bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transient Modeling and Optimization of a PEM Electrolyzer for Solar Photovoltaic Power Smoothing
Authors: Vudata Sai , Wang Yifan , Fenton James M. , Brooker Paul 
Published: July 2022

While renewable energy fuel has always had no cost, in the past the cost of the energy conversion technology was prohibitive. Today, due to improved efficiency in the technology and substantial increases in manufacturing volume the cost to generate electricity from the renewables and the cost to store this electricity in lithium-ion batteries for four hours has made these technologies more than competitive with traditional sources. As higher renewable energy penetrations occur the variability and intermittent nature of solar photovoltaic (PV) electricity can cause steep ramping of conventional power plants, so longer term energy storage (days, weeks, instead of hours) will be needed to increase the reliability of grid operation. In Florida cloud cover of a PV field can cause rapid fluctuations of PV output requiring a fast response to smooth out the PV electric power output. A polymer electrolyte membrane (PEM) electrolyzer can serve as a utility controllable load that can be available at all times and the produced hydrogen can be sold or converted back into electricity directly through a PEM fuel cell. To study the integration of renewable solar with hydrogen for increasing grid reliability, a multi-software power control method and a transient thermal electrochemical PEM electrolyzer model has been developed.
One-dimensional ("through-plane") and two-dimensional ("through-plane" and "in-plane") un-steady state models using gPROMS 2.1.1. were developed. The model considers mass, energy, momentum and current balance equations. The thermal energy balance considers the heat transfer through the backing layer, the flowfield plates and the gas and liquid flows. Kinetic parameters used in the model were determined using parameter estimation of single cell steady state polarization curves [1]. The single cell unsteady state models were extended to a stack model by adding cells in series and parallel. Real-time PV data taken from a 8.9 MWAC solar farm from Orlando Utilities Commission’s Stanton Energy Center was scaled up to 75 MWAC to design the electrolyzer that would be sized with the typical utility PV installation in Florida. The 75 MW PV data was smoothed using a power control strategy developed in MATLAB. The developed multi-software power control method and the electrochemical dynamic stack model shows the effectiveness of an electrolyzer in smoothing the PV signal to increase the grid stability and flexibility. Results are presented of different size electrolyzers to minimize short term cloud cover spikes in power while maximizing hydrogen production and the effectiveness of the electrolyzer.
[1] Vincenzo Liso, Giorgio Savoia, Samuel Simon Araya, Giovanni Cinti and Søren Knudsen Kær, “Modelling and Experimental Analysis of a Polymer Electrolyte Membrane Water Electrolysis Cell at Different Operating Temperatures”, Energies, 11 (2018) 3272. doi:10.3390/en11123273
Experimental and Numerical Studies of the Effect of Microstructure of Ionic Conductors on Generation of Hydrogen in Solid Oxide Electrochemical Cells (SOC)
Authors: Kupecki Jakub , Niemczyk Anna , Jagielski Stanisław , Zurawska Agnieszka , Kluczowski Ryszard , Kosiorek Magdalena 
Published: July 2022

Ceramic ionic conductors are applied in innovative systems for highly efficient and clean power generation. The oxygen separation membranes and solid oxide fuel cells (SOFC) and solid oxide electrolyzers (SOE) can be the examples.
Influence of various structural properties of ceramic ionic conductors which are used for solid oxide fuel cells was well-defined and described using several mathematical models. Such parameters as ionic and electronic conductivity, porosity, tortuosity, shape and distribution of pores were included. In case of solid oxide electrolysis cells, effects of these parameters on the electrolysis reaction remain unclear and obscure. There is no clearly defined correlation, neither there is an optimization tool for modification of the parameters to maximize the performance of solid oxide cell operating in regenerative mode. For that reason it is necessary to perform a complete comprehensive analysis combining both the experimental and numerical techniques to identify the key microstructural parameters and their correlation with the performance of electrochemical reaction. The work was aimed at verification of data presented in earlier studies which advised that porosity of electrodes of SOEs needs to be different than in the case of SOFCs, however different values were claimed. Mingyi et al. [1] indicated that optimum porosity for SOEC is about 45%, however several other studies advised on different values.
This paper presents results of numerical simulations and correlation of material properties with operational characteristic of a solid oxide electrochemical cell which were followed by initial experimental investigations towards validation of the numerical model, including the analysis of selected operational states. Model was established on the basis of theoretical correlations between microstructural parameters and macro-level performance. It was used for performing variant analysis of different modes of operation under varied conditions. The outcomes of the numerical investigations made it possible to define the requirements for fabrication of modified cells for high temperature electrolysis which were studied.
The work presents preliminary results of electrochemical characterization of modified cells and an attempt to generalize the model of SOC customized to highly efficient electrolysis.
The general concept of optimizing the performance of SOE by fine-tuning of the microstructure which was proposed earlier [2] is assessed throughout experiments using in-house 50 mm x 50 mm cells fabricated in the Institute of Power Engineering. The proposed path for tailoring the microstructural properties is presented and discussed.

