bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insights into Electrocatalytic Surface Chemistry Via Operando Spectroscopy, Spectrometry and Stress Measurements
Authors: Raciti David , Tackett Brian , Hight Walker Angela , Stafford Gery , Moffat Thomas P 
Published: November 2022

On the verge of harnessing CO2 as a building block for carbon-based fuels, electrocatalysis stands uniquely poised to revolutionize the chemical industry through renewable electrification. For this vision to become reality operando measurement techniques must be applied to study phenomena at the electrode-electrolyte interface. Understanding the dynamic interaction between ionic species in the electrolyte, active sites and intermediates is paramount for the systematic advancement in chemical reactivity, durability, and selectivity required to become commercially relevant. I will demonstrate a suite of operando techniques, such as shell-isolated nanoparticle enhanced Raman spectroscopy (Figure 1a), mass spectrometry (Figure 1a), and cantilever curvature measurements (Figure 1b), that enable direct measurement of adsorbates, phase state and stress dynamics, respectively, at the electrode interface. The combination of results from these measurements enables quantification of sub-monolayer coverages of surfaces species as well as coverage vs stress relationships providing the capability to effectively tune properties of the electrode surface. Complimentary use of these techniques to comprehensively study chemical reactions at heterogeneous interfaces provides new insights into atomic events critical for sustainable electrification to be realized.
Figure Caption: (a) Identification of surface hydride on Cu(111) via complementary operando Raman and online mass spectrometry measurements and (b) cantilever curvature measurements combined with DFT calculations reveal the mechanism behind compressive stress due to CO adsorption.

Figure 1
(Digital Presentation) Electrocatalytic CO2 Reduction to Formic Acid: Kinetics and Equilibrium Modeling for the Downstream Separation of Formic Acid with Anion Exchange Resins
Authors: Hoque Md Ariful , Abad Keemia , Kharel Pom , Omosebi Ayokunle , Liu Kunlei , Thompson Jesse 
Published: November 2022

Electrocatalytic carbon dioxide reduction reaction (CO2RR) technology can simultaneously minimize the CO2 concentration in the atmosphere and generate useful chemicals and fuels. Liquid formic acid (FA) produced from CO2RR is a chemical feedstock for industrial purposes as well as a potential hydrogen storage medium. The downstream separation of liquid FA from the CO2RR effluent increases the total costs in addition to the electrolysis and can also affect the environment adversely. Therefore, efficient, low-cost, and environmentally benign technologies for FA separation from the CO2RR are important for life cycle analysis and techno-economic analysis for this technology. Ion exchange has been proven as an advanced process for FA separation from aqueous solution. This method has attractive due to its high selectivity, low cost, ease of operation and recovery, availability to integrate with other systems, and environmentally benign nature.
In this work, three anion exchange resins: Ambersep 900 hydroxide, Amberlite IRA-96 free base, and Amberlite IRA-910 chloride forms have been tested to separate FA from the aqueous solution under varying resin loading (10-60 mg/mL) and initial FA concentration (0.05-0.50 M). The effect of potassium bicarbonate, a commonly used catholyte in electrochemical CO2RR on equilibrium FA adsorption capacity has been investigated with resin loading of 10 and 60 mg/mL under similar initial FA concentrations.
Kinetics and equilibrium studies data for the FA adsorption on three resins are interpreted using several kinetics and isotherm models. The kinetics data fits better with pseudo first order at high initial FA concentration and pseudo second order at low initial FA concentration. The results show that the Ambersep 900 hydroxide form with adsorption capacity of 430.8 mg of FA per g of resin is more efficient than the Amberlite IRA-96 free base form (369.9 mg/g) and Amberlite IRA-910 chloride form (291.2 mg/g) in the absence of potassium bicarbonate in the range of parameters studied. However, Amberlite IRA-96 (153.4 mg/g) and Amberlite IRA-910 (143.4 mg/g) can separate FA more efficiently from the potassium bicarbonate aqueous solution than the Ambersep 900 (94.1 mg/g). The experimental data for all resins can be well explained with the Freundlich isotherm model. In the presence of potassium bicarbonate, competitive adsorption of bicarbonate and formic acid reduces the FA adsorption capacity of resins. Experimental and modeling results will be discussed.
New Strategies for the Improvement of EC-SERS Effect in Organic Solvents
Authors: Fanjul Pablo , Ibáñez David , González-García María Begoña , Hernández-Santos David 
Published: November 2022

