bluuebunny/crossref_metadata_2025_split huggingface dataset:
Study of Alternative Binders for Battery Electrode in Aqueous System
Authors: Sepp Silver 
Published: September 2023

Materials used to prepare energy storage devices need to be affordable, durable, and safe for environment. PVDF, which is the most popular polymer used as a binder in battery electrodes, requires the use of and toxic solvents for processing, such as N-methyl-pyrrolidone (NMP).1 Water insoluble organic polymers could replace PVDF as the binder in aqueous batteries or redox flow batteries with solid boosters.2 For example, ethyl cellulose is a biodegradable and water-insoluble polymer. Ethyl cellulose-based slurry can be prepared using ethanol as solvent, which makes the process cheaper and more sustainable. Also cross-linked gluten could be used as a binder. In that case water-based slurry could be used to prepare the electrode. Replacing PVDF with more environmentally friendly binder would be beneficial in many ways. It would shorten the assembly procedure due to high speed of solvent evaporation, there are no strict requirements for humidity control and the recycling procedure is easier as there are no fluorinated compounds.3 Therefore, this replacement would enable to produce safer and cheaper energy storage devices.
In this work positive electrodes with different composition have been described using galvanostatic charging-discharging and cyclic voltammetry. Various cell setups have been tested. LiMn2O4 (LMO) has been used as active material for cathode and carbon black Super P as conductive additive. PDVF has been compared with various organic biodegradable polymers as the binder. Using ethyl cellulose as a binder, discharge capacity 100 mAhg−1 was achieved at 0.2C rate for LMO cathode which is comparable to the results obtained with PVDF as a binder. 500 cycles at the rate of 1C showed somewhat better capacity retention for electrodes prepared using PVDF. Also rotating disk electrode experiments were conducted to study the effect of binder to the kinetics of the reaction. The results show that some biodegradable and cheaper binders could be promising option to replace PVDF as binder in aqueous systems. This is highly important in aqueous redox flow battery with solid boosters, where large amount of solid charge storage material is used in tanks to increase the capacity of the system.2

Acknowledgements:

The research was supported by the Estonian Research Council grant MOBTP1023, Archimedes Foundation project SLTKT16432T and by the EU through the European Regional Development Fund under project TK141 (2014–2020.4.01.15–0011).

References:

I. Doberdò, N. Löffler, N. Laszczynski, D. Cericola, N. Penazzi, S. Bodoardo, G. T. Kim, and S. Passerini, J. Power Sources, 248, 1000–1006 (2014).

M. Moghaddam, S. Sepp, C. Wiberg, A. Bertei, A. Rucci, and P. Peljo, (2021) Molecules, 26 (8), 2111 (2021).

L. Ibing, T. Gallasch, P. Schneider, P. Niehoff, A. Hintennach, M. Winter, and F. M. Schappacher, J. Power Sources, 423, 183–191 (2019).
Supercapacitors with Gold Colloids That Are Placed at a Short Distance from Active-Carbon Electrodes; The Case for a Plasmonic Effect at the Electrolyte/Electrode Interface
Authors: Grebel Haim , Yu Shupei , Zhang Yuanwei 
Published: September 2023

Supercapacitors (S-C) are fast charge/discharge elements. These short-term energy storage found many applications; among which are, powering electronic devices, boosters of fast charging batteries and possibly, as buffers between highly fluctuating sustainable sources and the rather stable electrical grid. For double-layer S-C, one takes advantage of the very narrow interface between an electrolyte and a conductive porous electrode. In contrast, ordinary capacitors are made of a relatively thicker dielectric material, sandwiched between two electrodes.
In the past, polarity increase in capacitors was achieved by dispersing conductive colloids in the entire volume of the dielectric material. This approach was primarily used for microwave and optical devices – a field known as plasmonics. For S-C it means that the conductive colloids should be dispersed within the double-layer region, or fairly close to it. The impact of such an approach on the low frequency supercapacitors is not fully yet known. In order to maintain a full polarization effect (as opposed to simply increasing the electrode conductivity), we kept the AuNP at a short distance from the electrode. This is achieved by coating the colloids with a negatively charged ligand - the same approach used to keep a colloidal suspension intact.
Here we explore the addition of nano-size Au particles (AuNP) to active-carbon electrodes to find a large amplification in the specific capacitance. For example, C-V data at a scan rate of 20 mV/s indicated a specific capacitance amplification of more than 10 (!) (with respect to a reference sample without the colloids) when 30 micro-g of AuNPs were incorporated with 200 milli-g of active carbon while using a 1 M Na2SO4 electrolyte and a 5% cellulose acetate butyrate binder. These experiments were corroborated by simulations: the Au colloids are indeed to be placed at close proximity but not in contact with the electrodes.
The Influence of Additives on the Polybenzimidazole Membranes in Vanadium Redox Flow Batteries
Authors: Diaz-Abad Sergio , Jesse Kate Ashley , Davis Benjamin L , Maurya Sandip 
Published: September 2023