References

[1] L. Mingyi, Y. Bo, X. Jingming, Ch. Jing, Int J Hydrogen Energy. 2010,35,2670-2674.
[2] J. Kupecki, J. Milewski, ECS Trans. 2018,83(1),171-178.

Figure 1
(Invited) Understanding Oxygen Distribution in the Porous Transport Layer of Proton Exchange Membrane Water Electrolyzer (PEMWE) Using x-Ray Computed Tomogrpahy
Authors: Kulkarni Devashish , Zenyuk Iryna V. 
Published: July 2022

To reach Department of Energy (DOE) target of 1$ cost for 1 kg of H2 production in 1 decade the cost of green hydrogen generation needs to decrease. IrOx is a used as an electrocatalyst in anode electrode of proton exchange membrane water electrolyzers (PEMWE) and its loading must decrease below 2 mg/cm2 to reach the cost targets for electrolysis. One of the hurdles of catalyst layers with low IrOx loading is the inplane electric conductivity, which will be low as IrOx is not supported by carbon or other conductive additive. Therefore, the design of porous transport layers (PTLs) becomes critical to ensure a good interface contact area with the catalyst but at the same time optimal oxygen removal from the catalyst. In our earlier study we showed that PTLs with intermediate porosities of ~60 % achieved this goal [1]. In this work we use operando x-ray computed tomography to visualize oxygen transport inside the PTLs for the cells having various catalyst loadings and various PTLs (sintered and fiber). Using a staining agent of NaI we were able to differentiate between water and oxygen as shown by Figure 1. Oxygen transport pathways and oxygen content within the PTLs was studied using various cell configurations and current densities. This work will identify a path forward for designing PTLs for PEMWE.
References:

Peng, X., Satjaritanun, P., Taie, Z., Wiles, L., Keane, A., Capuano, C., Zenyuk, I. V., Danilovic, N., Sci.2021, 8, 2102950.

Figure 1
(Invited) Electrified Resource Recovery Via Nutrient Reduction from Wastewater
Authors: Daramola Damilola , Trembly Jason 
Published: July 2022

Significant anthropogenic activity has been crucial in maintaining global population growth by fixing macronutrients required for crop growth into the soil. Two of these macronutrients – nitrogen (N) and phosphorus (P) – are also responsible for detrimental environmental impact via eutrophication. This eutrophication is driven by excess application of inorganic fertilizer products and organic animal waste from animal feeding operations; components that eventually end up in natural bodies of water due to erosion and leaching. Furthermore, in digester-equipped municipal wastewater treatment facilities, elevated N and P levels in the liquid stream recycled to the head of the facility drives increased resource consumption for nutrient reduction: chemicals for P management and energy for N management. Therefore, opportunities exist to simultaneously minimize environmental impact and energy consumption through improved nutrient management techniques, thus addressing issues at the Food-Energy-Water nexus.
Various electrochemical techniques are in early-stage development for an electrified approach to recovering these nutrients and reducing their environmental impact including bio-electrochemical1, electro-deionization2 and electrocoagulation3 approaches. This talk will focus on the indirect electrochemical approach: oxygen/water reduction to promote favorable pH conditions at the electrode surface for nutrient precipitation. Preliminary work4,5 has shown the viability and utility of this approach for nitrogen and phosphorus reduction in synthetic wastewater simulating animal waste. Additional findings describing the impact of competing ions, mass transport and electrolyte thermodynamics on nutrient reduction and recovery will be presented at the conference. An outlook on how this approach impacts energy consumption within the context of decarbonization of the manufacturing sector will also be discussed.
References