Over the last years, combination of electrochemistry (EC) and surface-enhanced Raman scattering (SERS) has received growing attention due to the powerful features associated with EC-SERS effect. In particular, electrochemical activation of metal electrodes allows the generation of SERS substrates which provides the enhancement of Raman intensity in a single experiment. Although effective electrochemical methods have been developed [1,2], they are traditionally limited to aqueous solutions. Raman spectroelectrochemistry in organic media is an interesting alternative, but the development of new EC-SERS procedures is still required.
In this work, different organic solvents were tested for the improvement of Raman features by EC-SERS. Taking into account that organic solvents usually have many Raman bands (Figure 1) that could hamper the analysis of the characteristic bands of the molecule of interest, the selection of the solvent must be considered for each application. As proof of concept, the detection of nicotinamide in organic media is carried out by the electrochemical activation of Au electrode. Electrochemical protocol based on an initial oxidation of the electrode surface followed by its reduction, allows the generation of SERS substrates and provides the enhancement of the Raman signal.
Figure 1. Raman spectra of ACN, EtOH, DMSO, DMF and THF.
References
[1] D. Martín-Yerga, A. Junquera-Pérez, M. B. González-García, J. V. Perales-Rondon, A. Heras, A. Colina, D. Hernández-Santos, P. Fanjul-Bolado, Electrochim. Acta 264 (2018) 183-190.
[2] D. Ibáñez, A. Junquera-Pérez, M. B. González-García, D. Hernández-Santos, P. Fanjul-Bolado, Talanta 206 (2020) 120190.

Figure 1
(Digital Presentation) A Low-Modulus, Soft and Stretchable Wearable Electrocardiography Sensor-System Patch
Authors: Zhang Anan , Tessier Alexandra , Williams Chris , Ameri Shideh Kabiri 
Published: November 2022

Electrocardiography (ECG) is a primary tool for diagnosis of various types of disease and disorders such as arrhythmias, coronary heart disease, heart attack, mental disorders, etc. Reliable wearable ECG devices can be a valuable tool in early diagnosis and effective treatment of such disease and disorders. Convention wearable ECG sensor-systems are rigid, bulky, expensive, and the recorded ECG signals using these wearable devices lack required accuracy for medical diagnosis mainly due to motion artifacts that is originated from slippage of sensors on skin and/or instable interface between the soft sensor and the rigid electronic circuits.
Here, we report a low-modulus, soft and stretchable wearable electrocardiography (ECG) sensor-system patch which enables continuous and long-term recording of ECG signals with minimal motion artifacts. This system consists of two reusable, detachable-attachable patches: sensor patch and circuit patch, as shown in Figure 1a. The reusable multi-wall carbon nanotube (MWCNT) based sensor patch is fabricated on stretchable elastomer substrate by our developed cost and time-effective method. Reusable, front-end and wireless circuit patch is made by integration of the off-the-shelf integrated circuit components with three-dimensional (3D) stretchable-deformable interconnects (SDI). SDIs are 3D springs of liquid metal (EGaIn). Unlike other reported liquid metal based interconnects, SDI has been designed in 3D form to increase the stretchability and make it low-modulus and robust to deformations in all directions. The stretchability of SDI structure is beyond 500% (the limit of our measurement system) without any negligible change in electrical resistivity of the interconnects. With less than 1% change in the resistance of SDIs after 50,000 cycles of applied tensile strain of 200%, the SDI structure ensures reliable stretchability and durability of the circuit patch for long-term electrocardiography.
The sensor patch is soft, stretchable and it is fabricated using a low-cost scalable method. This soft and stretchable ECG sensor-system shows comparable performance with respect to medical grade Ag/AgCl wet gel electrodes. Our CNT-PDMS sensors shows low electrode-skin interface impedance and low susceptibility to motion artifact which similar of it in medical grade Ag/AgCl wet gel sensors (Fig. 1b). Further, it is waterproof, reusable and comfortable to wear.
The circuit patch includes a rechargeable battery and ECG signals is wirelessly sent to a personal device such as cellphone, tablet and laptop through Bluetooth low energy (BLE) and it is displayed in real-time (Fig. 1c) Our developed sensor-system is a multi-use platform which can be applied for the detection of EMG, EEG or EOG signals.

