bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalyst Deactivation on Transition Metal Oxides during Ammonia Electrooxidation
Authors: Chen Sijie , Zheng Weiran 
Published: December 2024

Electrochemical ammonia oxidation reaction (AOR) offers a sustainable approach for waste ammonia remediation, energy conversion, and valuable product production.[1] Despite the promise of transition metal oxides as effective catalysts, the AOR mechanism on their surface remains elusive, along with factors leading to deactivation, which often involve surface poisoning species formation and site corrosion. Moreover, the AOR potential overlaps with the oxygen evolution reaction (OER), leading to the formation of O2 as a byproduct and an overall decline in energy efficiency. Therefore, it is critical to understand the molecular behavior of ammonia and other species on the oxide surface under reaction conditions.
In this work, we systematically investigate the AOR mechanism on NiOOH and CuOOH, emphasizing the influence of OER and dissolved O2, which has been previously largely overlooked. Utilizing three in situ techniques: differential electrochemical mass spectrometry (DEMS) for detecting gaseous intermediates and products, Raman spectroelectrochemistry for monitoring surface transformations, and UV-vis spectroelectrochemistry for observing species within the electrical double layer, we reveal that the formation of NiOOH/CuOOH, the AOR catalytic activity and selectivity, and the deactivation pathway are all significantly modulated by OER and the presence of O2.
It is established that AOR on NiOOH is potential-dependent, with N2 production being initiated at potentials coinciding with OER commencement and the generation of NOx species being favored at elevated potentials (Figure 1 left). Moreover, OER competes with the AOR to N2 pathway but promotes the AOR to NOx (N2O, NO, and NO2), which is further elucidated through the protective role of O2 to remove *N poisoning species, mitigating surface deactivation and decreasing charge transfer resistance (Figure 1 right). On CuOOH, however, the O2 can promote NO formation and Cu dissolution from the CuOOH layer, leading to complete deactivation at high potential. Our findings offer an in situ insight into the AOR mechanisms on metal oxides with co-existing OER and provide a critical direction for designing electrocatalysts for environmental applications, particularly for systems where long-term electrolysis is desired.

Figure 1. Left: DEMS results during linear sweep voltammetry of NiOOH electrode in Ar/O2-saturated electrolytes (1.0 M KOH + 100 mM NH3).
Right: Electrolysis results of NiOOH electrode in Ar/O2 saturated electrolytes (1.0 M KOH + 100 mM NH3) at various potentials.

References

MacFarlane, D. R.; Cherepanov, P. V.; Choi, J.; Suryanto, B. H. R.; Hodgetts, R. Y.; Bakker, J. M.; Ferrero Vallana, F. M.; Simonov, A. N. Joule, 4 (6), 1186-1205 (2020).

Figure 1
Utilizing Cladding Processes to Enhance Structural Stability of Aluminum-Foil Anodes for Rechargeable Lithium Batteries
Authors: LIU Weiqi , Li Hongyi , Nakata Yuki , Matsumoto Shingo , Yamaguchi Takitaro , Hoshikawa Hiroaki , Kumagai Toshiaki , Ichitsubo Tetsu 
Published: December 2024

Al-foil anodes are attractive candidate materials for rechargeable lithium batteries owing to their high theoretical capacities (993 mAh g-1, Al+Li++e
-=LiAl) and low production costs. Within appropriate hardness and composition, the Al foils can work as self-standing anodes, where the surface layer reacts with Li as the active material, and the base layer remain unreacted to hold the structural stability as the current collector. However, during battery cycling, the base layer of Al foils is prone to be consumed due to surface passivation by cathodic decomposition products of electrolyte species. Eventually, the Al-foil anodes are totally pulverized, and the reversible capacity is completely diminished.
To limit the reaction depth and protect the base layer, we combine Al foils with various alloy additions (such as Si, Mn, and Mg) by roll-bonding processes to prepare clad foils. [2] The alloy additions change the mechanical properties of Al matrix and affect the lithiation potentials.[3] Thus, the clad Al foils with different alloy additions can create lithiation potential gaps to prevent the Li penetration into the base layer. In particular, the lithiation potentials of 99.99%Al, Al-1%Si, Mn-based A3003 and Mg-based A5052 foils are compared using galvanostatic intermittent titration technique (GITT) measurements. Among the various Al foils, A5052 shows lowest lithiation potential close to 0 V vs Li, where the hard matrix significantly retards the lithiation reaction. The clad foils of Al / A5052 and Al-1%Si / A5052 exhibit a lithiation potential gap up to 0.15 V. By setting the appropriate cutoff potential to utilize the lithiation potential gap, the Li penetration to the base layer is successfully blocked and the structural stability is enhanced.
[1] H. Li, T. Ichitsubo et al, Nat. Commun.
11, 1584 (2020).
[2] H. Li, T. Ichitsubo et al, J. Mater. Chem. A
11, 23311 (2023).
[3] T. Ichitsubo et al, J. Electrochem. Soc. 159, A14 (2011).
Bayesian Deep Operator Network-Based Optimization for Battery Thermal Management System
Authors: Kim KyungHyun , Choi Jung-Il 
Published: December 2024