Y. Lei et al., ACS Sustain. Chem. Eng., 7, 8860–8867 (2019).

Y. Bian, X. Chen, L. Lu, P. Liang, and Z. J. Ren, ACS Sustain. Chem. Eng., 7, 7844–7850 (2019).

L. Kékedy-Nagy et al., J. Am. Chem. Soc., 142, 18844–18858 (2020).

Z. Belarbi and J. P. Trembly, J. Electrochem. Soc., 165, E685–E693 (2018).

Z. Belarbi, D. A. Daramola, and J. P. Trembly, J. Electrochem. Soc., 167, 155524 (2020).
Cell Culture Monitoring using Coplanar Electrochemical Transistors
Authors: Williams Kia , Fanjul Pablo 
Published: July 2022

In vitro cell death process monitoring is a method widely used in medical and pharmacological studies to know the effect of drugs and toxins on tissue models. This work presents a study of cell viability using commercial platforms designed for the generation of electrochemical transistors as sensor devices for different cultures of HEK294 embryonic kidney cells. In this work, we cover the idea of using an electrochemical transducer-based device to measure the number of cells deposited or growing on the source-drain channel. Using this method, it has been observed that the deposited cells behave like the semi-conductor material. Therefore, drain-source intensity versus gate-source voltage varies depending on the number of cells that are covering the drain-source system, with the measured intensity increasing with the growing number of cells.
The electrochemical signals of different cultures have been compared to the number of cells measured by microscopy and a correlation has been performed. Different cell cultures have been evaluated before and after, and considerable decreases in current intensity have been observed, indicating that damage has taken place.
Therefore, these transistors have proven to be an alternative for the study of cell viability, maintaining the integrity of the sample and being able to increase the number of studies performed on it. In addition, the monitoring of the evolution of cellular activity can be performed simpler and faster, providing comparable results with the advantage of maintaining a usable sample.
This work was supported by the Project "NANOBIO-TEER" (IDE/2018/000485 and IDE/2018/000415), co-financed through IDEPA and ERDF fund.
(Digital Presentation) Facile Synthesis of Pillar[6]Quinone and Investigation of Its Electrochemical Properties
Authors: Hirohata Tomoki , Shida Naoki , Ogoshi Tomoki , Tomita Ikuyoshi , Inagi Shinsuke 
Published: July 2022

Pillar[n]arene (n: number of units), macrocyclic para-arylene methylene molecules, have attracted attention owing to their symmetrical structures, host-guest properties, and original supramolecular assembly characteristics.1 Similarly, their quinone counterparts, pillar[n]quinone (P[Q]n), are also fascinating macrocycles containing electron-deficient quinone units, and therefore have potential application for novel host-guest chemistry and redox active materials. A hexagonal molecule, pillar[6]quinone (P[Q]6), is expected to form densely packed structures and a candidate for organic active material but the synthesis of P[Q]6 still remains a challenge.
We previously demonstrated that the electrochemical oxidation (1.0 V vs. SCE) of 1,4-dihydroxypillar[6]arene (P[HQ]6) in methanol afforded micrometer scale hexagonal cylindrical depositions on electrode surfaces, which were composed of partially oxidized P[HQ]6-m[Q]m (composed of both hydroquinone and benzoquinone units) aggregating via quinhydrone formation.2

In this work, we successfully synthesized P[Q]6 for the first time by oxidation of its hydroquinone precursor P[HQ]6. Electrochemical oxidation (1.2 V vs. SCE) of P[HQ]6 in methanol gave the similar hexagonal cylindrical crystal of P[Q]6 evidenced by single crystal X-ray diffraction, NMR and HRMS analyses. In the crystallographic data, all quinone moieties seem to have intermolecular CH-O interaction between adjacent macrocycles, resulting in the formation of a hexagonal packing structure. In addition, we also found that scalable synthesis of P[Q]6 was possible by chemical oxidation of P[HQ]6 with phenyliodine(III)bis(trifluoroacetate) in 1,1,1,3,3,3-hexafluoro-2-propanol.
To understand the electrochemical properties and electron-transfer behavior of P[Q]6, various voltametric studies were carried out. We revealed that three electrons are injected first, followed by stepwise three one-electron reductions due to the electrostatic repulsion in the latter electron-transfer process.
Reference

T. Ogoshi, T. Yamagishi, Y. Nakamoto, Chem. Rev.,
116, 7937 (2016).

C. Tsuneishi, Y. Koizumi, R. Sueto, H. Nishiyama, K. Yasuhara, T. Yamagishi, T. Ogoshi, Tomita and S. Inagi, Chem. Commun., 53, 7454 (2017).

