bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Electrochemical Acetone/Isopropanol Hydrogenation Cycle: Full-Cell Performance of the Electrochemical Dehydrogenation of Isopropanol
Authors: Venus Dominik Maximilian , Marth Axel , Freiberg Anna T.S. , Brodt Matthew , Thiele Simon 
Published: August 2024

Molecular hydrogen has exceptionally high gravimetric energy density but low volumetric energy density at ambient conditions. This discrepancy requires technical measures to increase its volumetric energy density for widespread hydrogen applications. Compressed hydrogen and liquified hydrogen are the most established hydrogen storage technologies. In addition, thermocatalytic liquid organic hydrogen carriers (LOHC) have drawn significant attention in the last decade.[1] LOHC couples consist of a hydrogen-lean and a hydrogen-rich form that can be reversibly converted into each other on demand. So far, only a few approaches adapted this hydrogen storage concept to electrochemistry. However, there is strong interest in electrochemical liquid organic hydrogen carriers (EC-LOHC) as electrochemical processes offer significant advantages like flexible operation, device size, scalability, and system simplicity.[2]

This contribution demonstrates the concept of acetone/isopropanol as an electrochemical liquid organic hydrogen carrier focusing on the electrochemical dehydrogenation of isopropanol in a polymer electrolyte membrane electrode assembly (PEM-MEA) setup. The isopropanol oxidation at a PtRu electrode shows two distinct oxidation peaks at 0.18 V vs. RHE and 0.75 V vs. RHE, whereby the first oxidation peak is associated with a selective oxidation of isopropanol to acetone, electrons and protons.[3] The produced protons travel from the PtRu anode through the PEM and recombine with the electrons at the Pt cathode to form hydrogen. Therewith, this configuration is an electrolysis cell that produces hydrogen out of isopropanol upon polarization above the reversible cell potential.
The study investigates the influence of acetone/isopropanol concentrations, temperature, and flow rates on the I-V characteristics of the electrochemical dehydrogenation of isopropanol at voltages below 0.35 V, revealing its possible potential as EC-LOHC.
References
[1] D. Teichmann, W. Arlt and P. Wasserscheid, International Journal of Hydrogen Energy
2012, 37, 18118–18132.
[2] A.J. Bard, M. Stratmann, Encyclopedia of Electrochemistry Volume 5 Electrochemical Engineering, Wiley, 2007, 4.
[3] P. Khanipour, F. D. Speck, I. Mangoufis-Giasin, K. J. J. Mayrhofer, S. Cherevko, and I. Katsounaros, ACS Applied Materials & Interfaces
2020 12 (30), 33670-33678.

Figure 1
Long Term Durability Investigation of Cu-Doped La2NiO4 Oxygen Electrodes in Solid Oxide Electrolysis Cells
Authors: Karki Surendra B , Springer Renaldo , Seymour Lorraine , Le Long , Liu Tian , Coyle Chris , Marina Olga A 
Published: August 2024

State-of-the-art oxygen electrodes in SOECs, lanthanum strontium cobalt iron oxide (LSCF) and lanthanum strontium cobalt oxide (LSC), contain strontium. Undesired reactivity and migration of Sr cations during long-term operation was found to be detrimental to the electrochemical performance as they triggered formation of multiple oxide phases, including insulating phases and electrode or barrier layer delamination. Developing alternative electrodes that are devoid of Sr is very important for long-term operation of SOECs.
In this work, we synthesized and evaluated properties of La2NiO4-based compositions with a Ruddlesden-Popper structure. The Cu-doped La2NiO4 compositions made of nano-size particles exhibited an enhanced electrochemical performance when tested in SOECs during steam electrolysis for hydrogen production. Long-term durability of these electrodes was studied using planar Ni-YSZ electrode-supported cells with an active area of 1.5 (button cells) and 13 cm2 (2.5 cm x 5 cm cells). Compared to the Sr-containing electrodes, the La2Ni0.8Cu0.2O4 (LNCuO-20) demonstrated lower degradation rate at 1.3 Volt resulting in a current density over 1 A/cm2 at 750⁰C. Chrome and sulfur tolerance of these electrodes during long term operation will be discussed as well.
Design and Performance Evaluation of a Specialized Bubbler System for Accurate and Repeatable Solid Oxide Electrolysis Cell (SOEC) Testing
Authors: Gomez Joshua , Kane Nicholas , Hartvigsen Jeremy , Priest Cameron , Wang Lucun , Ding Dong , Casteel Micah , Wu Gang 
Published: August 2024