This study tackles the critical need for efficient thermal management in battery systems, a key factor in improving the lifespan and performance of electric vehicles and energy storage applications. A groundbreaking method is introduced by utilizing the Bayesian Deep Operator Network (B-DeepONet) framework to develop a surrogate model capable of predicting and optimizing thermal behavior in battery systems across various operating conditions.
We first identify key variables that significantly influence the thermal management of battery packs. These variables lay the groundwork for generating simulation data through Finite Element Method (FEM)-based models. This data, spanning a broad range of battery configurations and thermal load scenarios, is crucial for training the surrogate model.
The model, constructed within the B-DeepONet framework, efficiently maps diverse battery configurations and operating conditions to their corresponding temperature distributions, effectively capturing the complex thermal dynamics. Incorporating uncertainty quantification capabilities enhances the model’s predictive accuracy and reliability, enabling significant advancements in system design even when data availability is limited. This proves particularly advantageous when obtaining high-quality training data is difficult or economically unfeasible.
Finally, the B-DeepONet-based surrogate model is employed to optimize the performance of battery thermal management systems, contributing to more efficient and sustainable energy solutions. This study not only advances predictive modeling in thermal regulation but also improves the ability to effectively manage thermal behaviors in complex battery systems.

Figure 1
Testing and Characterization of Tubular Na-ZnCl2 Battery Cells for Stationary Energy Storage
Authors: Solem Cathrine Kyung Won , Simonsen Thomas Park , Rørvik Stein , Wang Zhaohui , Sommerseth Camilla , Kjos Ole Sigmund 
Published: December 2024

The SALT battery (ZEBRA® battery) was first patented in 1978, and its technology is based on a liquid sodium (Na) anode in charged state, and a solid nickel (Ni) cathode in discharged state, having an electrolyte consisting of a molten nickel chloride/sodium chloride with sodium tetrachloroaluminate (NiCl2/NaCl-NaAlCl4) salt and a solid beta alumina (β''-Al2O3) electrolyte. The Na-NiCl2 cell operates at ~300°C to ensure a molten electrolyte and good Na+ conductivity, as the β''-Al2O3 also operates as a membrane allowing the Na+ ions to pass, but not the e-.
Today, the technology is commercialized, and industrial production sites exist in Switzerland and China. The SALT batteries are used for railways as a back-up energy supply, and in electric vehicles for the mining and construction market. The Na current collector is also the cell housing, making sure that the SALT battery cell is completely hermitized to avoid any contact with air and humidity, as the electrolyte is hygroscopic salts. It is, however, important to reduce the amount of Critical Raw Materials (CRMs) utilizing more abundant materials to make it more competitive for future markets.
In the SOLSTICE project, it has been investigated how the SALT battery can reduce and/or substitute Ni/NiCl2 with Zn/ZnCl2. The present work has covered characterization of a tubular Na-ZnCl2 battery cell, and measured the cell resistance by Electrochemical Impedance Spectroscopy (EIS), cell resistance when fully charged and discharged, as well as the post-mortem analyses, such as SEM and XRD. The study proved that Ni can be replaced by Zn in the full-size SALT battery cell, but the morphology still needs to be studied to optimize the chemistry.

