bluuebunny/crossref_metadata_2025_split huggingface dataset:
Screen-printed Electrodes with Stable Solid-state Reference Electrode for Oxidation-reduction Potential (ORP) Measurement Applications
Authors: Williams Kia , González-García María Begoña 
Published: July 2022

ORP is defined as the electromotive force between a noble metal electrode and a reference electrode when immersed in solution [1]. The electrochemical setup typically involves a platinum wire as a working electrode (sometimes gold, rarely silver) and a well-controlled reference electrode. When these electrodes are immersed together into a solution, an electron migration is produced between the working electrode and the solution. Depending on the nature of the species diluted, the working electrode loses electrons if the media is an oxidant, so the potential measured becomes positive. If the media is reductive, the working electrode gains electrons, and the resulting potential will be negative. Voltage is measured between both electrodes (working and reference electrode), so the ORP value is usually given in millivolts.
ORP provides valuable information because it is a measure of sanitizer activity and water quality, due to the changes in ORP being associated with the existence of contaminants or biological activity. ORP measurements are also useful in several major industrial applications where maintaining potential in a production stage under control is a critical parameter or when it is necessary to assure the quality of water. Examples include cyanide oxidation or chrome reduction in wastewater treatment of metal-plating industry residues, bleach production and bleaching of paper, biological growth control in cooling towers and water quality monitoring in swimming pools, hot tubs, spas, or aquafarming.
Screen-printed electrodes (SPEs) offer several interesting advantages in industrial applications such as point-of-care testing, usability, and a wide range of possible customizable setups. However, most SPEs include a pseudo-reference electrode fabricated with silver or silver/silver chloride. Since the KCl electrolyte is absent, this pseudo-reference electrode is exposed to media implying that the reference electrode is not under control, especially in aggressive media. In this publication, an SPE with a platinum paste working electrode and a controlled solid-state reference electrode is presented. Several experiments are included to show that these platforms offer ORP monitoring in household, industrial or laboratory applications.
References:
[1] ASTM D1498 - 14 - Standard Test Method for Oxidation-Reduction Potential of Water
Carbon-Capped Monometallic and Bimetallic Catalysts for Hydrogen Oxidation Reaction (HOR) and Their Positive Features on Durability in Alkaline Conditions
Authors: Sgarbi Ricardo , Doan Huong , Chatenet Marian 
Published: July 2022

Alkaline fuel cells (AFC) and anion exchange membrane fuel cells (AEMFC) have exhibited attractive advantages versus their acid counterparts, including the strategical possibility of using PGM-free catalysts in the electrode composition.[1,2] PGM-free catalysts remain a challenge regarding the hydrogen oxidation reaction (HOR) catalysis, due to the reduced initial and long-term performance so far.[3,4] PGM-based materials have the highest HOR performances,[5] but Pt- and Pd-based catalysts undergo detrimental metallic nanoparticles detachment from the carbon support and agglomeration (in minor extent) upon extended potential cycling in the alkaline environments.[6,7] In this work, we explore the effect of long-term durability on the nanoparticles wrapped by a carbon layer, labeled here as capped catalysts; two different types of carbon-capped catalysts are evaluated, such as monometallic (PdG2/C) and bimetallic (PdNiG2/C) against their commercial ones (Pd/C and PdNi/C from Premetek). All the catalysts were evaluated in RDE set-up, in couple with IL-TEM, XPS and ICP-MS techniques for before and after accelerated stress test (0.1 – 1.23 V vs. RHE – 3s each potential), up to 6000 cycles. The durability enhancement is achieved when: i) there is a carbon-cap and ii) there is a second metal (i.e. Ni) on the surface of Pd. Thus, in the case of carbon-capped bimetallic (PdNiG2/C), there is a double protection of the Pd nanoparticles (from the carbon-cap and the presence of nickel). In the same time, the HOR activity is high. In the end, the best compromise of durability follows the trend: PdNiG2/C > PdNi/C > PdG2/C > Pd/C. These positive features of the carbon-capped bimetallic material open the way to the design of robust catalysts for highly-durable anodes for alkaline fuel cell systems.
[1] D. R. Dekel, J. Power Sources
2018, 375, 158–169.
[2] E. Wagner, H. ‐J. Kohnke, Fuel Cells
2020, 1–12.
[3] A. G. Oshchepkov, G. Braesch, A. Bonnefont, E. R. Savinova, M. Chatenet, ACS Catal.
2020, 10, 7043–7068.
[4] W. E. Mustain, M. Chatenet, M. Page, Y. S. Kim, Energy Environ. Sci.
2020, 13, 2805–2838.
[5] W. Sheng, M. Myint, J. G. Chen, Y. Yan, Energy Environ. Sci.
2013, 6, 1509–1512.
[6] C. Lafforgue, F. Maillard, V. Martin, L. Dubau, M. Chatenet, ACS Catal.
2019, 9, 5613–5622.
[7] A. Zadick, L. Dubau, N. Sergent, G. Berthomé, M. Chatenet, ACS Catal.
2015, 5, 4819–4824.
(Digital Presentation) Uncertainty Analysis on Activity Coefficients Determination Using Vapor Pressure Osmometry on Electrolyte Solutions
Authors: Aguilar-Arias Jaime , Carvajal Perdomo Sergio Andres , Gutiérrez Cristian 
Published: July 2022

