bluuebunny/crossref_metadata_2025_split huggingface dataset:
Layered Monoclinic Perrierite Oxo-Silicate La4Mn5Si4O22+Δ: A New Interstitial Oxide Ion Conductor for Low Temperature Applications
Authors: Sheikh Md Sariful , Meng Jun , Jacobs Ryan , Liu Jian , Nachlas William O. , Morgan Dane 
Published: September 2023

Oxide-ion conductors are important for various energy applications such as solid oxide fuel cells, solid oxide electrolyser cells, oxygen separation membranes, oxygen sensors, etc. State-of-the-art stable oxygen active materials often have adequate oxygen ion diffusion and chemical surface exchange only at high temperatures (> 700 oC). A promising strategy to improve the oxygen ion transport is to use the interstitial oxygen ion conductors as the interstitial diffusion barriers are often lower than vacancy-mediated diffusion barrier, potentially enabling reduced operation temperatures. However, due to the large size of the oxide ion, the formation of an adequate concentration of interstitials is difficult and hence the number of interstitial oxygen conductors is currently limited to just a handful of compounds, e.g., Ruddlesden-Popper, apatite, melilite, scheelite, fluorite and disordered hexagonal perovskites.
We screened a large number of oxide materials using high-throughput ab initio methods (Please see separate poster from Jun Meng on this screening) and predicted stable formation and fast diffusion of interstitial oxygen in a new class of material La4Mn5Si4O22+δ (LMS), motivating us to synthesize this material and experimentally study its oxide ion transport properties. The room temperature X-ray diffraction study followed by Rietveld refinement confirmed its layered monoclinic perrierite structure. Electron probe micro-analysis (EPMA) and iodometric titration revealed the presence of the hyper stoichiometric oxygen anion (δ ~ + 0.5) confirming the interstitial oxygen ions within LMS lattice. Thermogravimetric analysis showed a small mass increment in LMS when heated at high temperatures suggesting the high temperature stability of interstitial oxygen ions. The measured ionic conductivity of LMS is higher than the yttria stabilized ZrO2, perovskite oxide La1-xSrxCo1-yFeyO3 and Ruddlesden-Popper oxide materials. Electrical conductivity relaxation studies demonstrated that self-diffusion and surface exchange coefficients of oxygen ion are comparable to or higher than many state-of-the-art oxide ion conductors. Finally, the high temperature stability of the synthesised material was confirmed using X-ray diffraction after each measurement.
Overall, this experimental study confirms computational predictions that layered perrierite LMS is a new class of interstitial oxide ion conductors and suggests our overall approach may help the rational design of interstitial mediated oxide ion conductors-based devices suitable for efficient and stable applications at low temperature.
(Digital Presentation) Biogenic Electrodes for Low-Temperature Solid Oxide Fuel Cells
Authors: Bhattacharjee Jyoti , Roy Subhasis 
Published: September 2023

Biogenic Electrodes for Low-Temperature Solid Oxide Fuel Cells

Jyoti Bhattacharjee, Subhasis Roy*

Department of Chemical Engineering, University of Calcutta, 92 A. P. C. Road,

Kolkata-700009, India

* Email: subhasis1093@gmail.com/srchemengg@caluniv.ac.in

Abstract:

Solid oxide fuel cells (SOFCs) are potential energy-generation devices. They operate at high
temperatures, typically between 800°C-1000°C, limiting their utility. The primary challenge
in developing these fuel cells is synthesizing strong biogenic electrodes that function at low
temperatures, maintaining high performance. This experimental study examines how eco-friendly,
facile, and novel techniques for synthesis can be used to make robust, effective, and affordable
electrodes for low-temperature recyclable SOFCs (LT-SOFC). A green approach
was implemented by using biomass waste and biochar, specifically coconut shells and rice
husks, as raw materials. The synthesis comprised the hydrothermal carbonization of biomass
precursors, such as lignocellulosic nanostructures, and carbon nanotubes under controlled
conditions, followed by activation with potassium hydroxide(KOH). The resulting electrodes
had a large surface area, catalytic oxygen reduction, excellent conductivity, and sufficient
electrochemical performance. The efficacy of the biomass-derived electrodes was enhanced
by employing transition metal oxides as electrocatalysts, such as nickel oxide(NiO) and
cobalt oxide(Co3O4). The morphology and elemental composition of the electrode material
were studied using the scanning electron microscope(SEM) and energy-dispersive X-ray
spectroscopy(EDS). Electrochemical impedance spectroscopy(EIS)was used to examine the
electrochemical properties of cell electrolytes. Findings demonstrated that the hydrothermal
strategy led to the formation of homogeneous and porous electrode structures with high
galvanic activity. The biodegradable LT-SOFC stack achieved an optimal power density of
346mW/cm2 at around 550°C, indicating a substantial increase over previous experiments.
Our results have significant economic consequences for the expansion of sustainable and
renewable energy innovations in industry and nanotechnology, providing auxiliary power in
automobiles and hydrogen generation. Greenhouse gas emissions and carbon footprint can be
diminished by using biomass waste streams as feedstocks, reducing the need for fossil fuels.
The outcomes of this research provide important insights into the development, challenges,
and future possibilities of biomass-derived electrodes, and minimal temperature electrolytes
for stable SOFCs.

