1330.
[3] J. Matsuda, Y. Nakamura, E. Akiba, J Alloys Compd, 509 (2011) 7498–7503.
[4] T. Meng, K. H. Young, D. F. Wong, and J. Nei, Batteries, 3 (2017) 4.

Figure 1
Speciation and Diffusivity of Hydrogen in Molten 2LiF-BeF2 for Nuclear Fission and Fusion Applications
Authors: Williams Haley , Falkowski Zachary , Scarlat Raluca O. 
Published: August 2024

The behavior of hydrogen isotopes in molten 2LiF-BeF2 (FLiBe) is of interest to both advanced fission and fusion reactor designs. Tritium (hydrogen-3) is both a fission product and neutron activation product of lithium-6 fluoride in fission reactors which use FLiBe as a heat transfer fluid. In this case, tritium is an undesirable side product. In fusion reactors, FLiBe may be used as a blanket around the plasma which, upon neutron irradiation, generates tritium by the same neutron–Li-6 reaction. Here, tritium is a necessary and desirable product; the tritium is used to continuously fuel the deuterium-tritium fusion reaction. A thorough understanding of tritium’s behavior and residence time is relevant to managing tritium inventories in fission and fusion systems, which is essential for both the safety cases and functional operation of these reactors. Using hydrogen as a non-radioactive surrogate for tritium, we study the speciation and diffusivity of hydrogen in molten FLiBe at various temperatures relevant to reactor operating conditions.
Here we present results of electrochemical investigations of hydrogen in FLiBe using cyclic and square wave voltammetry. We introduce hydrogen to FLiBe through 1) LiH additions and as 2) H2 gas, electrochemically desorbed from graphite. The expected solubility of H2 in FLiBe at 1 atm partial pressure is as low as 1 appm. Previous studies saw a higher apparent solubility of H2 at atmospheric pressure (up to 8000 appm). The possible presence of the postulated quasi-stable intermediate BeH2 is explored to explain the high apparent solubility of H2. The two methods of introducing H (as LiH reacting with BeF2 to form BeH2, which decomposes to H2, and the surface reduction of H2 on graphite) are compared to investigate the different species in which hydrogen may exist in molten FLiBe. Additionally, we attempt to quantify the diffusivity of these hydrogen species in FLiBe at 500ºC and 800ºC and compare findings with predicted diffusivities from computational models of Be and H additions to FLiBe. Overall, these studies seek to elucidate the speciation of hydrogen in FLiBe to aid in the management and operation of fission and fusion systems.
Preparation of Semiconducting Films By Electrooxidation of Naphthalene
Authors: Prus Agnieszka Marta , Leszczyński Piotr Jerzy , Jurczakowski Rafał 
Published: August 2024

Due to promising electronic and optical properties, conductive polymers are attracting significant interest. Conductive polymers find applications in electronic devices, e.g. substituted polynaphthalenes are used as blue light sources in OLEDs1. The ability to block the substitution sites where the subsequent polymer unit may be added by functional groups allows the polymer structure to be designed2. Moreover, one of the benefits of conductive polymers is the ability to modify the band gap of these materials by adding substituents to the main chain.
Naphthalene, as the smallest polycyclic hydrocarbon, is an interesting precursor for synthesis semiconducting materials. The anodic oxidation of naphthalene has been described several times in the literature3,4, however, only formation of 1,4-polynaphthalene in the form of a granular product has been reported.
In our research, we performed naphthalene electrooxidation and investigated the impact of the experimental conditions such as naphthalene concentration, water content, and electrode material on the obtained semiconducting materials. We used mass spectrometry to observe mass progression and determine molecular mass of the obtained polymers. The results of electron microscopy imaging showed fine quality coating. We studied the electronic properties of the polymers by cyclic voltammetry and impedance spectroscopy. Based on the results, we discussed the possible mechanism of the reaction.

Samanta, S. K. et al. Synthesis of high molecular weight 1,4-polynaphthalene for solution-processed true color blue light emitting diode. Macromolecules
51, 8324–8329 (2018).

Debad, J. F. & Bard, A. J. Electropolymerization of acenaphtho[1,2-k]fluoranthene derivatives: Formation of a new conductive electroactive electrochromic hydrocarbon ladder polymer. J Am Chem Soc
120, 2476–2477 (1998).

Zecchin, S., Tomat, R., Schiavon, G. & Zotti, G. Polynaphthylene films from anodic coupling of naphthalene. Synthetic Metals vol. 25 (1988).