Vapor Pressure Osmometry (VPO) is a reliable technique for experimental measurement of both activity coefficient of solvents and molar weight of solutes. In this work were analyzed the uncertainty sources that affect the measurements on VPO, establishing a general model for uncertainty, and applying this model to the particular case of a VPO prototype designed and constructed in this work as well. In the analysis was included the effect of strong electrolyte solutes of different ratios on the uncertainty of the measurements.
In order to obtain a reliable mathematical model, a simplified thermodynamic model for the activity coefficient was used. Two types of electrolytes (1:1 and 1:2) were used for experimental runs in the diluted and non-diluted concentrations.
The osmometer was designed using thermistors, so, four commercial thermistors of two different types were calibrated in the range of 0-40°C according to ASTM E879 Standard, obtaining an expanded uncertainty of 0.014°C with a confidence level of 95%.
For the uncertainty budget, the relevant sources were identified and quantified. The expected uncertainty of the measurements ranged from 1.03x10-6 to 1.81x10-4 for the estimation of the activity coefficient with a confidence level of 95%.
Characterization of the Reductive Desorption of Self-Assembled Monolayers on Platinum Surfaces
Authors: Martínez-Blanco Gilberto Josué , Casanova-Moreno Jannu 
Published: July 2022

Thiol-based self-assembled monolayers (SAMs) have been widely characterized on gold surfaces, with the desorption potentials of these SAMs being of special interest for nanotechnology and biological applications. However, the study and determination of desorption potentials of thiol SAMs on platinum surfaces has been limited by the hydrogen evolution reaction (HER) catalyzed by the metal, which dominates response signals when studying the system through conventional electrochemical techniques.
Through the coupling of electrochemical techniques with fluorescence microscopy, the problem of the HER signal can be avoided in the study of desorption potentials for the platinum-thiol monolayer systems. By using fluorescent thiols, as well as monocrystalline platinum spheres, the desorption potential for different crystallographic orientations and thiol length combinations can be determined. The results obtained show that the desorption of Bodipy C10SH thiols from platinum surfaces occur at more positive potentials in [111] crystallographic orientations, and at more negative potentials at [100] ones. On the other hand, no notable difference was found in the desorption order of Bodipy C16SH from these two orientations.
However, the use of fluorescence microscopy for the solution of this problem poses other challenges: the time the thiols need to separate enough from the metallic substrate to not be affected by quenching, as well as the facts that thiols fluoresce less as they dilute and the existing spectral overlap for the molecules, adds difficulties to the establishment of the desorption potentials.
Through COMSOL Multiphysics simulations, we try to simulate the systems hereby proposed of platinum with thiol-based SAMs. Using them, the desorption potentials, as well as the monolayer coverage under specific conditions, can be determined. We expect that, with further development of the model, more specific values for these variables can be determined.

Figure 1
Designing a Li-N-H Based Solid Electrolyte
Authors: Lowen Jeremy Paul , Makepeace Joshua W 
Published: July 2022

