bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Gas-Phase Nitric Oxide Adsorption on ORR Activity of Fe-N-C Catalysts
Authors: Wang Xiaoping , Ferrandon Magali , Park Jae Hyung , Zeng Yachao , Wu Gang , Myers Deborah J. 
Published: September 2023

Significant progress has been made in recent years in developing platinum group metal-free catalysts, particularly so-called Fe-N-C materials, for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells.1 However, further improvement in both activity and, especially, durability are still necessary for practical applications. One of the major factors that hinder the further enhancement of the catalysts is the lack of clear understanding of the nature of the active sites in the Fe-N-C catalysts due to the complexity of the Fe-N-C catalysts’ composition and structure. Gaseous nitric oxide was reported to be a suitable probe molecule that can bond to Fe and impede the ORR of the Fe-N-C catalysts.2,3 In this work, the effect of nitric oxide gas-phase adsorption on Fe-N-C catalyst redox feature and ORR activity for a variety of Fe-N-C catalysts from different origin will be investigated. The implication of these results on the nature of the ORR active sites of the Fe-N-C catalysts will be discussed.
Acknowledgements
This work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). This work was partially authored by Argonne, a U.S. Department of Energy (DOE) Office of Science laboratory operated for DOE by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357.
References

X.X. Wang, M.T. Swihart, and G. Wu, "Achievements, challenges, and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation", Nature Catalysis, 2 (2019) 578-589.

J.L. Kneebone, et al., "A Combined Probe-Molecule, Mossbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst", J. Phys. Chem. C 121 (2017) 16283-16290.

P. Boldrin, D. Malko, A. Mehmood, U.I. Kramm, S. Wagner, S. Paul, N. Weidler, A. Kucernak, “Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: Gas sorption, physical and electrochemical investigation using NO and O2”, Applied Catalysis B: Environmental 292 (2021) 120169.
Fundamental Insight into Phenyl-Free Polynorbornene Ionomers Enables High Performance Anion Exchange Membrane Fuel Cells
Authors: Leonard Daniel , Lehmann Michelle , Matanovic Ivana , Fujimoto Cy , Saito Tomonori , Kim Yu Seung 
Published: September 2023

Anion exchange membrane fuel cells (AEMFCs) are seen as a possible successor to proton exchange membrane fuel cell technologies. A major motivation behind AEMFC development is the potential to use less costly materials, such as non-platinum group metal catalysts, thus reducing the stack cost. Anion exchange ionomers (AEIs) are polymers that facilitate ion transport in the catalyst layer play and a critical role in the performance of fuel cells. In fact, cell performance is profoundly affected by fundamental interactions between the catalyst surface and the AEI. Two such interactions are of particular importance: phenyl adsorption on hydrogen oxidation catalysts and electrochemical oxidation of phenyl moieties on oxygen evolution catalysts. Both are detrimental to an alkaline device’s performance and durability.
We compared the adsorption energy of phenyl-containing ionomers for implementing phenyl-free ionomers. Density functional theory calculations indicated that the norbornane fragment has minimal adsorption energy on Pt(111) due to the absence of aromatic electrons. A soluble quaternized polynorbornene ionomer was prepared by vinyl addition polymerization. This ionomer enables high performance in fuel cells, (peak power density > 2 W cm-2), proving the advantage of the phenyl-free structure. This study establishes the phenyl adsorption energy-electrode performance relationship, highlighting the importance of material interactions between the catalysts and ionomers.
Stabilization of Platinum Catalyst Surface-Treated by Atomic Layer Deposition of Cobalt for Polymer Electrolyte Membrane Fuel Cells
Authors: Shim Jung Woo , Lee Yong Seok , Choi Yun Sung , Seo Beum Geun , Shim Joon Hyung 
Published: September 2023

