bluuebunny/crossref_metadata_2025_split huggingface dataset:
Adsorbate Molecular and Electronic Structure Effect on Metal-Adsorbate Interactions
Authors: Hasan Mohammad Hasibul , McCrum Ian T. 
Published: July 2021

(Electro)catalysis is a powerful tool which can be used to produce fuels and chemicals, such as hydrogen and ammonia. Economical catalysis requires catalysts which are highly active, selective in producing the desired product, and inexpensive too. Meeting these design goals is challenging and requires intelligent catalyst design. Catalytic activity and selectivity is dictated by the relative energy and activation barriers between adsorbed reaction intermediates, which in turn are determined by how strongly these intermediates interact with the (electro)catalyst surface. Therefore, if we can unveil the mystery behind the driving forces for metal-adsorbate interaction, this could be a step forward towards predictive active & selective catalyst design. From the earlier works of B. Hammer et al. [1] & Federico Calle-Vallejo et al. [2] we know that some of the properties of metals, such as the energy of the metal d-bands, and the surface coordination number, determine how strongly a metal surface will bind to an adsorbate. However, we still do not have enough information on what properties of the adsorbate can influence this metal-adsorbate interaction. The goal of our research is to find what properties or parameters of an anionic adsorbate dictates the interaction between the anion and the metal surface. To bring some light into this, we have experimentally measured the adsorption strengths of a series of anions to an electrode surface and examined how the electronic or molecular structure of these anion adsorbates are correlated with changes in adsorption energies. We will also discuss possible descriptors for adsorption strength based on the structure of the adsorbate.
[1] B. Hammer, J.K. Norskov, Nature, 376, 238-240 (1995).
[2] F. Calle-Vallejo, J.I. Martínez, J.M. García-Lastra, P. Sautet, D. Loffreda, Angew. Chem. Int. Ed., 53, 8316-8319 (2014).
(Invited) Operando Characterization of Transient Material Changes in Battery Cathode Materials By X-Ray Diffraction and Spectroscopy
Authors: Gallaway Joshua W 
Published: July 2021

Operando characterization of battery materials provides several benefits. For example it eliminates the chance that materials are oxidized or further transformed during removal from the cell and sample preparation, and increases the odds that short-lived material changes and intermediate species can be observed and correlated to electrochemical data. Receiving adequate experimental signal from complicated electrochemical cells can be problematic, and the use of synchrotron light is one solution. X-rays with high brightness, flux, or energy can provide data that is adequately temporally (and sometimes spatially) resolved to correlate material changes with cycling data. This talk will present characterization by both X-ray diffraction and X-ray absorption spectroscopy, which provide information about long-range and short-range structural order respectively.
The first example is that of a sulfide all solid-state cathode that is a composite of FeS2, conductive carbon, and Li6.6Ge0.6Sb0.4S5I solid electrolyte (SE).1 Voltage stability window of sulfide SEs is a critical issue, and we directly observe crystal structure distortion of the SE that occurs during discharge. This occurs in the cathode but not elsewhere in the cell, and is reversible provided a minimum potential limit is not passed (see Figure 1). Given the air and moisture sensitivity of the SE, experiments had to be performed within the sealed cell, under significant applied pressure. Operando energy-dispersive x-ray diffraction (EDXRD) allowed data to be collected from buried locations in the bulk of intact and sealed batteries during cycling.2

The second example is that of a rechargeable alkaline Bi-modified MnO2 cathode, in which both Bi and Mn are electrochemically active and provide cycled capacity. The mechanism of MnO2 cycling is complex, first involving insertion of cations into the layered structure, followed by conversion to a new structure. By using rapid collection of X-ray absorption near edge structure (XANES) data at the Mn K-edge and Bi LIII-edge, an interaction between Mn and Bi was identified during early stages of the charging step.3 This gives insight into the cycling mechanism that makes rechargeability possible.

Acknowledgments

This work was supported by the U.S. Department of Energy (DOE) Office of Electricity Delivery and Energy Reliability, Dr. Imre Gyuk, Energy Storage Program Manager. We also acknowledge financial support from the National Science Foundation under Award Number CBET-ES-1924534.