Accurate assessment of Solid Oxide Electrolysis Cell (SOEC) performance demands standardized testing conditions, particularly in stable steam delivery. Fluctuations in steam concentration and flow rate can significantly impact measured open-circuit voltage (OCV) and polarization behavior. Although direct steam injection is straightforward, it is often hindered by instability resulting from intermittent liquid water flux, pressure fluctuations, and fractional distillation effects. Bubbler humidification systems have the potential to offer consistent steam, but tailored designs for SOEC testing are currently absent.
This study introduces a specialized bubbler system designed to deliver stable steam to SOEC test stands accommodating both oxygen-conducting (O-SOEC) and proton-conducting (H-SOEC) cells. The bubbler components include a refill water reservoir, a level control module, heating elements, pressure relief valves, check valves, tubing, and fittings integrated with the test stand. The system humidifies the sweep gas, transporting steam to the cell test fixture situated within a high-temperature furnace.
The design process involved meticulous considerations of materials compatibility, hydrogen safety, and overtemperature protection. All wetted components employ stainless steel, glass, or PTFE materials in their construction construction. Redundant thermocouples ensure safe process temperatures with automated overtemperature shut off. The refill reservoir and bubbler headspace operate near ambient pressure, facilitated by an exhaust line vent sized for minimal backpressure.
In various executed O-SOEC tests, the bubbler maintained OCV stability within ±5 mV over several hundred hours for each cell operating at 750°C, eliminating spikes caused by steam fluctuations observed with direct injection methods. This facilitates precise electrochemical analysis and determination of area-specific resistance losses. Polarization curves align with expected behavior based on the Nernst equation. The system has demonstrated safe and stable functionality for over thousands of hours across various operating conditions.
The bubbler design presents researchers with notable advantages over existing steam supply options for SOEC test stands, addressing performance, safety, and flexibility concerns. Online instrumentation enables closed-loop control of steam conditions, enhancing stability. Standardization of test equipment is crucial for quality results, and this work contributes progress toward reproducible protocols in the international SOEC community. The modular bubbler approach, integrated with safety features, also signifies safer methodology choices for lab-scale experimental research.
Facile in-Situ Straining Platform for Transmission Electron Microscopy with Quantification of Strains
Authors: Wood Nathan , Sari Bengisu , Dhall Rohan , Dandu Medha , Hochhalter Jacob , Doeff Marca M. , Warren Roseanne 
Published: August 2024

This work aims to design and model an experimental platform to perform in-situ straining experiments in a transmission electron microscope (TEM), enabling structural characterization of materials under tensile strain. The ability to visualize changes in the crystal structure of materials under strain can provide important insights into failure modes and improve understanding of process-structure-property relationships. Existing methods of in-situ straining typical involve complex sample preparation and are not well-suited to the study of thin films or sensitive battery materials. In this work, thin films of materials are deposited on a conventional TEM grid adhered to a copper template. The template is mounted in a Gatan 654 single tilt straining holder and strained within the TEM. Electron diffraction patterns are taken from the specimens, and strain can be calculated based on shifts in the Bragg reflections.
An essential component of in-situ straining experiments is the quantification of applied strains. For our facile straining platform, we calculate the expected values of strain on our specimen using a finite element model. The finite element strain simulation data was compared with experimental data collected during in-situ straining experiments. Experimental results on a variety of material systems, including those applicable to lithium-ion batteries, are within the bounds of our model. Overall, the ability to accurately simulate in-situ strains using the finite element model enables researchers to better explain observation in the TEM, improve the reproducibility of the experiments, and optimize straining geometries to be tested.

Figure 1
(Invited) Probing the Reaction Microenvironment during Electrochemical Nitrate Reduction to Ammonia
Authors: Corson Elizabeth R. , Guo Jinyu , Brimley Paige N , Liu Matthew Junjie , Munoz Carolina , Smith Wilson A , Tarpeh William Abraham 
Published: August 2024