Polymer electrolyte membrane fuel cells (PEMFCs) are attracting attention as next-generation energy-conversion devices because they are environmentally friendly and have high energy-conversion efficiencies. A membrane electrode assembly (MEA), composed of an anode, membrane, and cathode, is the most important part of a PEMFC where electrochemical reactions occur. A Pt/C catalyst, wherein Pt is supported on a carbon, is used as the catalyst layer for the anode and cathode. However, as Pt is a precious metal, current research is focused on reducing its loading and improving durability of PEMFCs.
This study focused on improving the durability of catalysts by suppressing agglomeration, one of the degradation mechanisms of Pt catalysts. A protective layer of Co metal was deposited using the atomic layer deposition (ALD) process to improve the durability of catalysts. The ALD process is a type of chemical vapor deposition (CVD) process. This process is suitable for the PT/C catalyst as it allows for the deposition of a uniform thin film even on the porous catalyst layer. If the protective layer is thick, it may block the active site of the catalyst, resulting in decreased activity and reduced performance. However, ALD can form a thin protective layer because it can be controlled at the atomic level by adjusting the number of cycles. After fabricating a single cell using ALD Co-Pt/C as a catalyst for the cathode, The U.S. Department of Energy's electrocatalyst durability protocol was used for an accelerated degradation test (ADT). After Co-ALD was used as a cathode for 10 and 20 cycles, the active area of the Pt catalyst particles was reduced owing to the metal Co protective layer. The initial performance and electrochemical surface area (ECSA) of Co-ALD 10, 20 cycles decreased compared to the case of using Co-ALD 0 cycle. However, after ADT, the performance and ECSA reduction rate rather decreased, confirming that the co-protective layer through the plasma-enhanced atomic layer deposition (PEALD) process can improve the durability of the Pt/C catalyst. To identify the cause of the durability improvement, the cathode catalyst particles before and after ADT were compared through high resolution transmission electron microscopy (HR-TEM) analysis. As a result, in the HR-TEM images after ADT, the Pt catalyst particles were relatively uniformly distributed on the carbon support in the Co-Pt/C catalyst compared to Co-ALD 0 cycle. In addition, it was confirmed that the size of the Pt catalyst particles of Co-Pt/C was smaller than that of bare Pt/C (Co-ALD 0 cycle). It was concluded that when the Co protective layer was deposited on the Pt/C cathode, the protective layer suppressed the agglomeration of Pt catalyst particles, therefore, the increase in Pt particle size improved compared to the Co-ALD 0 cycle, and it was revealed that durability improved by suppressing catalyst degradation.
Catalytic Activity of LnCo0.5Ni0.5O3-Δ (Ln = La, Pr, Nd) "Positrodes" on Ceramic Protonic Electrolytes
Authors: Kwati Leonard , Staykov Aleksandar , Wiff Juan Paulo , Meulenberg Wilhelm , Matsumoto Hiroshige 
Published: September 2023

Proton-conducting solid-oxide electrolyzers and fuel cells represent viable, intermediate-temperature green energy conversion and storage technologies. Interest in this class of materials as electrolytes stems from their high ionic conductivity and inherent advantages in the gas flow configuration over traditional solid oxide cells in which the electrolyte is an oxygen ion conductor. However, their commercial viability has been hindered, in part, by the development of corresponding single-phase electrode components with mixed proton-electron conductivity and effective catalytic activity toward oxygen reduction and evolution reactions (ORR/OER). This paper investigates the origin of catalytic activity in LnCo0.5Ni0.5O3-δ (Ln=La, Pr and Nd) perovskites positrodes (positive electrode) by low energy-ion scattering (LEIS) and DFT studies. LEIS results reveal that La, Pr, and Pr cations dominate the outer atomic layer, with profound implications for catalytic activity. Whereas First principle calculations were performed using the plane-wave DFT method and hybrid HSE06 functional suggest, the catalytic activity and electronic properties depend on the valence shell structure of the Ln-site cation and their redox properties.
Acknowledgments
The authors gratefully acknowledge financial support through JSPS KAKENHI Grant-in-Aid for Scientific Research (C), No. 19K05672, NEDO (International collaboration work in the field of clean energy) JPNP20005, the International Institute for Carbon-Neutral Energy Research (I2CNER) sponsored by the World Premier International Research Center Initiative (WPI),
Electrochemical C-N Coupling Reaction Mediated by π-Extended Haloarene Catalyst
Authors: Shida Naoki , Yoshinaga Shohei , Atobe Mahito 
Published: September 2023