References

Sun, X.; Stavola, A.M.; Cao, D.; Bruck, A.M.; Wang, Y.; Zhang, Y.; Luan, P.; Gallaway, J.W.; Zhu, H., Advanced Energy Materials,2020, 2002861.

Marschilok, A. C.; Bruck, A.; Abraham, A.; Stackhouse, C.; Takeuchi, K. J.; Takeuchi, E. S.; Croft, M.; Gallaway, J.W., Physical Chemistry Chemical Physics, 2020, 22, 20972-20989.

Bruck, A.M.; Kim, M.A.; Ma, L.; Ehrlich, S.N.; Okasinski, J.S.; and Gallaway, J.W., Journal of the Electrochemical Society,
2020,
167, 110514.

Figure 1
Highly Stable Co3O4 Nanofibers in Alkaline Oxygen Evolution Reaction
Authors: Aljabour Abdalaziz 
Published: July 2021

Electrocatalysis of hydrogen and oxygen evolution is an essential route in performing renewable and sustainable energy alternatives. Although hydrogen technologies are largely advanced, the oxygen electrochemistry is mainly limited due to the complexity in seeking suitable and stable electrocatalysts, in unifying electrolytic conditions and hence sluggish reaction kinetics. Herein, we demonstrate the electrocatalytic activity of the nanofibrous cobalt oxide in alkaline oxygen evolution reaction with a generous operation lifetime of 120 hours. The unique and facile preparation pathway of fibers by electrospinning allows enlarged electrode networking and nanofibrous interaction thus leading to extended catalytically active surface area, imperative for well-performing electrolysis. Operating at low overpotential of 293 mV at a current density of 10 mA cm- 2, as well as low Tafel slope of 60.5 mVdec-1 in 1M KOH prove the efficient utilization of nanofibrous Co3O4 electrocatalyst towards oxygen evolution with an excellent long-term stability over 100 hours.[1]
[1] A.A., Long-Lasting Electrospun Co3O4 Nanofibers for Electrocatalytic Oxygen Evolution Reaction, ChemistrySelect 2020, 5, 748, doi.org/10.1002/slct.20.
Monitoring of Doping Polybenzimidazole Membranes with Phosphoric Acid: Insights with Spatial and Temporal Resolution
Authors: Arslan Funda , Böhm Thomas , Kerres Jochen , Thiele Simon 
Published: July 2021

Keywords: Acid Doping Level (ADL), Fuel Cells (FCs), High Temperature (HT), Polymer Electrolyte Membrane (PEM), Phosphoric Acid (PA), Polybenzimidazole (PBI), Raman spectroscopy
High temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) are one of the most promising energy conversion devices with zero local CO2 emission. The polymer electrolyte membrane placed between the anode and cathode plays an important role for the overall fuel cell efficiency. The current state-of-the-art membranes used in HT-PEMFCs are PBI-based materials. Compared to Nafion®-based systems used in low temperature PEMFCs, they allow operation at temperatures up to 180-200 °C and do not require water management. Other advantages of the elevated operation temperature are e.g. accelerated reaction kinetics and tolerance improvement against impurities such as carbon monoxide. However, PBI-based membranes are not intrinsically proton conductive and therefore need to be doped with acid in order to ensure proton conductivity. The acid of choice is phosphoric acid due to its non-volatility and thermal stability.
Acid doping levels are important since they have a huge influence not only on conductivity, but also onto mechanical and thermal properties of a membrane. Commonly, weighing and titration are used to determine the doping level, but they are bulk sensitive only. In this work, confocal Raman microscopy was used to provide temporal and spatial insights into the acid doping process. It can be performed on the membrane before or after application in a fuel cell due to its non-destructive nature. Our results show that acid doping is a diffusion-limited process. Considerable changes in spatial distribution of dopant were observed within the membrane before reaching saturation. Further monitoring of diffusion of phosphoric acid after removal from the doping solution shows that the diffusion continues even after months. Confocal Raman microscopy offers the option to gather information non-destructively and contact-free from within the membrane. The insights into the phosphoric acid doping process of PBI-based membranes presented here are of great importance for the manufacturing and optimization process of high temperature fuel cells and their overall efficiency.
Study of Deuterium Isotope Separation By Anion Exchange Membranes Water Electrolysis
Authors: Sato Haruka , Matsushima Hisayoshi , Ueda Mikito , Ito Hiroshi 
Published: July 2021