T. Hirohata, N. Shida, H. Uekusa, N. Yasuda, H. Nishihara, T. Ogoshi, I. Tomita, S. Inagi, Chem. Commun., 57, 6360 (2021).

Figure 1
(Digital Presentation) Bipolar Electrolytic Micelle Disruption Method: Fabrication of Gradient and Patterned Organic Thin Films
Authors: Inagi Shinsuke , Zhou Yaqian , Shida Naoki , Tomita Ikuyoshi 
Published: July 2022

The method for the preparation of organic thin films (TFs) is significant due to its attractive potential applications in various devices such as photovoltaic cells, transistors and sensors. However, the conventional preparation methods are expensive and time-consuming. Besides, it is difficult to control the shape and the thickness of the film. In this study, a facile and general bipolar electrolytic micelle disruption (BEMD) approach was firstly established to fabricate a variety of gradient and circular TFs,1 benefiting from the in situ generated controllable potential distribution on a bipolar electrode (BPE).2

The micellar electrolytic solution was prepared by the addition of organic compound to an aqueous micellar solution containing electroactive surfactant of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA) or α-(11-ferrocenylundecyl)-ω-hydroxypoly(oxyethylene) (FPEG), and lithium sulfate (Li2SO4).3 The prepared electrolyte was used for bipolar electrolysis under different conditions.
A polymerizable monomer of N-vinylcarbazole (NVC) was solubilized in micelles composed of a cationic surfactant of FTMA, while copper phthalocyanine (CuPc) and aggregation-induced emission (AIE) compounds were dispersed in micelles constructed from a nonionic surfactant of FPEG. Here, a U-shaped bipolar electrolytic setup generated a sigmoidal potential distribution on the BPE, while a cylindrical bipolar electrolytic setup provided a site-selective potential feature on the BPE. When the micelles composed of electroactive surfactants moved to the BPE surface, the structure of micelles was disrupted selectively on the BPE surface with the oxidation of surfactants. In this process, various organic compounds incorporated into micelles were released on the localized area of the BPE, following the potential distribution. Finally, a variety of gradient and patterned organic thin films formed on the BPE surface. The gradient feature was characterized by UV–Vis analysis, thickness measurement and surface morphology analysis. Besides, modulation of the voltage applied to the driving electrodes or electrolytic solution allowed control of the film thickness.
References:

Y. Zhou, N. Shida, I. Tomita, S. Inagi, Angew. Chem. Int. Ed., 60, 14620 (2021).

N. Shida, Y. Zhou, S. Inagi, Acc. Chem. Res.,
52, 2598 (2019).

T. Saji, K. Hoshino, Y. Ishii, M. Goto, J. Am. Chem. Soc., 113, 450 (1991).

Figure 1
(Digital Presentation) Electropolymerization of Aromatic Monomers Using Streaming Potentials
Authors: Iwai Suguru , Shida Naoki , Tomita Ikuyoshi , Inagi Shinsuke 
Published: July 2022

Recently, there has been increasing attention on bipolar electrodes which work as a wireless electrode in the presence of external electric field.1 Since bipolar electrodes are driven with low concentration of supporting electrolytes, an electrosynthesis process using bipolar electrode can reduce the amount of waste after the electrolysis. We have already reported the electrochemical fluorination using a bipolar electrode system, in which the amount of supporting electrolyte used could be reduced to less than 1/100 compared to the conventional method.2 On the other hand, when pumping the solution with low concentration of supporting electrolyte into a narrow channel, potential difference between inlet and outlet of the channel, i.e., a streaming potential, generates to potentially be a driving energy for a bipolar electrode system.3

In this study, we have investigated the conditions in a flow cell to generate enough streaming potentials for electrode reactions. Then, electropolymerization of aromatic monomers such as pyrrole and 3,4-ethylenedioxythiophene has been achieved by driving a bipolar electrode using a streaming potential.
References