Acknowledgments: This work has been funded by the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 963599.
Ether-Functionalized Phosphonium Ionic Liquids: Molecular Dynamics, Ion Conformation, and Intermolecular Interaction
Authors: Matsumoto Mitsuhiro , Nawate Shoki , Inoue Yohtaro , Tsunashima Katsuhiko , Yamada Hirohisa 
Published: December 2024

Ionic liquids have many potential applications because they have non-flammability, high thermal stability, high ionic conductivity, and so on. Among various types of ionic liquids, quaternary-phosphonium-cation-based ionic liquids (P-ILs) have better physicochemical properties such as ionic conductivity, potential window compared with corresponding quaternary-ammonium-cation-based ionic liquids (N-ILs). Therefore, we have considered that P-ILs are better suitable for applications in electrochemical devices such as electrolytes for lithium-ion batteries than N-ILs [1].
Recently, we spectroscopically demonstrated that such higher ionic conductivity for P-ILs can be explained by weaker intermolecular interaction between anion and cation [2]. This provided us a consideration that molecular interactions are controlling factors in translational motion of ions. For deeper discussion, we focused on the ether-functionalized P-ILs displayed in the Figure 1 because ether structure in phosphonium cations enhanced ionic conductivity and investigated by pulsed field gradient NMR (PFG-NMR), Raman, and terahertz spectroscopies.
Based on the PFG-NMR, we calculated transport number of each ion specie and found that transport number of P111(1O1) cation was slightly higher than that for P1113 cation. In Raman spectroscopy, we obtained enthalpy change in conformational change of anion (ΔH) and demonstrated that ΔH for P111(1O1)cation was somewhat lower than that for P1113 cation. Terahertz spectroscopy indicated the weaker intermolecular interaction of P111(1O1) cation with anion than that of P1113 cation. Despite these differences in P111X cations, such ether group effects were hardly observed in P222X cations, which would be due to the different symmetry of cation and steric hindrance.

References

[1] M. Matsumoto et al., (2023). Available at SSRN: http://dx.doi.org/10.2139/ssrn.4690007
[2] M. Matsumoto et al., J. Phys. Chem. B, 126, 10490 (2022).

Figure 1
Insight into Modulation of Ionic Liquids for Na-Ion Batteries: Cation Modification
Authors: Zhang Shaoning , Wada Hiroki , Wu Shengan , Hwang Jinkwang , Yoshii Kazuki , Matsumoto Kazuhiko 
Published: December 2024

Sodium-ion batteries (SIBs) have gained global attention as cost-effective energy storage solutions, thanks to the abundance of sodium resources. Ionic liquid electrolytes (ILs) are increasingly recognized as promising candidates for SIBs due to their advantageous properties, including low volatility, reduced flammability, and high electrochemical stability.[1-3] However, their application in SIBs is hindered by irreversible decomposition during the initial charging of negative electrodes, resulting in low initial Coulombic efficiency. Our recent research suggested that the addition of lithium with high Lewis acidity into ILs weakens the interaction between organic cations and anions, leading to the formation of unprotected cations.[4]
In this study, we investigate the interaction properties of ILs based on [C3C1pyrr][FSA]-based ILs ([C3C1pyrr]+= N-methyl-N-propylpyrrolidinium and [FSA]− = bis(fluorosulfonyl)amide) and their effects on the Coulombic efficiency at hard carbon negative electrodes for sodium-ion batteries. Furthermore, we explore the impact of pyrrolidinium cations with ether functional group ([Pyr1,2O1]+; N-methoxyethyl-N-methylpyrrolidinium) on the coordination environment of ions and the interfacial properties with negative electrodes through computational analysis.
Our series presentation, titled "Insight into Modulation of Ionic Liquids for Li-ion Batteries: Unprotected Cation", explains the effects of Li concentration on the coordination environment of ionic liquid in lithium systems.

Reference

[1] K. Matsumoto, J. Hwang, S. Kaushik, C.-Y. Chen, R. Hagiwara, Energy Environ. Sci. 12 (2019) 3247.
[2] K. Yoshii, T. Masese, M. Kato, K. Kubota, H. Senoh, M. Shikano, ChemElectroChem 6(2019)3901.
[3] M. Watanabe, M. L. Thomas, S. Zhang, K. Ueno, T. Yasuda, K. Dokko, Chem. Rev. 117, (2017), 7190.
[4] S. Zhang, S. Wu, J. Hwang, K. Matsumoto, R. Hagiwara, J. Am. Chem. Soc. 146 (2024) 8352-8361.
(Invited) Photoreactors for Benchmarking Outdoor Solar Hydrogen Production: Future Designs Based on Lessons from the Past
Authors: Deutsch Todd G , Oh Kiseok , Lenef Julia , Young James L. 
Published: December 2024