1. Introduction
Hydrogen energy is one of solutions for decarbonized society. Water electrolysis is promising as hydrogen production. Currently, water electrolysis with a solid polymer electrolyte membrane has been developed. The electrolysis using a cation-exchange membrane (PEM) has been widely used, while one using an anion-exchange membrane (AEM) is studied as a next-generation method with nonprecious catalysts.
Hydrogen isotope separation is applied as a new application of water electrolysis. The nuclear fusion reactor ITER, which uses deuterium and tritium as fuel, will be operated around 2035 when the isotope separation/enrichment technology will be required.
We have studied deuterium (D) separation by both PEM- and AEM-type. The separation ability of PEM electrolysis remarkably depended on the ratio of water supplied to the current density (stoichiometric ratio: λ) [1]. Interestingly, AEM one was better than PEM [2]. In this study, AEM electrolysis was investigated at various λ in order to improve the separation performance.
2. Experimental
The electrolyte was 0.1 M KOH with 10 at% D. The D concentration was adjusted by D2O. The electrolyte was supplied from the lower part of only the anode side. The ready-made AEM (A201, Tokuyama) was employed as electrolyte. Pt catalyst was used as the anode catalyst and CuCoOx was used as the cathode one. The electrolysis was conducted at constant current densities or water feed at room temperature. The hydrogen gas was analyzed by a quadrupole mass spectrometer to determine the mass number (m = 2 (H2), 3 (HD), 4 (D2)), while the solution discharged from the anode was investigated by FTIR using the attenuated total reflection (ATR) method with a diamond prism.
3. Results and discussion
Figure 1 shows the D content in hydrogen gas evolving from the cathode. In the figure, αgas indicates the separation factor, which is the ratio of protium (H) atomic concentration of the gas to the supplied water. The value of αgas decreased with decreasing λ. The present result suggests H dilution in the gas as well as PEM-type. It should be noted that AEM one could be electrolyzed and keep draining the electrolyte from the anode even at λ ≤ 4, while PEM-type discharged the almost all volume of the electrolyte from the cathode side [1]. This might be explained by the mass transportation by the diffusion and electroosmosis whose flows direction depend on the membrane type.
In our presentation, the other results such as D concentration in electrolyte and pH variation depending on λ will be introduced. We will discuss the D separation mechanism by AEM electrolysis from the viewpoints of the water distribution and the mass transportation in the membrane.
References

K. Harada et al., Int. J. Hydrog. Energy, 45 (2020) 31389-31395.

.H. Matsushima et al., Int. J. Electrochemical Society, 166 (10) F566-F568 (2019)

Figure 1
The First Analytical Method Allowing the Quantitative Determination of a Novel Promising Anticancer Agent Candidate
Authors: Kozak Jędrzej , Tyszczuk-Rotko Katarzyna 
Published: July 2021

The subject of this study is a chemical compound called ethyl 8-(4-methoxyphenyl)-4-oxo-4,6,7,8-tetrahydroimidazo[2,1-c][1,2,4]triazine-3-carboxylate (EIMTC). This substance was found to have good bioavailability as well as low toxicity both in vitro and in vivo.
This work presents for the first time a sensitive voltammetric procedure for the determination of a compound with anticancer activity in human serum using a screen-printed sensor with a carbon working electrode modified with carbon nanofibers. After optimizing the procedure, a linear calibration curve was obtained in two concentration ranges from 2 × 10-9 to 2 × 10-8 mol L-1 and from 2 × 10-8 to 2 × 10-7 mol L-1. The calculated limits of detection and quantification were 5.0 × 10-10 and 1.7 × 10-9 mol L-1 respectively. The method was applied for the determination of the EIMTC in human serum samples after the previous removal of the protein using trichloroacetic acid (TCA).
[1] Tyszczuk-Rotko, K., Kozak, J., Sztanke, M., Sztanke, K., Sadok, I. Sensors
2020
, 20(18), 5217-5227.
A Greener Synthesis of Fe-N-C Catalysts for the Oxygen Reduction Reaction
Authors: Gernhard Marius , Roth Christina 
Published: July 2021