Hypervalent iodine is a useful reagent in synthetic organic chemistry,[1] but because these reagents are synthesized by reaction with stoichiometric amounts of oxidants, their large-scale use is associated with safety and environmental impact concerns. Hypervalent iodine can also be synthesized by electrochemical oxidation of the corresponding iodoarenes, and the electrochemically generated hypervalent iodine can be immediately reacted and used catalytically, i.e., as an electrochemical mediator, to enable a reaction system that is safe and generates little waste.[2]

The use of hypervalent iodine as an electrochemical mediator has been reported previously, [3,4] but the number is still limited. In addition, no quantitative kinetic analysis of catalytic reactions has ever been performed. The presenters hypothesized that the following two issues are responsible for this situation: (i) the high oxidation potential of iodoarenes makes their selective oxidation difficult, and (ii) the instability of the radical cation.
In this study, we designed and synthesized a novel π-extended iodoarene 1, and developed it as an efficient electrochemical mediator (Figure 1). The extended π system realized stabilization of the radical cation intermediate, as well as lowering the oxidation potential. Electrochemical oxidations of various N-Boc-2-aminobiphenyl analogues (2) were performed, and successfully gave cyclized product 3 in high yield in the presence of a base. Kinetic analysis of the electrocatalytic process based on Foot-of-the-Wave analysis (FOWA)[5] was also investigated.[6] In addition, we have also investigated the electrocatalytic reaction and kintetics using mediators with bromo- and chloro-anthracene structures to uncover the structure-reactivity relationship of haloarene mediators.
[1] A. Yoshimura, V. V. Zhdankin, Chem. Rev., 2016, 116, 3328–3435. [2] M. Elsherbini, T. Wirth, Chem. Eur. J.
2018, 24, 13399–13407. [3] T. Fuchigami, T. Fujita, J. Org. Chem.
1994
, 59, 7190-7192. [4] A. Maity, B. L. Frey, N. D. Hoskinson, D. C. Powers, J. Am. Chem. Soc.
2020, 142, 4990−4995. [5] C. Costentin, S. Drouet, M. Robert, J.-M. Savéant, J. Am. Chem. Soc.
2012, 134, 11235–11242. [6] S. Yoshinaga, M. Atobe, N. Shida, ChemRxiv, 2022, DOI: 10.26434/chemrxiv-2022-sggqd.
Electrochemical Cycloaddition Reactions of Alkene Radical Cations – a Route Towards Cyclopropanes and Cyclobutanes
Authors: Rybickajasinska Katarzyna , Szeptuch Zuzanna , Kubiszewski Hubert , Kowaluk Agnieszka 
Published: September 2023

New methods to promote single-electron transfer reactions play an increasingly important role in driving modern organic chemistry. Significant advances have been made in the field of photoredox catalysis1 and synthetic organic electrochemistry2 to expand the utility of radicals in organic synthesis.3 While the initial developments in synthetic organic electrochemistry date as far back as the early 19th century, only recently has it undergone an explosive revival and it is now an important part of synthetic organic chemistry.4 Undeniably, it provides a green alternative to known and new reactive intermediates by the promotion of organic reactions under mild conditions without the necessity for excessive amounts of hazardous and wasteful oxidants and reductants, metals4 or catalysts, making chemical synthesis highly atom economical.5

Our work describes mild and efficient electrochemical methods for [2+1] and [2+2] cycloaddition reactions of alkene radical cations. Anodic oxidation of olefins produces electrophilic alkene radical cations, which further react with nucleophilic diazo compounds in a formal [2+1] cycloaddition towards cyclopropane synthesis. This methodology is also applicable for [2+2] cycloadditions with styrene derivatives, validating this efficient electrochemical system for both cyclopropane and cyclobutane ring synthesis. The advantages of this methods include the mild, metal and catalyst free conditions, simple setup, and scalability of the procedure, as well as its potential use for industrial applications since the method requires non-expensive graphite electrodes.
References:

a) Skubi, K. L., Blum, T. R., Yoon, T. P. Chem.
Rev.
2016, 116, 17, 10035-10074. b) Romero, N. A., Nicewicz, D. A. Chem.
Rev.
2016, 116, 17, 10075-10166 c) Prier, C. K., Rankic, D. A., MacMillan, D. W. C. Chem.
Rev.
2013, 113, 7, 5322-5363. d) Donabauer, K., König, B. Chem. Res.
2021, 54,1, 242-252.