Keywords:

Biomass-derived; carbon footprint; electrochemical efficiency; green energy; low-temperature solid oxide fuel cells; nanotubes.
Electrochemistry of Selected Acetaminophen Derivatives
Authors: Mikysek Tomas , Česla Petr , Váňová Jana , Roušarová Erika , Musílek Kamil , Maliňák David , Roušar Tomáš , Ludvik Jiri 
Published: September 2023

Acetaminophen (N-(4-hydroxyphenyl)acetamide, APAP) belongs to the most frequently used pharmaceuticals with analgesic and antipyretic effect [1]. The metabolization of APAP via oxidation pathway lead to formation of highly reactive intermediate N-acetyl-p-benzoquinone imine (NAPQI). It immediately reacts with a nucleophile e.g. with glutathione by formation of respective conjugate. The level of such conjugates can be directly linked to the toxicity of APAP in humans.
Hence, three derivatives of acetaminophen were synthesized and characterized [2]. In this contribution, we focus on the characterization of redox properties of selected acetaminophen derivatives (see scheme 1) which were studied by means of cyclic voltammetry, rotating-disk voltammetry and UV-VIS absorption spectrometry. The oxidation mechanism was studied in phosphate buffers of different pH as well as in non-aqueous environment of N,N-dimethylformamide The influence of substituents on the electron transfer mechanism was estimated and corresponding rate constants were evaluated. We found that the protonation/deprotonation of acetaminophen derivatives act as a rate determining steps in aqueous media. The obtained electrochemical results were accompanied by chemical ones using reaction of the conjugates with diphenylpicrylhydrazyl (DPPH radical assay) in order to examine their interaction with radical, hence radical scavenging ability.

Acknowledgement

This work was supported by the Czech Science Foundation (GA19-11867S).

References

L. O. Boreus, F. Sandberg, Acta physiologica Scandinavica
1953, 28, 261-265.

J. Vanova, D. Malinak, R. Andrys, M. Kubat, T. Mikysek, E. Rousarova, K. Musilek, T. Rousar, P. Cesla, J. Chromatogr. A
2022, 1669, 11.

Figure 1
Novel Synthetic Access to Para-Quinones Via Direct Electrochemical Oxidation
Authors: Sprang Fiona , Waldvogel Siegfried R 
Published: September 2023

Equipped with unique and straightforward tunable redox properties quinones find manifold applications ranging from bio-active compounds to material science.[1] Current state of the art synthesis still resorts to stoichiometric amounts of problematic chemical oxidizing agents and noble catalysts adding to the growing environmental strain by depletion of scarce resources.[2] In order to overcome this challenge, we have developed novel and scalable protocols for the synthesis of para-quinones applicable to readily available, inexpensive phenols and benzaldehydes.[3] In advancement of previous methods, the oxidation is performed free of catalyst, mediator, or terminal oxidizing agent, effectively minimizing waste. Electricity serves as a sustainable, reagent-free oxidant and enables excellent selectivity. Effortless scalability is ensured by the development of a flow protocol, which is operable at mild, ambient conditions. The novel protocols provide quinones in yields up to 99% and possess high synthetical utility through tolerance of a wealth of functional groups, including halogens, fulfilling the prerequisite for facile late-stage modification. The scalability of the reaction was proven on a gram-scale without corrosion in yield. Moreover, the versatility of the method was demonstrated by successful extension of the protocol to generate value-added quinones from the biopolymer lignin.
Literature:
[1] a) E. J. Son, J. H. Kim, K. Kim, C. B. Park, J. Mater. Chem. A
2016, 4, 11179; b) L. A. Sazanov, Nat.
Rev. Mol. Cell Bio.
2015, 16, 375.
[2] a) R. Yoshida, K. Isozaki, T. Yokoi, N. Yasuda, K. Sadakane, T. Iwamoto, H. Takaya, M. Nakamura, Org.
Biomol. Chem.
2016, 14, 7468; 19, b) K. Omura, Synthesis
1998, 1998, 1145.
[3] F. Sprang, J. D. Herszman, S. R. Waldvogel, Green Chem.
2022, 24, 5116–5124.