All-solid-state-batteries (ASSBs) have long promised to be the next-generation of high-performance energy storage devices, with a step-change in energy density, stability and cell safety touted as potential advantages compared to conventional Li-ion battery cells.[1] The development of fast lithium-ion conductors is key to realising commercially-viable ASSBs, however significant challenges remain with the leading candidate materials. Complex metal hydrides, in particular BH4
- derived materials, have gained recent attention due to their high ambient temperature lithium ionic conductivities and good stability with lithium metal.[2] Nitrogen-based complex hydrides, such as materials within the Li-N-H system, have largely been studied as solid-state hydrogen stores. However, a key characteristic that links the impressive properties of the Li-N-H system in this application is the high Frenkel defect-based Li-ion conductivity, which facilitates the formation of amide-imide and imide-nitride-hydride antifluorite structured solid solutions.[3,4] These solid solutions represent an opportunity through careful stoichiometry control to tailor the properties of a Li-N-H based material for application as a solid electrolyte.
Careful characterisation using X-ray diffraction and Raman measurements have allowed us to evaluate the structure of the solid solutions between lithium imide (Li2NH), lithium amide (LiNH2) and lithium nitride hydride (Li4NH), all dominated by a disordered anti-fluorite phase. We demonstrate the ability to tailor the conductivity of these materials between an ionic insulator and a superionic conductor by simple stoichiometry control. Lithium imide, and stoichiometries close to this compound, in particular display favourable properties as solid electrolyte materials. We herein exhibit the first demonstration of a Li-N-H material in an ASSB, with the materials displaying high lithium ion conductivities, wide electrochemical stability windows and potential for further tuning for this application.
Ultimately, these results identify Li-N-H based complex hydrides as an interesting avenue of research for solid electrolyte application that is yet to be fully explored. We hope this presentation will highlight these materials and spark further development such as has been seen for oxide and sulphide based fast-ion conductors.
1) Z. Zhang, Y. Shao, B. Lotsch, Y. Hu, H. Li, J. Janek, L F. Nazar, C. Nan, J. Maier, M. Armand and L. Chen, Energy Environ. Sci., 2018, 11, 1945-1976
2) A. Unemoto, M. Matsuo, and S. Orimo, Adv. Funct. Mater., 2014, 24, 2267-2279
3) W. Li, G. Wu, C. M. Araujo, R. H. Scheicher, A. Blomqvist, R. Ahuja, Z. Xiong, Y. Fengb and P. Chen, Energy Environ. Sci., 2010, 3, 1524-1530
4) J. W. Makepeace, J. M. Brittain, A. S. Manghnani, C. A. Murray, T. J. Wood and W. I. F. David, Phys. Chem. Chem. Phys., 2021, 23, 15091

Figure 1
Temperature Dependent Study of AcFc-FeIII(acac)3 Redox Couple for Non-Aqueous Redox Flow Battery
Authors: Mazumder MD Motiur Rahaman , Islam Rezoanul 
Published: July 2022

Energy storage is a vital aspect for the successful implementation of renewable energy resources on a global scale. Non-aqueous redox flow battery (NARFB) is one of the primary response to fulfill the next generation energy demand.1–6 This study describes the temperature dependence electrochemical analysis of acetyl ferrocene (AcFc) and iron(III) acetyl acetonate ([Fe(acac)3]) for NARFBs. An electrochemical cell consisting of AcFc and ([Fe(acac)3]) as catholyte and anolyte species, respectively, was constructed with a cell voltage of 1.41 V and Coulombic efficiencies >99% for up to 50 total cycles at 25o C (RT) and 0o C. Rotating ring disk electrode (RRDE) experiments suggest that diffusion coefficient decreases as the temperature decreases but overall storing capacity far better than aqueous redox flow battery (ARFBs). The electrochemical kinetic rate constant (k0) of AcFc found larger than Fe(acac)3 but remains similar at both temperatures. NMR study shows no structural change in changing temperature and after battery experiments.

References

(1) Mazumder, M. M. R.; Burton, A.; Richburg, C. S.; Saha, S.; Cronin, B.; Duin, E.; Farnum, B. H. Controlling One-Electron Vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate. ECS Meet. Abstr.
2021, MA2021-01 (1), 52–52. https://doi.org/10.1149/ma2021-01152mtgabs.
(2) Islam, R.; Mazumder, M. M. R.; Farnum, B. H. Solvent Dependent Spectroscopic and Electrochemical Studies of Nickel (II) Diethyldithiocarbamate for Energy Storage. ECS Meet. Abstr.
2021, MA2021-01 (1), 54–54. https://doi.org/10.1149/ma2021-01154mtgabs.
(3) Saha, S.; Sahil, S. T.; Mazumder, Md. M. R.; Stephens, A. M.; Cronin, B.; Duin, E. C.; Jurss, J. W.; Farnum, B. H. Synthesis, Characterization, and Electrocatalytic Activity of Bis(Pyridylimino)Isoindoline Cu( ii ) and Ni( ii ) Complexes. Dalton Trans.
2021, 10.1039.D0DT03030A. https://doi.org/10.1039/D0DT03030A.
(4) Mazumder, M. M. R.; Farnum, B. H. Two One Electron vs One Two-Electron Redox System of Nickel Diethyldithiocarbamate for Redox Flow Battery; ACS, 2021. https://doi.org/10.1021/scimeetings.1c00951.
(5) Mazumder, M. M. R.; Farnum, B. H; Burton Andricus. Mechanistic Study of Multi-Electron Redox Cycle of Nickel Dithiocarbamate Complex for Redox Flow Battery Application; ACS, 2021. https://doi.org/10.1021/scimeetings.1c00387.
(6) Mazumder, M. M. R. Ni(IV/II) Redox Couple 2e- Reversibility Improvement for Redox Flow Battery. ECS Meet. Abstr.
2021, MA2021-02 (5), 1855–1855. https://doi.org/10.1149/ma2021-0251855mtgabs.