Nitrate pollution of wastewater from agricultural runoff and industrial waste streams is common around the globe. Nitrate negatively impacts the environment through harmful algal blooms and can be dangerous for human consumption. Strict limits have been set on nitrate discharge and the concentration in drinking water (< 50 ppm). Nitrate is currently removed from water by conversion to nitrogen through a biological process that requires chemical inputs (e.g., methanol) and post-treatment to remove biomass and organics.
Electrochemical reduction of nitrate (NO3RR) to ammonia can remove nitrate from water and is an alternative to Haber-Bosch (HB) ammonia production, a significant source of global CO2 emissions. Ammonia is an important chemical precursor with potential applications in sustainable energy as a fuel or H2 carrier, or can be used as a fertilizer in the form of ammonium sulfate. This research addresses the water–energy nexus by converting nitrate to a valuable product, off-setting the cost of water treatment, and reducing demand for HB.
NO3RR can be done from small to large scales, use renewable electricity, and eliminate the need for expensive and hazardous chemicals. However, NO3RR processes must exhibit selectivity toward ammonia to avoid the formation of other undesired products and occur at a low overpotential to minimize operating costs from electricity. To address these challenges, we must understand the reaction environment at the electrode–electrolyte interface, where heterogeneous electrochemical reactions occur. We use in situ attenuated total reflectance–surface-enhanced infrared adsorption spectroscopy (ATR–SEIRAS) to investigate the adsorbed reactants, intermediates, and interfacial pH. We studied the repeatability of the technique for in situ interfacial pH measurement and recommend controls to the community when using this method. The ATR–SEIRAS results are correlated with electrochemical experiments measuring NO3RR selectivity, activity, and efficiency. NO3RR products are measured by ion chromatography and gas chromatography. Our results relate bulk electrolyte properties with interfacial properties, and interfacial properties with reaction activity and selectivity. This understanding could lead to the development of electrolyte engineering strategies to optimize ammonia production in electrochemical NO3RR.
Electrocatalytic Synthesis of Urea
Authors: Costa Figueiredo Marta 
Published: August 2024

Many industrial chemical processes involve a high-energy demand (often still derived from fossil fuels). Urea is an important chemical for the agricultural industry, which accounts for 70% of the global nitrogen-containing fertilizer usage. Currently, urea is produced by the reaction of liquid NH3 and CO2
[1] in a process known as the Haber-Meiser process. Despite its importance, this process suffers from high energy demand and CO2 emissions, mainly due to the NH3 synthesis step (Haber- Bosch process), which relies on fossil fuel resources. Making urea with electrochemical methods has recently gained interest from the scientific community as this approach provides a way to reduce the high CO2 emissions currently associated with urea production. Among the various nitrogen sources explored for urea electrosynthesis, nitrate (NO3-) is attractive because of its high solubility in water, low dissociation energy and potential to mitigate NO3
− contaminations in water. Even though the mechanism of urea synthesis via CO2 and NO3
- coupling is still controversial and not broadly studied, most reports implicate CO* and NH2* surface intermediates in urea synthesis.[2] Cu is an attractive electrocatalyst as it can reduce CO2 to CO and further products and it is also an active catalyst for the reduction of nitrate to ammonia Previous reports on Cu and Cu-based materials showed that urea can be obtained from NO2
-.[3,4] Early research by Shibata et al. with various catalysts demonstrated that the highest faradaic efficiency towards urea from NO3
- was achieved with a Zn catalyst.[5] In this presentation, I will show our latest results on the development of Cu bimetallic catalysts ( CuRh) for urea electrosysnthesis from CO2 and NO3
-[6,7].

References:

[1] P. N. Cheremisinoff, Waste Minimization Cost Reduct. Process Ind.
1995, 222–284.
[2] X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Nat. Commun.
2022, 13, 1–9.
[3] S. Liu, S. Yin, Z. Wang, Y. Xu, X. Li, L. Wang, H. Wang, Cell Reports Phys. Sci.
2022, 3, 100869.
[4] N. Cao, Y. Quan, A. Guan, C. Yang, Y. Ji, L. Zhang, G. Zheng, J. Colloid Interface Sci.
2020, 577, 109–114.
[5] M. Shibata, K. Yoshida, N. Furuya, J. Electrochem. Soc.
1998, 145, 595–600.
[6] D. Anastasiadou, B. Ligt, Y. He, R van de Poll, J. Simons, M C Figueiredo. . Communications in Chemistry, 6, 199, 2023
[7] D. Anastasiadou, B. Ligt, , M C Figueiredo, in preparation.
Electrical TP-Resistance Measurement at Gas Diffusion Layers (GDL) for Pemfcs – Separation of Bulk and Contact Resistances
Authors: Koenig Lukas , Messerschmidt Matthias 
Published: August 2024