In recent years, membrane development has been a focus to replace Nafion as the only viable choice for Vanadium redox flow batteries (VRFBs). Efforts were made to develop polymeric membranes with a lower cost and especially with lower vanadium ions crossover to minimize the costs and hassles associated with frequent electrolyte rebalancing. Among researched VRFB membranes, polybenzimidazole (PBI) membrane stands out as one of the most promising candidates thanks to its incredibly low vanadium permeability and lower cost than Nafion. However, its lower ionic conductivity when compared to Nafion which results in low voltage and energy efficiency – is a main barrier for its widespread acceptance in VRFBs.
In order to improve the conductivity of PBI membranes, efforts have been made, such as chemical alteration of PBI backbone, and addition of ionic and non-ionic side groups. However, these approaches add complexity in the synthetic procedure resulting in a higher membrane cost. Therefore, simple approaches such as blending PBI polymer with additives (e.g. Nafion, polypentafluorostyrene, etc.) provide composite membranes with suitable conductivities for VRFBs. However, these additives leach into the vanadium electrolyte solution depending on their solubility. They can affect the kinetics of the anode and cathode reactions which is largely omitted in the literature. Therefore, in this study, we have investigated the effects of different additives, used for the fabrication of composite PBI membranes, on the electrode and VRFB performance. The kinetic performance loss is studied in-situ and ex-situ by electrochemical impedance spectroscopy. We have also established the Structure–Performance Relationship of additives with VRFB performance.
Pemion®, a High-Performance Hydrocarbon Proton-Exchange Membrane Demonstrating >100 °C Stability for Next-Generation Heavy Duty Fuel Cell Systems
Authors: Britton Benjamin , Jones Scot , Chen Nathan , Adamski Mike , Lee Hsu-Feng , Skalski Thomas 
Published: September 2023

Until recently it was thought that hydrocarbon-based (i.e. non-fluorinated) proton-exchange membranes faced intractable issues in achieving the high performances, chemical stability, and mechanical integrity for effective integration into fuel cells. However, Pemion® PF1-HLF8-15-X, a composite membrane incorporating a new class of polyarylene sulfonic acids, has been commercialized to meet and exceed precedents set for decades by perfluorosulfonic acids (PFSAs) membranes. These attributes include:

The first demonstrable success in all three categories of US Department of Energy accelerated stress tests (open circuit, humidity cycling, combined oxidative-mechanical cycling) without additives, using mass-market components and processes.

This suggests greater system lifetimes are achievable and readily incorporated by fuel cell OEMs.

Consistent high performances that exceed heavy duty targets (e.g. peak power densities >1.4 W/cm² with a 15 µm membrane) exhibiting comparable area resistances to state-of-the-art PFSA-based materials but across a broader operational temperature range, including a higher temperature operating window of 95 °C without area resistance gain and 110 °C without degradation,

This enables long-targeted benefits, chief among which are heat exchanger size reductions and an end to over-specification for heavy duty transportation and aviation applications.

Significantly reduced gas crossover in all conditions

This enables greater fuel efficiency and the potential for increased component lifetimes or operational pressures.

A green and “future proof” chemistry

In light of EU-REACH and EPA threat of regulation and the fact that PFSAs emit fluorinated acid derivative PFAS of concern during operation, hydrocarbon materials are the only way to ensure a robust supply chain into the future, with additional benefits of simplifying recycling at end-of-life.
These combined benefits represent the near-term potential to realize a step-function alteration in the economic viability of fuel cell systems for both transportation and stationary applications.
High Capacity Sn Metal Anode for Aqueous Proton-Based Batteries
Authors: Zhang Haozhe , Lu Xihong , Meng Shirley 
Published: September 2023