N. Shida, Y. Zhou, S. Inagi, Acc. Chem. Res., 2019, 52, 2598–2608.

K. Miyamoto, H. Nishiyama, I. Tomita, S. Inagi, ChemElectroChem, 2019, 6, 97–100.

I. Dumitrescu, R. K. Anand, S. E. Fosdick, R. M. Crooks, J. Am. Chem. Soc., 2011, 133, 4687–4689.

Figure 1
(Invited) Extracting Kinetics from Scanning Electrochemical Microscopy Images through Least-Squares Fitting of Reactive Discs
Authors: Leslie Nathaniel , Mena Morcillo Emmanuel , Morel Alban , Mauzeroll Janine 
Published: July 2022

The strength of scanning electrochemical microscopy measurements (SECM) is its ability to give insights into the kinetics of an underlying surface. Up to now there was no established way to extract kinetics from an SECM image. Our study fills this gap by proposing a method that fits the active area and kinetics of reactive sites from SECM images using the Levenberg-Marquardt algorithm and finite element method simulations.
Currently, the kinetics of reactions at a surface are quantified through SECM by performing approach curves: measuring the SECM current as the microelectrode approaches a surface vertically.[1] The theory used to fit approach curves assumes that the kinetics at the surface are uniform across an infinitely large surface. Realistically, sites at which reactions occur in SECM imaging are not infinitely large, leading to an under-estimation of kinetics at finite reactive sites. In some cases, approach curve theory can misidentify diffusion-limited surface reactions at small sites as being electron-transfer-limited. Our new method instead assumes that reactive sites are uniformly reacting discs. High agreement between the fitted and true areas of reactive sites are shown for both simulated and experimental SECM images. Less than 10% error was common for nearly-circular reactive sites. Diffusion-limited processes are not mislabelled as electron-transfer-limited by this method. The rate constants for electron-transfer-limited reactions were usually fit to within 15% error, much lower than the error experienced by the approach-curve method when applied to finite reactive sites.
[1] C. Lefrou, R. Cornut, Analytical Expressions for Quantitative Scanning Electrochemical Microscopy (SECM). ChemPhysChem
2010, 11, 547-556.
Why Methanol Electro-Oxidation on Platinum in Water Takes Place Only in the Presence of Adsorbed OH
Authors: Aran-Ais Rosa , Mekazni Dalila S. , Ferre-Vilaplana Adolfo , Herrero Enrique 
Published: July 2022

To optimize fuel cells performance using alcohols as fuel it is essential to untangle the mechanism of the methanol electro-oxidation on platinum in aqueous medium as a model reaction. Recent studies have pointed out the particular necessity of adsorbed OH for this electro-oxidation process to take place1. The here reported results, carefully obtained under low methanol concentrations on the three basal planes of platinum at different scan rates to discriminate between oxidation and adsorption processes, confirm such an unforeseen preceding observation2. It is elucidated that only when adsorbed OH is already present on the surface, adsorbed CO from methanol is formed. This observation is a clear indication that adsorbed OH is involved in the mechanism beyond providing the oxygen group required to oxidize adsorbed CO, which has never been considered before. The role played by adsorbed OH in the methanol electro-oxidation to CO on platinum in aqueous medium is supported by DFT calculations, as well as the reason why this reaction is not observed in the absence of adsorbed OH. A combination of kinetic and thermodynamic factors, such as the presence of multiple water molecules per methanol molecule, the high adsorbed OH mobility on the surface, the favorable co-adsorption of methanol in the presence of adsorbed OH, and the favorable and virtually barrier-less hydrogen transference from the hydroxy group of methanol to adsorbed OH to yield water, result in the immediate activation of methanol (as soon as the molecule approaches the surface) through the favorable substitution of adsorbed OH by adsorbed methoxy. In this contribution it will be presented a change of paradigm in the understanding of how alcohols are electro-oxidized in reference systems thus having crucial implications in the search for better electrocatalysts.
References:
(1) Kamyabi, M. A.; Martínez-Hincapié, R.; Feliu, J. M.; Herrero, E. Effects of the Interfacial Structure on the Methanol Oxidation on Platinum Single Crystal Electrodes. Surfaces . 2019. https://doi.org/10.3390/surfaces2010014.
(2) Mekazni, D. S.; Arán-Ais, R. M.; Ferre-Vilaplana, A.; Herrero, E. Why Methanol Electro-Oxidation on Platinum in Water Takes Place Only in the Presence of Adsorbed OH. ACS Catal.
2022.