Outdoor testing under realistic environmental conditions, including natural (diurnal) solar illumination, is a necessary step in moving photoelectrochemical water-splitting technologies from the laboratory towards a deployed technology. This is because many have found that a good laboratory result does not translate to success in the field. This is both due to the scale of devices tested as well as simulated conditions not adequately representing the stresses materials will experience under “real” operating conditions. In the first part of this talk, we will describe lessons learned from previous experience in designing photoreactors and results from their outdoor testing in Golden, Colorado. Bubble management, temperature control, and auxiliary component durability are some of the issues we had to address.
In the second part of this talk, we will discuss how we have applied the knowledge gained our prior experience to design more advanced photoreactors. We will also describe a new testing platform we are designing and building that will be used to benchmark the performance of photoreactors based on several different photoabsorbers developed by partners in the HydroGEN advanced water-splitting technologies consortium.
(Invited) Experimental Insights into the Local Chemical Environment of Sulfur Atoms and Their Relevance in Photoelectrochemical Water Splitting Devices Made of Cu(In,Ga)(S,Se)2 and Other Things
Authors: Heske Clemens 
Published: December 2024

It is the purpose of this presentation to demonstrate how the unique capabilities of novel x-ray spectroscopy methods (in particular element-specific soft x-ray emission spectroscopy, XES) can be employed to derive important insights into PEC and other solar devices from the viewpoint of sulfur. Of course, other elements will also play a role, as will delocalized valence and conduction bands, but sulfur is unique and deserves to be celebrated.
The presentation will include results from lab-based x-ray and UV photoelectron spectroscopy, inverse photoelectron spectroscopy, and x-ray-excited Auger electron spectroscopy, complemented by XES and soft x-ray absorption spectroscopy using high-brilliance synchrotron radiation. A particularly powerful approach is their resonant combination, Resonant Inelastic soft X-ray Scattering (RIXS), best displayed in a “RIXS map”.
In the presentation, we will discuss the impact of sulfur on the electronic level alignment at surfaces and interfaces, and how to go about learning more about local chemical bonding (hybridization) in the vicinity of sulfur atoms, using a large variety of compounds as examples – sulfides, sulfates, chalcopyrites, ... The presentation will thus also include a bit of a discussion of cutting-edge instrumentation recently developed for studying buried layers and materials in in situ and operando environments, such as the novel X-SPEC beamline and its unique endstations at the KIT Light Source in Karlsruhe, Germany.
Deposition and Characterization of Photocatalytically Active Nanowires Viascanning Electrochemical Probe Microscopy
Authors: Caniglia Giada , Oswald Eva , Hellmann Andreas , Gaus Anna-Laurine , von Delius Max , Kranz Christine 
Published: December 2024

Producing clean energy is one of the world's greatest challenges today. The use of solar energy to split water into hydrogen and oxygen is therefore of great interest. In addition to semiconductor materials, heterogenized molecular catalysts for the hydrogen evolution reaction (HER) and water oxidation catalysts (WOC) have attracted considerable interest. The development and design of artificial molecular devices (i.e. artificial photosynthesis systems) using visible light requires the heterogenization of catalysts (CAT) and photosensitizers (PS). However, the correlation of structural heterogeneity, leaching of active components and degradation processes during illumination, as well as the continuous monitoring of reactivity have not been fully addressed.1,2 Scanning electrochemical probe microscopy such as atomic force microscopy (AFM), scanning electrochemical microscopy (SECM), scanning electrochemical cell microscopy (SECCM), and scanning photoelectrochemical microscopy (SPEM), have been used to map light-driven water splitting and local electron transfer kinetics under in situ and operando conditions.3-5

In this contribution, we present the deposition of mixed CAT/PS nanowires using earth-abundant BPh2-bridged, organometallic cobaloxime CATs and Ru-based ([Ru(tbbpy)2(mmip)]Cl3) PS on various substrates using SECCM. Based on different studies an cabolime microarrays6, the nanowires are characterized with respect to their stabilty, elemental composition as well as their light-driven H2 evolution activity. The H2 evolution of nanowire arrays is imaged via SECM using Pd- and Pt-Black modified microelectrodes. In addition, submicron-sized electrocatalytically active cantilever-based probes, recently developed by our group, are used for improved lateral resolution. These probes can be used for colloidal force spectroscopy7,8 providing nanomechanical properties of the studied materials. A thorough characterisation of the cantilever-based sensors will be presented together with nanomechanical and activity mapping of nanowires with different CAT/PS ratios.