Aqueous proton-based batteries (APBs) as a good choice to respond battery diversity, delivering safety, cost, environmental friendliness and high-power necessary for renewable energy storage.1 However, most promising conventional aqueous battery anodes have relatively poor compatibility in acid. The limited existing anode options like Pb and MoO3 can hardly match the high-performance of advanced cathodes, leading low-voltage and unsatisfactory energy density of APBs.2-4 Therefore, the exploration of high-performance anode materials is thus of critical issue for the APB assembling.
Sn metal should be one of the most suitable APB anode choices due to its relatively high hydrogen evolution reaction (HER) overpotential, large theoretical capacity (451.6 mAh g−1) and negative redox potential (−0.14 V vs. SHE). With a body-centered tetragonal crystal structure and similar facet surface energy, Sn metal deposit in polyhedral morphology isotropically. This may cause serious “dead Sn” issue when deposition capacity increases because large Sn particle has limited contact with the substrate and easily to shed from the electrode, resulting in low Coulombic efficiency and short lifespan.
We will present our efforts of developing Sn anode with high capacity and long lifespan by an interfacial alloying regulation approach. Smaller grain size and more uniform Sn deposition can be achieved by higher propensity for nucleation and Sn migration energy barrier. Extra interfacial interaction suppresses shedding of Sn polyhedron particles, thus prohibiting the formation of “dead” Sn. Based on the optimized Sn metal anode, we propose several promising designs for APBs, with high performance such as high output voltages, good specific energy densities, fast kinetics, and long life.

References

X. Wu, J. J. Hong, W. Shin, L. Ma, T. Liu, X. Bi, Y. Yuan, Y. Qi, T. W. Surta, W. Huang, J. Neuefeind, T. Wu, P. A. Greaney, J. Lu, X. Ji. Nat. Energy
2019, 4, 123-130.

W. Chen, G. Li, A. Pei, Y. Li, L. Liao, H. Wang, J. Wan, Z. Liang, G. Chen, H. Zhang, J. Wang, Y. Cui. Nat. Energy
2018, 3, 428-435.

Y. Liang, Y. Jing, S. Gheytani, K. Y. Lee, P. Liu, A. Facchetti, Y. Yao. Nat. Mater.
2017, 16, 841-848.

X. Wang, Y. Xie, K. Tang, C. Wang, C. Yan. Angew. Chem. Int. Ed.
2018, 57, 11569-11573.
Synthesis and Excited State Charge Separation Involving Coordinated C60 of π-Extended Pyrazinepyrene Fused Zinc Phthalocyanines
Authors: Sastre-Santos Ángela 
Published: September 2023

Polycyclic aromatic hydrocarbons (PAHs) play an important role in organic electronics.[1] To increase the stability and the conjugation, pyrene units could be further attached through heteroatoms to improve the photo/chemical stability to oxygen or light.[2] In terms of the synthesis of these types of large acenes through pyrene, many routes have been studied and one of the best protocols is to synthesize the quinoxaline derivative from the dione and the corresponding diamino subunit.[3]
Herein, we will present a series of pyrazinepyrene fused zinc phthalocyanines (ZnPc-Pyrn) as a new class of π-extended phthalocyanine systems. Bathochromically shifted absorption as a function of the number of pyrazinepyrene entities due to extended π-conjugation, and quenched fluorescence due to the presence of fused pyrazinepyrene were witnessed. The electronic structures of these phthalocyanines were probed by systematic computational and electrochemical studies while the excited state properties were examined by pump-probe spectroscopies operating at the femto- and nanosecond time scales. Like the excited singlet lifetimes, the excited triplet states also revealed diminished lifetimes with an increased number of pyrazinepyrene entities. Further, the coordinatively unsaturated zinc in these molecules was coordinated with phenyl imidazole functionalized fullerene, ImC60 to form a new series of donor-acceptor conjugates. Upon full characterization of these conjugates, the occurrence of excited-state charge separation was established by transient pump-probe spectroscopy covering wide temporal and spatial regions. With an increase in pyrazinepyrene entities, an increased rate of forward charge separation was witnessed while rate constants for charge recombination were slower resulting in the final lifetime of charge-separated states of about 40-50 ns, better than that reported earlier for a similar pristine zinc phthalocyanine derived dyad. [4]
Acknowledgments
Authors acknowledge the support from the Spanish Ministerio de Ciencia e Innovación (MICINN/FEDER, PID2020-117855RB-I00 to ASS) and Generalitat Valenciana (CIPROM/2021/059 and MFA/2022/028 to ASS) and US-National Science Foundation (2000988 to FD). The computational work was completed at the Holland Computing Center of the University of Nebraska, which receives support from the Nebraska Research Initiative.