Huang, Z., Qu, L., Shi, G., Chen, F. & Hong, X. Electrochemical polymerization of naphthalene in the electrolyte of boron trifluoride diethyl etherate containing trifluoroacetic acid and polyethylene glycol oligomer. Journal of Electroanalytical Chemistry
556, 159–165 (2003).
First-Principles Kinetic Monte Carlo Modeling of Passivation in Ni-Based Alloys
Authors: Kaufman Jonas , Xiao Penghao , Wood Brandon C. 
Published: August 2024

Corrosion by metal oxidation is a major problem for many structural materials, including Ni-based alloys in high-temperature applications. Passivation can be achieved through various alloying strategies, but common theoretical approaches to understanding key factors such as the critical concentration of the minor element are limited in their predictive capability. In particular, existing models often do not explicitly capture competing metal cation migration mechanisms in the oxide. In this study, we examine passivation kinetics of Ni-Cr and Ni-Al alloys by modeling the evolution of initial NiO oxide films as Cr/Al are incorporated. Surrogate models for the energies of various oxide configurations and the migration barriers of metal cations are parameterized from density functional theory calculations. These inputs are used to drive kinetic Monte Carlo simulations over long time scales. By tracking the time-dependent oxidation behavior across alloy composition, we predict critical concentrations of Cr/Al to form continuous passivation layers. Compositional and structural analyses of the simulated oxides are used to quantify fractions of different phases and provide insight into the nature of passivation in each alloy system. The effect of increasing or decreasing the exchange rate of metal atoms near the alloy-oxide interface, which can be related to alloy processing, is also explored. We discuss the applicability of our method to other systems and its incorporation into an existing open-source software package.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Nature's Catalyst: Investigating the Mechanisms behind Nitrogenase's N2rr Activity
Authors: Dheer Lakshay , Ablid-Pedersen Frank , Bajdich Michal 
Published: August 2024

Electrochemical nitrogen reduction reaction (eNRR), one of the most studied problems in catalysis, has the potential to replace the century-old Haber-Bosch process for ammonia synthesis. However, a low-cost, highly selective and efficient catalyst for eNRR is yet to be discovered. Nitrogenase, a naturally occurring biocatalyst responsible for nitrogen conversion to ammonia under ambient conditions, is the most efficient catalyst for eNRR. The Iron-Molybdenum cofactor (FeMo-co) in the enzyme is identified as the catalytic part with bridging irons being active sites. Despite decades of work the exact mechanism of its operation and various intermediates along the pathway are still debated. We revisit eNRR on FeMo-co and decipher the key mechanisms at play.
Most studies on FeMo-co tend to ignore the magnetic nature of transition metals (TMs) in the cofactor. Proper treatment of these TMs (Fe and Mo) is necessary to pinpoint the intermediates and potential limiting step along the eNRR pathway. We start with an iterative optimization of the Hubbard U parameter to capture the correct magnetic structure of the cofactor. We also explore the effect of local chemical environment including, H-coverage and various ligands attached to the cofactor, on its activity and selectivity. The potential limiting step is found to be sensitive to the magnetic orientation of the TMs in the cofactor and it is thus imperative to provide the U correction to capture the true bottleneck of eNRR. The cofactor also shows an affinity towards a medium H-coverage under eNRR operating conditions. These findings provide a comprehensive and elaborate view of nitrogen reduction on FeMo-co and insights from this study paves the path towards designing heterogeneous counterparts to the catalyst.
Acknowledgments:
This work was supported by the U.S. Department of Energy, via Grant DE-FOA-0002676 to the SUNCAT Center for Interface Science and Catalysis.
Bubble Transport in Porous Media for Electrochemical Applications
Authors: Guo Jack , Lin Tiras Y , Seung Kansas , Davis Jonathan T. 
Published: August 2024

Bubbles and their flow dynamics strongly impact the performance of gas-evolving electrochemical systems with porous electrode architectures. The presence of bubbles on the electrode surface reduces the number of active catalytic sites that are accessible for the liquid electrolyte, leading to limitations in mass transport and/or reaction kinetics. Additionally, bubbles can obstruct the flow of liquid electrolyte that is able to pass through the porous structure, leading to pressure buildup. Therefore, to mitigate bubble blockage, optimal electrolyzer performance requires understanding bubble dynamics within the porous electrode in the presence of an applied flow; an accurate and complete physical model of this setup is not yet available. Here, we present volume-of-fluid simulation results and a theoretical framework to describe the bubble/electrolyte/electrode interaction, i.e. the triple phase boundary, ultimately with an aim to predict whether the bubble does or does not break through the porous media. Informed by the numerical results, the constructed theory describes the interaction of buoyancy, surface tension, and pressure drop for the range of different porosities, bubble sizes, and electrolyte flow rates. Comparison of these results with experimental findings are discussed. This work serves as a first step in building the framework for the design and optimization of relevant porous media systems that aim towards the improved control of bubble dynamics.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL release number: LLNL-ABS-857509.