At electrical TP-resistance measurements of PEMFC GDLs often the separation of bulk and contact resistance is of interest. There are two possibilities for this task: 2-pole measurement with stacking of GDLs and 4-pole measurement with two non current conductive poles for pure voltage measurement. Both methods are discussed and evaluated within this poster.
The results presented are acquired within the project QM-GDL (GDL quality assurance for the market run-up), which is funded by the German Federal Ministry for Digital and Transport under grant agreement number 03B11016C.
Understanding Phosphoric Acid Dynamics in High-Temperature Pemfcs: Mechanisms and Durability of PA-PBI and Ion-Pair-Based Systems.
Authors: Lim Katie Heeyum , Lee So Young 
Published: August 2024

High-Temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) can operate at > 100 oC under anhydrous conditions, providing benefits such as system simplification and superior contaminant tolerance. Most researches on HT-PEMFC have focused on PA-PBI-based system since 1995, however the durability of this system is still on controversial. Some insisted the stable operation of PA-PBI HT-PEMFC, which showed the stability under mild conditions such as low current density about 0.2 A cm-2, while others pointed out the instability specifically under accelerated stress conditions with higher current densities above 0.6 A cm-2, lower ( < 140 oC) or higher ( > 180 oC) operating temperatures, or dynamic protocols like start-up/shut-down cycles, etc.
This limited durability of PA-PBI HT-PEMFC is known to be related to acid loss from the membrane-electrode-assemblies (MEAs). Several mechanisms were proposed to explain the linear and nonlinear acid loss behaviors. PA evaporation and steam-distillation are known to explain the constant PA loss. Despite the extensive efforts on mechanisms and acid loss mitigation strategies, current PA-PBI systems still struggle against the limited durability due to PA loss. To improve the durability of HT-PEMFC, a novel system was introduced based on the quaternary ammonium-biphosphate ion-pair coordinated PEM [1]. Due to a stronger interaction in the ion-pair PEMs, the durability was also improved by alleviating the PA loss during PEMFC operation. Nonetheless, the acid retention mechanism of this novel system is not explored yet.
Here, we investigate the mechanisms of PA loss and PA retention within electrodes of both PA-PBI-based and ion-pair-based HT-PEMFC systems. Through PA energetics studies and experimental investigations under controlled stress conditions, we elucidate distinct PA loss/retention mechanisms in these systems, leading to different durability behaviors. Our findings offer insights for enhancing the durability of both HT-PEMFC systems [2].
[1] Lim, K. H.; Lee, A. S.; Atanasov, V.; Kerres, J.; Park, E. J.; Adhikari, S.; Maurya, S.; Manriquez, L. D.; Jung, J.; Fujimoto, C.; Matanovic, I.; Jankovic, J.; Hu, Z.; Jia, H.; Kim, Y. S. Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells, Nature Energy, 7, 248 (2022).
[2] Lim, K. H.; Matanovic, I.; Maurya, S.; Kim, Y.; Castro, E. S.; Jang, J-H.; Park, H.; Kim, Y. S. High temperature polymer electrolyte membrane fuel cells with high phosphoric acid retention, ACS Energy Letters, 8, 529 (2023).
Enhancing PA-PBI Composite Membrane with Metal Oxides Incorporation for HT-PEMFC Operating Above 200 oc
Authors: Lee So Young , Kim Seongwoo , Kim Joonbyum , Gwak Gyeongseok , Nam Suk-Woo 
Published: August 2024

High-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) are renowned for their excellent CO tolerance and rapid reaction kinetics [1]. Among the various membrane types, phosphoric acid doped polybenzimidazole (PA-PBI) membranes, phosphoric acd (PA) acts as a proton conductor, facilitating proton transfer through hydrogen bond rearrangement between PA molecules and the PBI backbone [2]. However, the operating temperature of PA-PBI membrane-based HT-PEMFC is constrained by the condensation of PA, limiting their use to below 180 oC and posing a significant challenge for achieving efficient operation above 200 oC.
Recent research endeavors have focused on enhancing PA-PBI membranes by incorporating metal oxides to extend their operational temperature range beyond 180 oC. The addition of metal oxides into PA solution leads to the formation of metal hydrogen phosphate, effectively preventing PA evaporation at elevated temperatures ( > 180 oC) and maintaining membrane performance without degradation. Furthermore, the presence of metal oxides facilitates proton transfer to the metal hydrogen phosphate surface, thereby improving ionic conductivity even at temperatures exceeding 200 oC.
In this study, we present the synthesis of poly(2,2’-(1,4-phenylene)-5,5’ bibenzimidaozle) (pPBI) composite membranes through an in-situ method, where various metal oxides (SnO2, TiO2, ZrO2) are introduced into the synthesis solution. Through systematic investigation, we evaluate the impact of these metal compounds on fuel cell performance and durability at high temperatures exceeding 200 oC. Our findings shed light on the potential of metal oxide-modified PA-PBI composite membranes for advancing the performance and reliability of HT-PEMFCs in demanding operating conditions.