References

1. Zhang, Y. Cao, N. S. Colella, Y. Liang, J.-L. Brédas, K. N. Houk, A. L. Briseno, Acc. Chem. Res.
2015, 48, 500-509.
2. T. M. Figueira-Duarte, K. Müllen, Rev.
2011, 111, 7260-7314; b) P. Jin, T. Song, J. Xiao, Q. Zhang, Asian J. Org. Chem.
2018, 7, 2130-2146.
3. a) H. Shang, Z. Xue, K. Wang, H. Liu, J. Jiang, Eur. J.
2017, 23, 8644-8651; b) T. Khoury, M. J. A. Crossley, Chem. Commun.
2007, 4851-4853; c) K. Kise, A. Osuka, Chem. Eur. J.
2019, 25, 15493-15497
4. J. Follana-Berná, Andrew Dawson,Sairaman Seetharaman, Paul A. Karr, Ángela Sastre-Santos, and Francis D’Souza, submitted.

Figure 1
Self-Assembly of Functional Organic Chromophores
Authors: Hill Jonathan P. 
Published: September 2023

Aggregate structures of organic chromophores strongly affect their properties and so has become an active area of research. Self-assembly and supramolecular methods present important means to influence aggregation processes, and these have become active areas of research. We have studied the self-assembly of differently structured chromophore molecules with emphasis on porphyrins,1 pyrazinacenes,2 hexabenzocoronenes (HBC) and oligophenylenes (such as sexiphenyl), and the various methods of doing this including molecular design, surface assembly (under ambient or UHV conditions), and using interfacial media such as in the Langmuir and Langmuir-Blodgett techniques. For the latter, we have applied principles of amphiphilicity to generate on-interface structures,3 which can be lifted as multilayered films and exploited for the preparation of electronic devices.4 In this work, we will describe the self-assembly properties based on precipitation/gelation, assembly at solid surfaces, and interactions at an air-water interface. We will emphasize the molecular structure as a key feature including the effects of π-π stacking, conformational flexibility and amphiphilicity. Self-assembly and supramolecular techniques stand out as the most effective methods for obtaining nanomaterials having the molecule-level definition of structure important for any applications of the resulting materials.
References: 1) Y. Xie, M. Akada, Jonathan P. Hill, Q. Ji, R. Charvet, K. Ariga. Chem. Commun. (2011) 47, 2285–2287; 2) G. J. Richards, J. P. Hill. Acc. Chem. Res. (2021) 54, 3228–3240; 3) P. Mondal,G. Manna,T. Kamilya,M. Das,K. Ariga,G. J. Richards,J. P. Hill,S. Acharya. Adv. Mater. Interfaces (2022) 9, 2200209; 4) P. Mondal, et al. Submitted (2023).
Modern Applications of Porphyrin-Based MOFs in Agriculture
Authors: Harvey Pierre D. 
Published: September 2023

Nanosized metal-porphyrinic frameworks are an interesting class of porous electro- and photoactive materials finding applications in medicine (photodymanic therapy, photothermal therapy, drug delivery and chemotherapy, immunotherapy), [1], sanitary and antimicrobial devices [2], waste water purification [3], photocatalytic organic transformations [4], production of solar fuels [5], and more recently, in agriculture [6]. The fact that porphyrin derivatives are colored, they are prone for the photosensitization of singlet oxygen (1O2(g); a reactive oxygen species of type II) either at the solid state/air interfaces or in solution leading to applications listed above using visible light. In fact, they even do this efficiently. Reactive oxygen species of type I (for examples, H-O radical, HO-OH, superoxide radical, perhydroxyl radical, etc) are also photo-produced when given metals inside the porphyrins and metallic nodes in the frameworks are used, or when the metal-porphyrinic frameworks form a composite with another semiconductor. Moreover, the size of the nanoparticles can be tailored. All of these properties are cleverly exploited in the field of agriculture and include the following applications: controlled delivery of pesticides and agro-chemicals, detection of pesticides and pathogenic metals, elimination of pesticides and toxic metals, and photodynamic antimicrobial activity, and the nanosized metal-porphyrinic frameworks also have an important implication in food safety. This presentation will describe these features along with new experimental results.
References:
[1] Harvey, Pierre D.; Ple, Jessica, Journal of Inorganic and Organometallic Polymers and Materials (2021), 31(7), 2715-2756.
[2] Schlachter, Adrien; Asselin, Paul; Harvey, Pierre D., ACS Applied Materials & Interfaces (2021), 13(23), 26651-26672.
[3] Harvey, Pierre D., Journal of Materials Chemistry C, (2021), 9(47), 16885-16910.
[4] Harvey, Pierre D., Journal of Porphyrins and Phthalocyanines (2021), 25(7/8), 583-604.
[5] Asselin, Paul; Harvey, Pierre D. ACS Applied Nano Materials (2022), 5(5), 6055-6082.
[6] Sajjadinezhad, Seyed Mehrzad; Tanner, Kevin; Harvey, Pierre D., Journal of Materials Chemistry B, (2022), 10(44), 9054-9080.
Porphyrins – Effective Photocatalysts for Red Light-Induced Functionalizations of Biomolecules
Authors: Gryko Dorota 
Published: September 2023