Figure 1
Apple Pectin Based Hydrogel Electrolyte for Energy Storage Application
Authors: Chelfouh Nora , Coquil Gaël , Rousselot Steeve , Briqueleur Elsa , Foran Gabrielle , Dollé Mickaël 
Published: July 2022

With the increase of portable power sources demand, new technologies, e.g. wearable and flexible electronics, are projected to generate $1.25 billion market by 2022.[1] New storage energy devices are more than ever in demand which requires new specifications in order to be used in those future applications. To achieve this development, we have to minimize the environmental impact in the whole battery life cycle, from conception to degradation of the system, and reduce production costs. Polymer hydrogel electrolyte are one of the promising alternative for processing new flexible batteries.[2] A great hydrogel electrolyte should promise excellent ionic transport pathways and sufficient mechanical strength, not to cause short-circuits. As a matter of fact, hydrogel electrolytes are well-known for their good ionic conductivity. Nevertheless, the original polymers used in these systems don’t take into account the cost of the environmental impact and safety due to the processing or biodegradability of those hydrogels.[3]

In this study, we report a new hydrogel-based electrolyte material made by apple pectin. This presentation will mainly focus on the interactions between pectin functional groups, water and ions using solid NMR spectroscopy. Thermal properties will be discussed based on differential scanning calorimetry analysis. Electrical and electrochemical characterisctics obtained by electrochemical impedance spectroscopy, galvanostatic cycling and cyclic voltametry will demonstrate the applicability of such hydrogel electrolyte.
This study could promote a great innovation in the energy storage field, by recycling one of apple peel’s component (which is the main waste in preserves manufacturing[4]) into a hydrogel electrolyte.

References

[1] N. R. C. Canada in Environmentally friendly printed batteries, Vol. Boucherville, Quebec, 2021.
[2] C. Y. Chan, Z. Wang, H. Jia, P. F. Ng, L. Chow and B. Fei, Journal of Materials Chemistry A
2021, 9, 2043-2069.
[3] Y. Huang, M. Zhong, F. Shi, X. Liu, Z. Tang, Y. Wang, Y. Huang, H. Hou, X. Xie and C. Zhi, Angewandte Chemie International Edition
2017, 56, 9141-9145.
[4] B. S. Virk and D. S. Sogi, International Journal of Food Properties
2004, 7, 693-703.
Cation Size Effect on Oxygen Reduction Reaction in Aprotic Electrolytes
Authors: Fernández Vidal Julia , Galloway Thomas , Attard Gary , Hardwick Laurence J. 
Published: July 2022

The most important cathodic process in alkali metal-air (M-O2) batteries is the electrocatalytic oxygen reduction reaction (ORR) typically forming superoxide (MO2), and peroxide (M2O2).1 Cation size in aqueous solvents have been demonstrated to affect the ORR activity due to the cation hydration energy.2 However, within aprotic electrolytes, the reaction mechanisms and the activity of ORR with respect to cation size remains undetermined.
Traditionally, electrochemistry has been involved in the analysis of the reaction mechanisms of ORR. Nonetheless, this technique by itself is not suitable to identify intermediaries and products of the redox reactions taking place at the electrochemical interface. The combination of cyclic voltammetry with in situ Raman spectroscopy provide the opportunity to study and develop a fundamental understanding of the ORR under potential control, accessing reaction pathways and relating them directly to surface structure.3 In this sense, the breakthrough of Shell-Isolated Nanoparticles for Enhanced Raman Spectroscopy (SHINERS)4,5 is noteworthy. SHINERS is a non-destructive, powerful technique for surface analysis that has been demonstrated to provide SERS effect even in the absence of intrinsic roughness and without requiring Au, Ag or Cu to be used as working electrodes.3,5

In this work, electrochemical measurements and SHINERS are utilised to study the effect of cation upon electrified interfaces during ORR.