Figure 1
Electrochemical and Spectroscopic Investigations of L-Glutathione with Bismuth Pharmaceuticals
Authors: Cheek Graham , Dierickx Abram 
Published: September 2023

Introduction
The electrochemical and spectroscopic investigation of bismuth(III) compounds with L-cysteine has been carried out in this laboratory since our initial publication.1 Cyclic voltammetry has shown that the interaction of L-cysteine with bismuth nitrate, bismuth salicylate, and bismuth citrate increases the solubility of these compounds by complexation with L-cysteine, thereby increasing the reduction current for the bismuth complexes formed. The appearance of a UV-VIS spectroscopic band at 340 nm indicates the formation of a Bi-S bond, the sulfur being supplied by the L-cysteine. These investigations have been conducted at pH 1.00 and 3.00 to simulate conditions in the human stomach and at pH 7.40 MOPS [(3-N-morpholino)propanesulfonic acid] to simulate general physiological conditions, in particular the intestinal tract. In this presentation, continuing studies of L-glutathione, a tripeptide incorporating L-cysteine, under these conditions shall be discussed. This work is applicable to the important field of bismuth pharmaceuticals as a means of understanding the interaction of these compounds under various conditions in the human digestion system.2

Results and Discussion
Initial studies of L-glutathione with bismuth nitrate, bismuth salicylate, and bismuth citrate have been carried out under conditions similar to those of our initial work.1 It has been found that the general characteristics of the cyclic voltammograms for L-glutathione (GSH) are similar to those for L-cysteine; however, the slower rate of complexation of GSH with these bismuth compounds is evident in the changes in voltammetric features in successive sweeps. In the case of GSH addition to bismuth citrate in pH 7.4 MOPS buffer, for instance, the first sweep shows reduction of the bismuth:GSH complex at -0.71 V vs Ag/AgCl at a gold electrode, whereas a reduction process at -0.60 V is observed on the second sweep. Similar results are obtained at glassy carbon. The bismuth:GHS complex is destroyed during the reduction process as a bismuth film forms on the electrode surface. The following sweep, then, is indicative of the complexation environment in solution at that point. The bismuth ion, restored in the stripping step, apparently does not have time in the few seconds after the stripping process to fully form a complex with GSH. The observed reduction potential around -0.60 V is due to the reduction of another bismuth complex, perhaps with citrate. Further investigations are in progress to more fully describe this situation.
References

G. T. Cheek and D. Peña, J. Electrochem. Soc.,
167, 155522 (2020)

H. Li, R. Wang, and H. Sun, Acc. Chem. Res.,
52, 216 (2019).
Facilitated Enzymatic Chain Reaction-Based Bioelectrocatalysis via Solid Binding Peptide-Guided Bienzyme Co-Immobilization Strategy
Authors: Lee Hyeryeong , Bang Yuna , Chang In Seop 
Published: September 2023

The multienzyme complex in biological systems are highly ordered so that intermediate molecules occurred during enzymatic sequential reaction are efficiently delivered to downstream enzymes without diffused to bulk phase. Recently, the cascadic multienzymes have been adopted to enzymatic electrocatalytic platform to be applied for enzyme-based bioelectronics such as enzyme fuel cell, biosensors, and electrosynthetic system. This cascadic enzyme-electrode, in which interfacial electron transfer (ET) occurs concurrently with inter-enzyme chain reaction, has been regarded promising for the advancement of enzyme-based bioelectronics performance. However, co-regulation of interfacial electrical connection and inter-enzyme chain reaction efficiency has been known to be highly challenging due to systematic complexity. In this context, the generalized enzyme immobilization tool is significantly needed to be developed to control inter-enzyme and enzyme-electrode interface concurrently.
Herein, enzyme cascade-based direct bioelectrocatalytic system has been constructed by immobilizing enzymes using the solid binding peptide (SBP) linker that can control surface-orientation of enzymes on electrode. Here, invertase (INV) and FAD-dependent glucose dehydrogenase gamma-alpha complex (GDHγα) were utilized as upstream- and downstream enzyme so that the sucrose hydrolysis (at INV) and glucose oxidation (at GDHγα) is concomitantly occurred. Especially, the GDHγα that is direct electron transfer (DET)-capable oxidoreductase, has bi-function that are downstream catalysis and transport of produced electrons toward electrode that cause bioelectrocatalytic current signal. To immobilize enzymes and control relative orientation of coupling enzymes, the SBP linker was tethered various termini (C-, N-, or both termini) of INV when SBP fusion site of GDHγα was fixed to C-terminus of GDH α subunit to enable efficient interfacial DET, based on previous study. Therefore, the inter-enzyme relative orientation dependent chain reaction efficiency was evaluated with resulting DET-based electrocatalytic current. In the result, it was found that the interfacial DET at GDHγα-electrode could be affected by binding conformation of co-immobilized enzyme, fusion INV. Most importantly, the chain reaction efficiency between INV and GDHγα was revealed to be diverse depending on different relative orientation determined by SBP tethering sites in enzymes. The intermediate delivery route was changed by relative positioning of coupling active sites, affecting overall cascade reaction rate. Taking into account the factors related with interfacial DET and intermediate delivery, precise design of bienzymatic electrode is indeed necessary in order to introduce SBP-tethering technique to cascadic enzyme-derived direct electrocatalytic platform.