Figure 1
Peroxynitrite Electrochemical Signature on Selenium and Selenium-Decorated Graphene Depositions
Authors: Kalil Haitham , Ibrahim Magdy A , Fouad Farid , Bayachou Mekki 
Published: November 2022

Reactive oxygen species (ROS) such as peroxynitrite have been linked to oxidative stress-induced diseases such as cardiovascular failure. Determining the cause and progression of such disease, as well as testing the efficacy of potential treatments all hinge on the ability to accurately detect these species in biological systems. Antioxidant uses of selenium have garnered the attention of scientists in recent years. Latest investigations have revealed that selenium is essential for redox regulation as a ROS modulator and as a catalytic cofactor of endogenous antioxidative mechanisms.
The advantages of preparing selenium electrochemical depositions as sensitive surfaces for peroxynitrite detection and quantification were revealed in our research. Electrochemical sensors with high sensitivity and selectivity were developed by dissolving selenium dioxide in an acidic medium. Graphene nanostructures loaded with selenium were used to modify one set of glassy carbon electrodes (GCEs), while selenium nanoparticles were used to modify another set of GCEs for comparison purposes. The shape and surface chemistry of selenium and selenium-decorated graphene nanostructures were investigated using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The electrochemical catalytic activity of these systems was determined using cyclic voltammetry and chronoamperometry. The thickness of the deposited selenium interfaces was measured using Quartz Crystal Microbalance (QCM) analysis.
Elemental selenium nanoparticles showed an increase in the sensitivity toward peroxynitrite when embedded into graphene sheets. In addition, it allowed for the use of low positive potential, leading to improved segregation of peroxynitrite from other analytes that are sensitive to higher potentials.
(Digital Presentation) Graphene Oxide Modified Pencil Graphite Electrode for the Detection of H2O2
Authors: Mistri Jayanta , Rasel Md. , Jamal Mamun 
Published: November 2022

Hydrogen peroxide is a very simple molecule, it is an important chemical and analyte in various industry fields, such as mining, environment, pharmaceutical, food manufacturing and textile applications. Meanwhile, H2O2 is also a kind of toxic by-product of many biological oxidases, based on which H2O2 has been considered to be an indicator of related diseases, such as Parkinson disease, cancer, stroke, arteriosclerosis and Alzheimer disease [1-3]. In addition, H2O2 has been applied in liquid-based fuel cells as an efficient oxidant and has also been employed in organic synthesis. Therefore, it is one of the critical issues to detect H2O2 accurately for industrial needs.
In this work reduced graphene oxide-supported tin oxide nano clusters modified pencil graphite electrode (SnO2-rGO/PGE) was used as electrochemical sensing material for H2O2 detection. Cyclic voltammetry and amperometry were used to investigate the catalytic properties of SnO2-rGO/PGE. Hydrothermal synthesis method was used for the fabrication of SnO2 nanoparticles and GO prepared by modified Hummers method. For the detection of H2O2, the nanoparticles were mixed with Nafion and chitosan before drop coating onto the Pencil graphite electrode (PGE) surface. This studies we found a good catalytic activities on 3B pencil that modifier with GO and SnO2nano clusters at pH (7.4). Here, include that the current increasing after using modifier PGE with nanoparticles. Electrochemical studies showed that the sensing platform fabricated from SnO2-rGO possesses fast mass transport, good electrical conductivity and high sensitivity and selectivity for the detection of H2O2.Where, composite SnO2-Go/PGE exhibited amperometric sensitivity of 129 μAmM−1cm-2 and fast response time 2s.The interference study of SnO2-rGO has been found a significant current response for H2O2 compared to the uric acid and ascorbic acid.The electrode can be prepared simply and at low cost, and present a promising tool for sensing H2O2. Here we propose a new, robust and reliable way to detect of H2O2.
Acknowledgments
Ministry of Science and Technology of Bangladesh (special allocation 2021-22) for funding this research.
Reference

J. Islam et al., PLoS ONE, 2021 16(3), e0248142.

Roy, K., et al.
Int. J. Environ. Sci. Technol. (2022). DOI: https://doi.org/10.1007/s13762-022-04301-w
Measurement and Analysis of Mechanical Properties of All-Solid-State Electrodes Fabricated By Dry Process with Saicas
Authors: Bak Cheol , Lee Jong Jun , Kim Dohwan , Lee Yong Min 
Published: November 2022