Yan, M., Kawamata, Y., Baran, P. S. Chem Rev.
2017, 117, 21, 13230-13319. b) Zhu, C., Ang, N. W., Meyer, T. A., Qiu, Y., Ackermann, L. ACS Cent. Sci.
2021, 7, 3, 415-431. c) Pollok, D., Waldvogel, S. R. Sci.
2020, 11, 12386-12400. d) Meyer, T. H., Choi, I., Tian, C., Ackermann Chem
2020, 6, 2484-2496. e) Yan, M., Kawamata, Y., Baran, P. S. Angew. Chem. Int. Ed.
2018, 57, 4149-4155.

Tay, N., Lehnherr, D., Rovis, T. Chem.
Rev.
2022, 122, 2, 2487-2649.

a) Kingston, C., Palkowitz, M. D., Takahira, Y., Vantourout, J. C., Peters., B. K., Kawamata, Y., Baran, P. S. Chem. Res.
2020, 53, 1, 72-83. b)Wirtanen, T. Prenzel, J-P. Tessonnier, S. R. Waldvogel Electroorganic Synthesis, Chem. Rev.
2021, 121, 10241–10270. c) Sbei, N., Hardwick, T., Ahmed, N. ACS Sustainable Chem. Eng.
2021, 9, 61-48-6169.

Yuan, Y., Lei, A. Nature Communications.
2020, 802.

Figure 1
Electrochemical Synthesis of Selected λ3- and λ5-Iodanes
Authors: Bystron Tomas , Jirasko Martin , Devadas Balamurugan , Kvicala Jaroslav 
Published: September 2023

Numerous λ3- and λ5-iodanes are used as highly selective oxidants in organic synthesis and are considered as a green alternative to classical metal based (CrVI, MnVII, ...) oxidants. The main advantage of iodanes is substantially lower toxicity and environmental footprint. However, their synthesis is based on chemical oxidation of iodobenzenes which usually involves handling toxic or at least potentially unstable oxidants (e.g. bromate, chlorine, persulfate or percarboxylic acids). This represents safety issue which becomes significant especially when scale-up of the process beyond laboratory level is required. Application of electrochemical synthesis of iodanes offers substantial advantage over the classical chemical approach in a sence no chemical oxidants are required. However, up to this point, no cheap, sustainable and easily scalable process for electrochemical synthesis of λ3-iodanes has been published. The main problems is that majority of the authors use environmentally unfriendly solvents and often workup of the product is complicated or even missing. In the case of electrochemical synthesis of λ5-iodanes, the situation is even worse since there is just handfull of publications on the topic.
In the present contribution, a process of electrochemical synthesis of selected λ3- and λ5-iodanes (based on our previous publications [1-3]) including solid product workup, will be presented. In particular, the electrochemical process is based on anodic oxidation of 2-iodobenzoic acid to 2-iodosylbenzoic acid and 2-iodylbenzoic acid (IBX) using boron-doped diamond electrode. This step proceeds with high current efficiency, selectivity and product yield. Separation involves precipitation, crystallisation and filtration. No product washing with organic solvents is required. It is important to note that during the process development the attention was paid to minimisation of the environmental footprint of the process (high atom efficiency, low amount of waste, absence of toxic chemicals), low price of the chemicals and process scalability.
References
[1] T. Bystron, A. Horbenko, K. Syslova, K.K. Hii, K. Hellgardt, G. Kelsall, 2-Iodoxybenzoic Acid Synthesis by Oxidation of 2-Iodobenzoic Acid at a Boron-Doped Diamond Anode, ChemElectroChem, 5 (2018) 1002-1005.
[2] B. Devadas, J. Svoboda, M. Krupička, T. Bystron, Electrochemical and spectroscopic study of 2-iodobenzoic acid and 2-iodosobenzoic acid anodic oxidation in aqueous environment, Electrochimica Acta, 342 (2020) 136080.
[3] T. Bystron, B. Devadas, K. Bouzek, J. Svoboda, V. Kolarikova, J. Kvicala, Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study, ChemElectroChem, 8 (2021) 3755-3761.
Anodic Oxidation of Bisamides
Authors: Becker James Y. , Golub Tatiana 
Published: September 2023