Figure 1
Construction of Solid Binding Peptide (SBP)-Fused Non-Native Chimeric Enzyme to Promote Bienzymatic Cascade Induced Bioelectrocatalysis
Authors: Bang Yuna , Lee Hyeryeong , Chang In Seop 
Published: September 2023

In nature, most enzymes form a multienzyme complex called “metabolon” in the cellular system. The natural metabolon has been evolved to increase the efficiency of multi-step biocatalysis involved in such conditions. Such principle of enzymatic cascade reaction could be applied to the system which mimics pertinent reaction in vitro. Especially, its pertaining to bioelectrocatalytic system is quite promising to enhance its performance in terms of electrical generation or biochemical production, depending on systematic applications. In the previous studies , it was abundantly reported that multi-enzymatic reaction has been utilized to generate higher electrical current via sequential enzymatic oxidation of substrates (e.g., methanol, glucose, etc.) in bioelectrochemical systems, and to operate biochemical production system utilizing multi-enzymic conversion or reduction reactions. However, it is still challenging to implement multi-step enzymatic reaction in the electrode platforms due to unmanageable regulations of inter-enzyme distance or electrical connection between enzymatic cofactor and electrode, during multi-enzyme co-immobilization on electrode surface.
Herein, we intentionally design and construct variants of chimeric enzyme in which two enzymes, invertase (INV) and glucose dehydrogenase (GDH), are conjugated with peptide linkers. We expected that INV hydrolyzes sucrose into fructose and glucose, then glucose is oxidized at the catalytic subunit of GDH, releasing electrons toward the electrode. It also employed solid binding peptides (SBPs) fused to GDH in chimeric enzyme for the electrical connection of GDH-SBP and electrode. In order to accomplish the desired reaction with chimeric enzyme, we have conducted the following tests; 1) The recombinant plasmid harboring the genetic sequence of two enzymes with an in-between linker was constructed. 2) By production of chimeric proteins, the chain reaction efficiency of fusion constructs was compared depending on the length of the linker. 3) The gold binding peptide (GBP) was fused to sites (N- and C-terminus, or other sites) of the catalytic subunit of GDH. And finally, 4) the electron transfer rates were monitored and compared depending on the GBP tethering sites. Throughout the whole study, we found the factors affecting the occurrence of multienzyme cascade-based bioelectrochemical reactions and how to control these factors to improve the reaction efficiency

Figure 1
Expanding Our Cyclodextrin-Based Sensors with Automation and New Surfaces
Authors: Sajedi Ferdows , Edgar Julia , Halpern Jeffrey M 
Published: September 2023