References:

1 C. Kranz, M. Wächtler, Chem. Soc.
Rev.
50, 1407
,
2021
.

2 C. Santana Santos et al., Chem.
Rev.
123, 4972, 2023.

3 J. Kund et al., Angew. Chem. Int. Ed.
22, e202217196, 2023.

4 G. Askarova et al., Anal. Chem.
94, 7169, 2022.

5 J.T. Mefford, et al., Nature, 593, 67, 2021.

6 E. Oswald et al, Chem. Eur. J.
27, 16896
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2021.

7 H.-J. Butt, Biophys. J.
60, 1438, 1991.

8 S. Daboss, Anal.
Chem.
92, 8404, 2020.
This work is part of the TRR 234 “CataLight” project that has received funding from the Deutsche Forschungsgemeinschaft (German Science Foundation), DFG. Project number 36454990.
Unveiling Complex Interfaces: A Methodological Approach for Accurate Apxps Data Acquisition of Polymer Electrolyte Membrane Electrolysis Devices
Authors: Hamlyn Rebecca , Mahl Johannes , Crumlin Ethan J. 
Published: December 2024

Electrochemical water splitting is a promising pathway for the production of green hydrogen as an alternative fuel, chemical feedstock and storage medium for renewables. Yet, the process is hindered by slow kinetics of the oxygen evolution reaction at the anode. Also, large scale implementation will require reduced loadings of expensive and rare platinum group metals and development of new materials. Making progress on rational design for OER catalysts requires effective characterization of the electrode-electrolyte interface where the chemistry takes place. Synchrotron-based x-ray photoelectron spectroscopy (XPS) offers a versatile way to obtain surface chemical and elemental characterization of such materials. The use of X-rays in the tender regime (~2-6 keV) allows for deeper probing than the conventional soft X-ray (< 2 keV) energies that are common for this technique. The photoelectrons generated from tender x-rays have enough energy to penetrate tens of nanometers through low-density components such as a layer of liquid or polymeric electrolyte, allowing access to interfaces in operando conditions. At Beamline 9.3.1 of the Advanced Light Source, we have developed a fully operational two-electrode system to study these membrane electrode assemblies under active water-splitting conditions.
Accurate and representative data collection can involve a series of considerations and tests during acquisition. In this talk, I will explain our specific approach, which combines conventional and sub-second snapshot acquisition modes to minimize beam effects and test for phenomena that can contribute to erroneous interpretation of data. I will demonstrate the efficacy of this approach with results on a series of iridium-based polymer electrolyte membranes. With the application of elevated potential, we can correlate the iridium valency and surface species with the appearance of product traces in a mass spectrum.
Shedding Light on Active Site Reconstruction and Structural Transformation of Oxygen Evolution Reaction Catalysts for Water Electrolysis
Authors: Ham Kahyun , Lim Ahyoun , Spanos Ioannis 
Published: December 2024

Designing efficient and stable electrolcatalysts for the demanding oxygen evolution reaction (OER) in water electrolysis is challenging and we are still lacking fundamental understanding of the underlying processes related to catalyst transformations governing their final activity and stability. Only the combination of operando spectroscopy techniques with electrochemical measurements can promote a deeper understanding on the interplay of different phenomena taking place during OER [1].
In this work, we utilize operando techniques like X-ray Absorption Spectroscopy (XAS) and Surface Enhanced Raman Spectroscopy (SERS) [2], in combination with specifically designed electrochemical protocols to study i) the reconstruction/reactivation of active sites in Ir-based OER catalysts for acidic media (Fig. 1a-c) and Ni-based OER catalysts for alkaline media (Fig. 1d) and ii) the identification of the relevant OER active species which will eventually define the final electrocatalyst performance [3]. We show not only the formation of the active species for OER but also the dynamic operando transformation of the Ir- and Ni-based electrocatalysts before the onset of OER but also their structural transformation due to electro-oxidation during OER, processes that lead to the final active phase.
The underlying mechanisms studied via our operando analysis provide fundamental understanding of reaction mechanism but also guidance for the design of efficient OER catalysts optimized for their operation in technical devices.

References

[1] Spanos I, Tesch MF, Yu M, Tüysüz H, Zhang J, Feng X, Müllen K, Schlögl R, Mechler AK: ACS Catal 2019, 9:8165-8170.
[2] Lim A, Ham K, Tesch MF, Spanos I: to be submitted
[3] Lim A, Ham K, Tesch MF, Spanos I:Current Opinion in Electrochemistry 2023, 39:101272

Figure 1