The world is faced with an ever-increasing energy demand that, under the aspect of global warming, must be covered by renewable sources such as wind- and solar energy. However, the main challenge linked to these sources is to provide a continuous energy supply, demanding highly efficient energy storage and conversion devices.
One promising conversion technology are fuel cells. [1] These usually rely on expensive and rare platinum group metal (PGM) catalysts for the sluggish oxygen reduction reaction (ORR). In order to serve the human energy demand, cheap and scalable fuel cell systems are required. The class of M-N-C (M = Fe, Mn, Co) type catalysts shows particularly good catalytic behaviour comparable to PGM based catalysts. However, promising catalysts are usually synthesised from toxic materials with solvent and energy intensive methods. [2]
Here, we present a synthetic approach towards Fe-N-C type catalysts, that uses only non-hazardous chemicals, produces no wastewater and is more energy efficient than classical approaches. We used iron hydroxide as iron source for its lower environmental impact as compared to ferric chloride. Cyanoguanidine (non-toxic) was chosen over cyanamide (toxic) as a pore forming agent and nitrogen source. Tryptophan was used over PANI and the like for its availability from natural sources with no need for toxic precursors. Instead of classical wet chemical approaches we used a solvent free mechanochemical synthesis. And by using vulcan carbon as electron conducting scaffold, we were able to carbonize at 750 °C, increasing the overall energy efficiency. The catalytic activity towards the ORR of the obtained catalysts was determined by rotating disc electrode measurements in acidic and basic media. With a 100 mV lower onset potential, their performance in an alkaline environment is good but not quite comparable to Pt based catalysts.
Future studies will focus on the correlation of nitrogen content as well as porosity of the catalysts with their electrocatalytical behaviour.
[1] I. Staffell, D. Scamman, A. Velazquez Abad, P. Balcombe, P. E. Dodds, P. Ekins, N. Shah, K. R. Ward, Energy Environ. Sci.
2019, 12, 463–491.
[2] H. T. Chung, D. A. Cullen, D. Higgins, B. T. Sneed, E. F. Holby, K. L. More, P. Zelenay, Science
2017, 357, 479-484.

Figure 1
Development of the Electrochemical Chip for Early Detection of Mastitis-Somatic Cell Count and Evaluation of Immune Function
Authors: Kumagai Ryoma , Prasad Ankush , Takanashi Haruka , Kasai Shigenobu 
Published: July 2021