Due to battery fire accidents while driving and charging an electric vehicle, research on improving battery safety as well as increasing the energy density has been extensively performed. For this purpose, an all-solid-state battery without the flammable liquid electrolyte is being more actively conducted. Among various solid electrolyte types, the sulfide-based solid electrolyte has been investigated as the most promising candidate owing to its high ionic conductivity and ductility. However, since sulfide solid electrolyte is too reactive to organic solvents like N-methyl pyrrolidone, a few nonpolar solvents (xylene or toluene) can be used to fabricate sulfide solid electrolyte. Thus, except for rubber binders such as nitrile butadiene rubber, other conventional adhesive binders are excluded from candidates. So, to solve this limitation fundamentally, a dry process without any solvents must be an attractive method for using the sulfide electrolyte in battery manufacturing process. For example, polytetrafluoroethylene (PTFE) is frequently used for fabricating all-solid-state electrode (ASSE) with sulfide electrolytes due to its wonderful fibrilization property. However, comparing to the wet process, it is more challenging to distribute all the electrode components uniformly in the dry process, where all the components are mixed through kneading the electrode dough. That is, to maximize the electrochemical performances of ASSEs, it is essential to evaluate the mechanical properties of ASSEs fabricated from dry process and to quantify them for optimization. However, most of research on ASSEs have been focused on their electrochemical performances up to now.
Thus, in this work, we attempted to measure the mechanical properties of ASSEs with sulfide electrolyte using a surface and interfacial cutting analysis system (SAICAS). The ASSEs were fabricated through dry process while changing the PTFE binder content. Subsequently, both bulk and interfacial adhesive strengths were analyzed systematically and deliberately by a few μm resolution. Furthermore, to unveil the surface, bulk, and interfacial electrical properties are also measured using an electrode resistance measuring instrument (HIOKI RM2610). Thus, we can provide a correlation between binder content and mechanical/electrical properties of dry ASSEs. Finally, comparative results based on wet processed ASSEs will also be included in this work.
A Fluorine-Based Linear Carbonate Electrolyte Additive for Enhanced High-Voltage Cycle Performance of Li-Metal Secondary Batteries
Authors: Han Jiwon , Jin Dahee , Park Changhee , Lee Sunggi , Lee Yong Min 
Published: November 2022

Due to growing demand for electric vehicles (EVs) and energy storage systems (ESS), it is essential to meet the requirement for high energy density of Li secondary batteries. In this sense, an electrode chemistry matching high-Ni cathode materials and thin Li metal anode has been investigated most actively under high voltage operation. As a result, there are a variety of degradation issues on both electrodes like high-resistance cathode electrolyte interphase (CEI) as well as solid electrolyte interphase (SEI) on the anode, electrolyte depletion, or Li dendritic growth. Thus, advanced electrolytes containing functional additives are extensively being developed to mitigate those stresses occurred in the high-energy-density Li-metal secondary batteries (LMSBs). Especially, to minimize the amount of expensive additives, many research groups have made much effort in discovering new or multi-functional additives for LMSBs.
In this work, we report a bis(2-fluoroethyl) carbonate (B-FEC) as a new fluorine-based linear carbonate electrolyte additive to stabilize the SEI even in the high voltage conditions (4.5 V cut-off). To confirm the role of B-FEC on electrochemical properties, we evaluated its electrochemical properties with Li/Li symmetric cells as well as LiNi0.6Co0.2Mn0.2O2 (NCM 622)/Li cells with or without B-FEC. Also, various analysis data were also gathered to check the morphological and compositional changes caused by B-FEC through SEM, XPS, etc.
(Digital Presentation) The Effect of Phosphorus on the Mechanism of Pitting Initiation in Carbon Steel
Authors: Takayama Riku , Muto Izumi , Nishimoto Masashi , Sato Haruka , Sugawara Yu 
Published: November 2022