Recently, photoredox catalysis has begun to influence molecular biology and medical sciences for its mild conditions for generating highly reactive species (i.e., radicals), enabling novel and selective functionalisations of biomolecules.[1] In line with this, porphyrins, which can transfer energy (photosensitization) or electrons (photoredox catalysis) when exposure to light, seem to be highly advantageous. Given that their electron absorption shows a characteristic Soret band at 420 nm with a high molar extinction coefficient (105 M-1 cm-1),[2] they have been mainly used in blue-light-induced reactions. These molecules, however, absorb red light (four Q-bands at 518, 553, 592 and 648 nm with molar extinction coefficients of 104 M-1 cm), which has the benefit of low energy, lower health risks,[3] and more in-depth penetration of various media.[4]

Fig. 1: Porphyrins in red lightinduced transformations
We established that due to their diverse photophysical properties, porphyrins promote photoinduced electron transfer events under red light irradiation.[5] They act as effective photooxidants (alkylation of carbonyl compounds, thiol-ne reaction and reductive decarboxylation) and photoreductants (in arylation of heteroarenes, selenylation, thiolation and reduction of nitro compounds). These bioinspired photocatalysts exhibit features that outperform other catalysts operating under red light, as they are really non-toxic and can be applied in biological systems. Thus, we believe that free-radical porphyrins are a valuable contribution to the set of red-light photocatalysts, and this study will lead to more practical biosynthetic applications.

References

[1] Liu, W.; Watson, E. E.; Winssinger, N. Chim.
Acta
2021, 104, e202100179
[2] Giovanetti, R. The Use of Spectrophotometry UV-Vis for the Study of Porphyrins, Macro to Nano Spectroscopy, 2012, ISBN 978-953-51-0664-7, InTech
[3] Smith, A. M.; Mancini, M. C.; Nie, S. Nature Nanotechnology
2009, 4, 710–711.
[4] Szacilowski, K.; Macyk, W.; Drzewiecka-Matuscek, A.; Brindell, M.; Stochel, G. Rev.
2005, 105, 2647–2694.
[5] Rybicka-Jasińska, K.; Wdowik, T.; Łuczak, K.; Wierzba, A.J.; Drapała, O.; Gryko, D. ACS Org. Inorg. Au
2022, 2, 422–426.

Figure 1
Electrocatalytic and Spectroscopic Studies on Cytochrome Bd Oxidase, a Highly Diverse Bacterial Defense Factor
Authors: Makarchuk Iryna , Kaegi Jan , Melin Frederic , Friedrich Thorsten , Hellwig Petra 
Published: September 2023

The selective reduction of oxygen to water is crucial to life and a central process in aerobic organisms. It is catalyzed by several different enzymes, including cytochrome bd oxidases that are solely present in prokaryotes, including several pathogens. In addition, these enzymes play a crucial role in protection against oxidative stress, in virulence, adaptability and antibiotics resistance. The reduction of O2 occurs at the high spin D-type heme in all cytochrome bd oxidases, that is also the binding site for several ligands from signaling processes, including NO, H2S and CO.
Here we present the electrocatalytic study of the cytochrome bd I and bd II oxidases from Escherichia coli
(1,2) as well on other related bd oxidases. Structural parameters that are crucial for the reactivity towards oxygen are analyzed. The pH dependency of the binding and release of NO, an important signaling factor is presented. The influence of mutants in the proton channel on the NO release is discussed.
(1) Grauel, A. Kägi, J. Rasmussen, T. Makarchuk, I. Oppermann, S. Moumbock, A., Wohlwend, D., Müller, R., Melin, F., Günther, S., Hellwig, P., Böttcher, B., and Friedrich, T., ‘Structure of Escherichia coli cytochrome bd-II type oxidase with bound aurachin D’ (2021) Nat. Commun., 12:6498.
(2) Nikolaev, A., Safarian, S., Thesseling, A., Wohlwend, D., Friedrich, T., Michel, H., Kusumoto, T., Sakamoto, J., Melin, F., Hellwig P. ‘Electrocatalytic evidence of the diversity of the oxygen reaction in the bacterial bd oxidase from different organisms’ (2021) Biochim. Biophys. Acta 1862, 148436.