Somatic cell count (SCC) is widely used to monitor bovine mastitis. Dairy farmers in Japan must send bovine milk to a laboratory for this inspection because the SCC device is large and expensive. In recent years, focusing on the increase in neutrophils in the early stage of mastitis, the method that can test for an early stage of mastitis by evaluation of the immune function of somatic cells in milk have been studied.
In the current study, we previously evaluated cellular respiratory activity1. And we evaluated somatic cell count by elevation of respiration activity of somatic cells in milk and elevation of immune function by phorbol 12-myristate 13-acetate(PMA)-stimulated respiratory burst measurement using scanning electrochemical microscopy (SECM)2. In addition, we developed an electrochemical chip that enables counting of somatic cells in milk and evaluation of immune function. In SECM, we applied the oxygen reduction potential using a Platinum (Pt) microelectrode as a probe, scanned the vicinity of cells and between bulk and calculated the oxygen consumption of cells from the difference in current value between the two points to evaluate respiration activity.
Fig.1A shows the arrangement of the electrodes. We made electrochemical chips by photolithography with multiple Pt electrodes and used SU-8 to form an insulating film to determine the electrode size. Fig. 1B is a schematic representation of a well prepared with Polydimethylsiloxane (PDMS). This well can hold 100 µL of sample/solution. Fig. 1C shows the method of respiration activity evaluation and respiratory burst evaluation using the electrochemical chip. There is only the measurement solution (11.4 mM glucose-containing phosphate buffer) in Ch1 well and milk sample in ch2 well while ch3 well contains milk sample containing PMA. We evaluated the respiration activity of somatic cells in milk from the difference in oxygen reduction current value between Ch1 and Ch2 (ΔI1) and estimated the number of somatic cells. We compared the difference in oxygen reduction current value (ΔI2) of Ch2 and ch3 with ΔI1 and evaluated the immune function by evaluation of respiratory burst. Our study will report the results on the number of somatic cells and the real-time monitoring of the respiratory burst.
References
(1) H. Kikuchi, A. Prasad, R. Matsuoka, S. Aoyagi, T. Matsue, S. Kasai: Frontiers in Physiology 7, 25, 1-6 (2016)
(2) R. Kumagai, A.Prasad, S. Kasai, PACIFIC RIM MEETING on electrochemical and solid state science 2020, 11.4-9. 2020

Figure 1
Validation of a Low-Cost on-Demand Compact Ozone Covid-19 Sterilization Chamber
Authors: Ebeling Daniel , Werner John , Erbe Jarrod , Ebeling Silas , Miao Qiusu , Ebeling Alyssa , Sanford Laura , Boinski Connor , Salous Bilal , Scheunemann Alyssa , Peaslee David , Ploense Lloyd , Ploense Robert , Stetter Edward , Findlay Melvin , Meulendyk Bennett , Lee Mitchell , Patel Vinay , Stetter Joseph R. 
Published: July 2021

The COVID-19 pandemic has resulted in limited availability of N95 masks and other personal protective equipment (PPE). The sterilization and re-use of PPE can be of immediate benefit to help alleviate shortages and offer peace of mind to healthcare workers. Also, an inexpensive, precise, and portable sterilizer will have many applications beyond the current health crisis in a variety of field disaster relief operations. The sterilization of PPE and medical or other instruments will reduce costs, improve safety, and reduce waste. The portable sterilizer can also be utilized by individuals and businesses outside of the health care sector with similar benefits.
Ozone sterilization does not require chemical consumables, uses ambient oxygen to generate ozone on site, and results in no toxic residuals. KWJ Engineering led the development of a small benchtop sterilizer with on board ozone generation controlled by feedback from an electrochemical sensor module and complete with an ozone destruct cycle for safety. Relative humidity as well as temperature and O3 concentration are also continuously recorded and can be maintained at the most effective levels for sterilization.
Validation of the ozone sterilization protocol for deactivation of surrogate viruses on N95 masks has been demonstrated using TLS, an E. coli bacteriophage (bacteria-infecting virus), to provide a measure of effectiveness for variables such as time, ozone and viral concentrations, temperature, relative humidity, and virus-contaminated substrate. Additional organisms and conditions of sterilization are reported in this study to provide further analysis of efficacy of equipment and procedures as well as deleterious effects, if any, on PPE.
The experiments with bacteriophage indicate that there is 99.99% inactivation of the robust bacteriophage when placed on N95 mask material with a one-hour treatment at 200 ppm ozone as compared to a 0-ppm control. The inactivation was shown to be 99.8% with only 50 ppm ozone. These ozone levels are easily achieved with a low power source and the entire system is operated using 12 VDC from a charger or battery. This sterilization effect is highly dependent on humidity, and the higher inactivation rates require higher relative humidity. The inactivation was demonstrated on multiple types of substrates with and without prior drying of the deposited phage. We expect the covid19 to be easier to inactivate than the bacteriophage and will test the system on SARS-CoV2 in a separate series of experiments. The sterilizer apparatus is simple and low cost and can be constructed from readily available parts and software for automated control is open sourced by KWJ.