Phosphorus is typical impurity in steelmaking process. Phosphorus was tended to segregate at grain boundaries. Phosphorus segregation causes solidification clacking at welding and defects at forming. In the steel making process, Phosphorus cannot refine completely. We focused on the effect of phosphorus segregation and precipitation to corrosion resistance. Phosphorus in steel was expected solid solution, segregation, and precipitation and the size was submicron order. Therefore, we need microelectrochemical measurements to analysis. Solid solution carbon was improved corrosion resistance was known1). To analysis only the effect of phosphorus, we use Fe-P binary alloy. In this study, we assessed pitting initiation of Fe-P binary alloy using microelectrochemical measurement.
Two types of heat-treatment were conducted to Fe-P binary alloy. The one was heat-treated at 1100 ℃ at 1 h and quenched in water. The other was tempered at 1373 K for 1 h. As-tempered steel was aimed to precipitate of Fe3P. The specimen surface was polished down to 1 μm using a diamond paste. Pure iron was used as reference materials.
Potentiodynamic anodic polarization curves were measured in Boric-Borate buffer with 5 mM NaCl solution. The pH value of the solution was adjusted to 7.0. Size of electrode areas were 1 cm × 1 cm, 1 mm × 1 mm, and 0.5 mm × 0.5 mm.
When the size of electrode area was 1 cm × 1 cm, pitting potential of Fe-P was increased above pure iron. In 1 mm × 1 mm electrode area, as-tempered steel was shown the higher pitting potential than as-quenched steel. Pitting was only observed from edge of masking. In 0.5 mm × 0.5 mm electrode area, no pitting was observed on both as-quenched and as- tempered steel.
Reference;
1) Kadowaki, I. Muto, Y Sugawara, T. Doi, K. Kawano, and N. Hara, J. Electrochem. Soc., 165, C711 (2018).
Modifying the Cathode Catalyst Layer in PEM Fuel Cells with Ionic Liquids for Improved Oxygen Reduction Reaction
Authors: Gawas Ramchandra , Tang Maureen , Snyder Joshua David 
Published: November 2022

Increasing the accessibility of green, affordable hydrogen and reducing the cost of polymer electrolyte membrane fuel cells (PEMFC) devices are critical to the widespread commercialization of hydrogen powered fuel cells. The high cost of PEMFCs is in part due to the high Pt leadings in the cathode catalyst layer (CCL) to compensate for kinetic and transport losses during the sluggish oxygen reduction reaction. Therefore, substantial research efforts have been focused on modifying the CCL and its constituent components to achieve cost parity with other advanced energy technologies, particularly in the transportation sector.
Hydrophobic ionic liquids (ILs) have been used as interfacial additives for oxygen reduction reaction (ORR) electrocatalysts, demonstrating enhanced catalyst activity and durability.1,2 However, incorporating ILs or IL-modified catalysts into the electrodes of a PEMFC membrane electrode assembly (MEA) has proven to be challenging. To address this limitation, we developed a new ionomer chemistry with orthogonal properties of protonic conductivity and ionic liquid functionality: sulfonated poly(ionic liquid) block copolymers (S-PILBCPs). The new ionomer in the Pt/C CCLs yields a two-fold improvement in the kinetic activity, both in the half-cell and MEA. Furthermore, a Nafion/S-PILBCP composite ionomer substantially improves the high current density performance as well.3

In this work, we use rotating disk electrode (RDE) techniques to electrochemically characterize the Pt/S-PILBCP interface. Our analysis demonstrates the promise and utility of hydrocarbon-based poly(IL) ionomers over the traditional ionomer-Nafion and also provides important insights about observed MEA performance enhancements.
References:

Snyder, J., Fujita, T., Chen, M. W. & Erlebacher, J. Oxygen reduction in nanoporous metal-ionic liquid composite electrocatalysts. Nat. Mater.
9, 904–907 (2010).

Li, Y., Hart, J. L., Profitt, L., Intikhab, S., Chatterjee, S., Taheri, M. & Snyder, J. D. Sequential Capacitive Deposition of Ionic Liquids for Conformal Thin Film Coatings on Oxygen Reduction Reaction Electrocatalysts. ACS Catal.
9, 9311–9316 (2019).

Li, Y., Cleve, T. Van, Sun, R., Gawas, R., Wang, G., Tang, M., Elabd, Y. A., Snyder, J. & Neyerlin, K. C. Modifying the Electrocatalyst−Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells. ACS Energy Lett.
5, 1726–1731 (2020).