Previously [1] we studied the anodic oxidation of symmetrical bisamides of type RCONH(CH2)nNHCOR (n = 2-4) under constant current electrolysis (CCE), in methanol. Those with 3 and 4 methylene groups as spacers undergo mostly mono- and dimethoxylation at the alpha-position to 'N' atom. However, when the spacer contains two methylene groups only, the anodic process favors fragmentation products due to CH2-CH2 bond cleavage, as shown in Eq. 1.
Following the above results, for better selectivity, the anodic oxidation of symmetrical aromatic bisamides with ‘CH2CH2’ as a spacer (ArCONHCH2CH2NHCOAr), was investigated [2] in acetonitrile, and under controlled potential electrolysis (CPE). The outcome indicates that the major products involve unsymmetrical geminal bisamides (Eq. 2) that are difficult to synthesize by other methods.
References
[1] T. Golub and J.Y. Becker, Beilstein J. Org. Chem.
2018,
14, 861–868.
[2] T. Golub, G.-Y. Dou, C.-C. Zeng and J. Y. Becker, Org. Lett., 2019, 21, 7961-7964;
J.Y. Becker, unpublished results (2022).

Figure 1
Turning the Wheel through the Ages
Authors: Smith Sam Jackson , Donnelly Dan J , Fei Matthew , Matzker Sage , Roger Sofia , Doan Jonathan , Smotkin Eugene S. 
Published: September 2023

Methods for reliably generating alternating current via placing metal coils in a rotating magnetic field were discovered by two individuals almost simultaneously: Italian engineer and physicist, Galileo Ferraris, and Austrian-American engineer, Nikola Tesla. While Tesla attained the patent for the AC-generator, Ferraris, who published the discovery a few months prior, is credited with having paved the way for the modern-day alternator, now used ubiquitously.
The origins of rotational energy conversion can be traced back to sugar plantations in the 1600s. At that time, the milling process was initially sustained through slave-driven turning of a wheel, which was geared to large wooden rollers that would squeeze sugar cane. The Caribbean and South American variant of this system was known as a trapiche, which employed three geared rollers. Over time, slaves were replaced with oxen and horses, which were eventually supplanted by water wheels and finally by steam engines. The water wheels implemented for sugar milling ultimately paved the path for creating electrical currents. Water turbines for hydroelectric power subsequently took off. Principles of steam engine operation were adapted for electrical power as well, ultimately culminating in the use of nuclear plants to generate “wheel” turning for electricity.
Electricity and magnetism, as well as interactions between them, are frequently discussed in introductory undergraduate physics. However, practical applications of these principles are often omitted from lectures. If taught under an experiential environment, these concepts can be introduced at even the middle school level, taught by first year college students taking basic college physics - a synergistic learning environment. With this in mind, we developed a middle school kit consisting of simple 3D-printed components, recycled DVDs and four bearings for support of 4 mm nail shafts. Enameled wire (30 AWG) is used to prepare the wire-wound coils. A large rubber band is used as the pulley-belt. The above represents the generator component. The power use component is assembled on an accompanying bread board. Power processing is demonstrated using diodes for rectification to DC. The DC power is used to recharge a 3V, 40 mAh lithium-ion coin cell. AC power from the generator can also be directly applied to load resistors. Students will be able to see the effects of varying the load by changes in the time of the free rotation of the generator wheels. Students will experience the charge and discharge of batteries with safe voltages and currents.
Middle school students will record data from the generator and conditioning systems and draw conclusions on worksheets that accompany the hardware.
Electrical Circuit Tools for Simulating Student Lab Exercises on Electrochemical Processes
Authors: Fafilek Guenter 
Published: September 2023

In 2020, SarsCov2 pandemic imposed severe restrictions for practical student courses. In our course on chemical engineering one topic is corrosion and corrosion protection. However, lock-down prohibited regular laboratory work where students could acquire their own experimental data. As a workaround, the simulation of electrochemical experiments on corrosion systems provided data, which allowed the illustration of basic corrosion principles and further evaluation and discussion. For that purpose, a Pspice(C) electrical circuit simulation environment has been chosen.
This contribution presents specifically designed electrical circuit models for electrochemical processes. Their combination to larger equivalent circuits for the whole system can deliver realistic and individual data for the students. With this software students learn about the components of an electrochemical cell and their behavior similar to a real experiment.

Figure 1