Zhang, J., Zhang, X.-G., Dong, J.-C., Radjenovic, P. M., Young, D. J., Yao, J.-L., Yuan, Y.-X., Tian, Z.-Q. & Li, J.-F. Real-Time Monitoring of Surface Effects on the Oxygen Reduction Reaction Mechanism for Aprotic Na–O2 Batteries. J. Am. Chem. Soc.
143, 20049–20054 (2021).

Kumeda, T., Tajiri, H., Sakata, O., Hoshi, N. & Nakamura, M. Effect of hydrophobic cations on the oxygen reduction reaction on single‒crystal platinum electrodes. Nat. Commun.
9, 1–7 (2018).

Guan, S., Attard, G. A. & Wain, A. J. Observation of Substituent Effects in the Electrochemical Adsorption and Hydrogenation of Alkynes on Pt{hkl} Using SHINERS. ACS Catal.
10, 10999–11010 (2020).

Li, J. F., Huang, Y. F., Ding, Y., Yang, Z. L., Li, S. B., Zhou, X. S., Fan, F. R., Zhang, W., Zhou, Z. Y., Wu, D. Y., Ren, B., Wang, Z. L. & Tian, Z. Q. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature
464, 392–395 (2010).

Galloway, T. A., Dong, J.-C., Li, J.-F., Attard, G. & Hardwick, L. J. Oxygen reactions on Pt{hkl} in a non-aqueous Na+ electrolyte: site selective stabilisation of a sodium peroxy species. Chem. Sci.
10, 2956–2964 (2019).
Calculations of pH-Dependent Redox Potentials for Proton-Coupled Electron Transfer Reactions
Authors: de Silva Piotr 
Published: July 2022

We will present a computational protocol that combines density functional theory (DFT) and cheminformatics approaches to predict redox potentials of organic molecules as a function of the pH of the aqueous solution.[1] The methodology is based on an improved version of the Alberty-Legendre transform to account for varying protonation states of the redox reaction products at different pH values. Our approach circumvents the known problems with the use of DFT calculations and implicit solvation models for highly charged anions. To validate the protocol, we use a consistent set of quinones which can undergo up to two-electron two-proton redox reaction. As the reference we use the experimental redox potentials measured at pH 0, 7, and 13.[2] We demonstrate that with the proposed methodology we can achieve the MAE=0.144 V and MSE=-0.016 V at pH=13.
[1] Fornari, R.P.; de Silva, P. A Computational Protocol Combining DFT and Cheminformatics for Prediction of pH-Dependent Redox Potentials. Molecules 2021, 26, 3978.
[2] Wedege, K.; Dražević, E.; Konya, D.; Bentien, A. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility. Sci. Rep. 2016, 6, 39101.
Simulating Scanning Electrochemical Microscopy Images of Arbitrarily Shaped Reactive Sites without a Site-Specific Model
Authors: Leslie Nathaniel , Mauzeroll Janine 
Published: July 2022

Scanning electrochemical microscopy (SECM) yields two-dimensional electrochemical images when the current at a microelectrode is recorded as it moves above a surface generating redox species. As SECM images are often systematically compared to microstructure features obtained by electron microscopy there is a clear need to find ways to integrate electron microscopy images into SECM image simulations.
Recently, finite element method simulations of sites where electrochemical reactions take place is employed to evaluate reactive feature size.[1] Current models move the microelectrode or the reacting surface, continuously changing the geometry of the simulation and thus requiring re-meshing, which increases the computation time.
We present a modeling approach by which SECM images of arbitrarily-shaped reactive sites can be simulated using a grid of pixels that can be turned ‘on’ and ‘off’ using COMSOL® multiphysics. Specifically, COMSOL®’s Java API is used to change the selection of pixels that are turned ‘on’ to simulate the movement of the electrode without changing the geometry of the simulation. The mesh can be re-used for each data-point in the image, dramatically reducing the time needed to simulate SECM images. This work also presents a mostly automated workflow for using an electron microscopy image of a reactive site to determine which pixels should be turned ‘on’ and fitting the kinetics at these pixels by simulating their SECM image.
[1] L. I. Stephens, N. A. Payne, S. A. Skaanvik, D. Polcari, M. Geissler, J. Mauzeroll, Evaluating the Use of Edge Detection in Extracting Feature Size from Scanning Electrochemical Microscopy Images. Analytical Chemistry
2019, 91, 3944-3950.