We have had significant success in building cyclodextrin mediated sensors. We initially started with a gold surface, being able to detect analyte up to three times post modification [1]. Afterwards, we improved the stability and reusability by moving to a phenyl-modified carbon electrode via diazonium salt chemistry [2]. With his new surface, we were able to detect cortisol up to 10 different times with high accuracy, repeatability, and sensitivity in buffer, urine, and artificial saliva. We were limited by manually manipulating the electrode; therefore, we were not able to test the electrode for greater than 10 measurements. Within this poster, we intend to present our ideas and progress towards developing an automated detection system that can be preprogrammed to clean, reset, and test the cyclodextrin-mediated surface with target analytes. Further, we will share our various target analytes and our strategy to expand our sensor surface to include multiple cyclodextrin derivatives.
Research supported by New Hampshire- INBRE through an Institutional Development Award (IDeA), P20GM103506, from the National Institute of General Medical Sciences of the NIH.
[1] Z. Panahi, M. A. Merrill, and J. M. Halpern, “Reusable Cyclodextrin-Based Electrochemical Platform for Detection of trans -Resveratrol,” ACS Appl. Polym. Mater., vol. 2, no. 11, pp. 5086–5093, Nov. 2020.
[2] Z. Panahi, T. Ren, and J. M. Halpern, “Nanostructured Cyclodextrin-Mediated Surface for Capacitive Determination of Cortisol in Multiple Biofluids,” ACS Appl. Mater. Interfaces, Aug. 2022.
Electrodeposition of Ni-Co Alloys from Ionic Liquids and Their Electrocatalytic Properties
Authors: Turmine Mireille , Xie Yuelin , Miche Antoine , Vivier Vincent 
Published: September 2023

Amorphous and nanocrystalline Ni-Co alloys have been deposited on FTO glass in ethylammonium nitrate (EAN), a protic ionic liquid (PIL). In a first step, the physicochemical properties of EAN with Ni2+ and Co2+ salts have been studied as well as the electrochemical behavior of these metal cations in the PIL in order to optimize the electroplating process (Fig. 1). It was shown that when the electrodeposition of Co, Ni and Ni-Co alloys was performed on FTO glass in EAN at 60 ℃ in an oxygen-free environment, nanocrystalline Ni-Co alloys with different atomic ratios were obtained, depending on both the deposition potential and the ion concentration in solution.
The electrocatalytic properties of these materials were then investigated towards the hydrogen evolution reaction (HER). It was shown that the addition of Co in Ni-based alloys can promote the HER, and most notably, amorphous Ni-Co alloys show lower overpotential or reaction rate. This work provides a new route to prepare nanocrystalline and amorphous Ni-Co alloys with different ratio in PIL for practical applications in electrocatalysis such as water splitting.

Figure 1
Assessing Proton and Hydrogen Permeabilities for Nanoscopic Oxide Coatings Using a Rotating Disk Electrode
Authors: Yim Kyungmin , Cohen Lucas , Fraga Alvarez Daniela V. , Jin Jingjing , West Alan C. , Weimer Matthew S , Dameron Arrelaine A , Moulton Staci , Fortiner Serafina , Glenn Jennifer , Hawkes Justin , Capuano Christopher , Ayers Katherine E. , Esposito Daniel V. 
Published: September 2023

The transport of protons and molecular hydrogen (H2) are of relevance to a wide range of electrochemical applications ranging from fuel cells and electrolyzers to sensors and photoelectrochemical cells. One way to modulate the flux of these species to improve device performance such as selectivity and efficiency is to encapsulate electrodes with semi-permeable oxide coatings. [1-3] Thus, knowing the permeabilities of these species within thin oxide layers is of great importance for guiding the design of electrodes and devices. Towards this end, we have employed a modified rotating disk electrode (RDE) set-up to quantify proton and hydrogen permeabilities through sub- 20 nm thick silicon oxide coatings and understand how these transport properties change as a function of the structural and compositional characteristics of the coatings. Oxide coatings were fabricated by both atomic layer deposition (ALD) and photochemical deposition, and their physical and chemical properties characterized by X-Ray Photoelectron spectroscopy and ellipsometry. Based on measurements of the mass transfer limited current density for the hydrogen evolution and hydrogen oxidation reactions, permeabilities were computed. Species permeabilities are furthermore correlated with membrane density and composition, revealing structure-property-performance relationships that can be used to guide the selection of oxide thickness and processing conditions that will optimize performance for an application of interest.
References:
[1] Labrador, N. Y., et al. Hydrogen evolution at the buried interface between Pt thin films and silicon oxide nanomembranes. ACS Catalysis 8, 1767-1778 (2018).
[2] Beatty, M. E., Gillette, E. I., Haley, A. T. & Esposito, D. V. Controlling the Relative Fluxes of Protons and Oxygen to Electrocatalytic Buried Interfaces with Tunable Silicon Oxide Overlayers. ACS Applied Energy Materials 3, 12338-12350 (2020).
[3] Bhardwaj, A. A., et al. Ultrathin silicon oxide overlayers enable selective oxygen evolution from acidic and unbuffered pH-neutral seawater. ACS Catalysis 11, 1316-1330 (2021).