References

[1] J. M. L. e Canut, R. M. Abouatallah, D. A. Harrington, J. Electrochem. Soc, Sci, 153 (2006) A857.
[2] Z. Wang, J. Zhang, S. Lu, Y. Xiang, Z. Shao, S. P. Jiang, Adv. Sustainable Syst, 7, (2023) 2200432.
Electropolymerization of Pyrrole Using a Single-Electrode Electrochemical System
Authors: Inagi Shinsuke , Shi Yulin , Villani Elena , Xu Guobao 
Published: August 2024

Bipolar electrochemistry emerges as an appealing technique for gradient surface fabrication thanks to the controllable potential distribution on bipolar electrodes (BPEs) in a wireless manner [1]. Here we report a BPE array named the single-electrode electrochemical system (SEES) [2] for the high-throughput electrosynthesis of gradient polypyrrole (PPy) films via electropolymerization. The SEES consists of a plastic board with holes attached to an indium-tin oxide (ITO) electrode to create multiple microelectrochemical cell arrays. Benefiting from this technique, the effects of various electrolysis conditions on film growth, such as applied voltage, electrodeposition time and electrolyte, etc., were systematically investigated. The length, thickness, surface morphology, and wettability, of the obtained PPy films were investigated [3]. The SEES provides a straightforward comparison of experimental results and hence facilitates the condition screening process.
References:

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

W. Gao, K. Muzyka, X. Ma, B. Lou, G. Xu, Chem. Sci., 2018, 9, 3911.

Y. Shi, E. Villani, Y. Chen, Y. Zhou, Z. Chen, A. Hussain, G. Xu, S. Inagi, Anal. Chem., 2023, 95, 1532.
Radical Cation Alkene Functionalization Using Anodic Oxidation
Authors: Adachi Sota , Okada Yohei 
Published: August 2024

Oxidative functionalization of alkenes is a promising molecular transformation technique, where intramolecular reactions enable the synthesis of saturated heterocycles1), which are often found in natural products and pharmaceuticals. In addition to the widely studied palladium-catalyzed oxidative functionalization of alkenes2), electrochemical3), 4) and photocatalytic5) methods have recently been developed. These one-electron oxidation-based methods have been applied to trisubstituted and tetrasubstituted alkenes with large steric hindrance, which is difficult to achieve with conventional palladium-catalyzed reactions. In many cases, these methods reported previously form rings as neutral radicals under basic conditions. On the other hand, radical cationic cyclization is relatively rare and have not yet been fully discussed. In this study, we developed an alkene oxidative functionalization using electrolysis for radical cationic cyclization.
After optimizing the reaction conditions using trisubstituted alkene (1a) as a model substrate, we succeeded in obtaining the target compound (2a) in 90% yield (Scheme 1). In this reaction, a six-membered ring is formed as a byproduct, but the anion species of the supporting salt affects the reaction selectivity, and it was found that a five-membered ring was formed with high selectivity when ClO4- or TfO- were used. Furthermore, using a 1:9 mixture of highly polar CH3CN and low-polar 1,2-DCE as the reaction solvent improved the solubility and conductivity of the supporting salt, resulting in a significant increase in yield. The use of carbon felt, which has a large surface area, as the working electrode also contributed to the yield improvement by suppressing the voltage increase.
For sulfonamides (1b-d) with various substituents on the aromatic ring, we were able to obtain five-membered ring compounds (2b-d) in good yields in all cases. In addition to these results, the details of the condition studies and other substrates will be discussed.
1) Nakamura, I.; Yamamoto, Y. Chem. Rev.
2004, 104, 2127-2198.
2) McDonald, R. I.; Liu, G.; Stahl, S, S. Chem. Rev. 2011, 111, 2981-3019.
3) Xu, H.-C.; Moeller, K. D. J. Am. Chem. Soc. 2010, 132, 2839–2844.
4) Huang, C.; Li, Z.-Y.; Song, J.; Xu, H.-C. Angew. Chem. Int. Ed.
2021, 60, 11237–11241.
5) Reed, N. L.; Lutovsky, G. A.; Yoon, T. P. J. Am. Chem. Soc.
2021, 143, 6065-6070.

Figure 1