bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anodic Dissolution of Copper in the Aluminum Chloride-1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid
Authors: Reidy Lorlyn , Wang Chen , Hussey Charles 
Published: May 2020

The ever popular AlCl3-1-ethyl-3-ethylimidazolium chloride (EtMeImCl) ionic liquid (IL) system offers a unique solvation environment for many metal ions. In fact, the use of these chloroaluminate ionic liquids for the electrochemical surface finishing of metals was recently reviewed.1 These ionic liquids display adjustable Lewis acidity that depends directly on the mole ratio of the AlCl3 to the organic salt. The basic AlCl3-EtMeImCl mixture, which contains coordinately unsaturated Cl-, provides a solvation environment similar to aqueous HCl and NaCl, except of course without the complications due to the H2O solvent or H3O+. The opposite situation prevails in the Lewis acidic ionic liquid because the main chemically active ionic component of the ionic liquid is the coordinately unsaturated species, [Al2Cl7]-. Thus, there are no “hard” ligands available to form stable, isolable anionic complexes with the anodization product. Recently, both composition regions of the AlCl3-EtMeImCl IL system have been explored for the electrodissolution/electropolishing of Al.2 The advantages afforded by anodic dissolution of metals in this ionic liquid relative the aqueous acids and salt solutions commonly used for this purpose are quite obvious, i.e., the avoidance of the oxide surface films that invariably complicate the metal electropolishing process. In this paper, we report the thermodynamics and kinetics of the anodic dissolution of copper metal in the acidic and basic compositions of the AlCl3-EtMeImCl ionic liquid. In the former, the dissolution of copper at a Cu-RDE exhibits mixed control. No limiting current or passivation due to the formation of an insoluble surface film was apparent. In the basic composition region, mixed control was observed at small overpotentials, but as the overpotential was increased, a limiting current was obtained that scaled linearly with the Cl- concentration in the ionic liquid. The connection between these results and the mechanism of the dissolution process will be discussed.
____________________________________________
1. T. Tsuda, G. R. Stafford and C. L. Hussey, J. Electrochem. Soc., 164, H5007 (2017).
2. C. Wang and C. L. Hussey, J. Electrochem. Soc., 163, H1186 (2015).
Local Electrocatalytic Activity of Electrodeposited Ni-Fe Particles
Authors: Byers Joshua , Beugre Romaric C 
Published: May 2020

NiFe electrocatalysts have received increasing attention for the electrocatalysis of the oxygen evolution reaction.[1] Recently, using bipolar electrochemistry for the electrodeposition of nickel, we have demonstrated the formation of nickel particle gradients, which vary in size and particle density as a function of electrode position.[2] In this work, low ionic strength aqueous solutions containing Ni(II) and Fe(II) salts, without supporting electrolyte, were used for the electrodeposition of NiFe particles onto a conducting fluorine doped tin oxide substrate. In this talk, I will present our recent results exploring the effect of composition, size and morphology of NiFe particles on the local electrocatalytic activity towards the oxygen evolution reaction, measured using scanning electrochemical cell microscopy.[3]
[1] Song, F., Bai, L., Moysiadou, A., Lee, S., Hu, C., Liardet, L., Hu, X. Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance (2018) Journal of the American Chemical Society, 140 (25), pp. 7748-7759.
[2] Beugré, R., Dorval, A., Lavallée, L.L., Jafari, M., Byers, J.C. Local electrochemistry of nickel (oxy)hydroxide material gradients prepared using bipolar electrodeposition (2019) Electrochimica Acta, 319, pp. 331-338.
[3] Bentley, C.L., Kang, M., Unwin, P.R. Nanoscale Surface Structure-Activity in Electrochemistry and Electrocatalysis (2019) Journal of the American Chemical Society, 141 (6). pp. 2179-2193
Organic/Inorganic Hybrid Electrode Materials for Photo-Conversion of Solar Energy
Authors: Jouini Mohamed , Santoni Marie-Pierre , Ramanitra Hasina , Delices Annette , Xu Zijun , Dong Chang-Zhi , Bellynck Sebastien , Maurel François , Chevillot Alexandre , Szaniawska Ewelina , Wadas Anna , Rutkowska Iwona Agnieszka , Kulesza Pawel J. 
Published: May 2020

NiO nanoparticles deposited on FTO glass modified surface were used to adsorb an organic dye. The obtained device was covered with PEDOT/PSS polymers blend and later sprinkled with palladium nanoparticles.
This modified hybrid electrode was used under ligth and than under dark conditions to study the reduction reaction of CO2 in solution.
The results obtained indicated a large shift toward positive potential of the reduction wave of CO2 in solution under light when compared to the same reduction wave under dark in the same conditions.
The obtained results will be presented and discussed in the frame of the state of the art of CO2 reduction catalysed by palladium nanoparticles supported by hybrid charge transport material.
Observing the Growth Mechanism of Au-ZnO Core-Shell Nanoparticles by In-Situ Liquid Cell TEM
Authors: Tsai Shin-Bei , Huang Chih-Yang , Chen Jui-Yuan , Wu Wen-Wei 
Published: May 2020

Heterostructured nanoparticles have attracted significant attention due to its unique morphology and promotion of a wide range of applications. Among the different kinds of heterostructured nanomaterials, Au-ZnO core-shell nanoparticles have been widely used in dye-sensitized solar cells, photocatalysis, gas sensing and biological detection due to its distinctive physical and chemical properties. Understanding the growth behaviors of nanomaterials is essential for controlling their size, morphology and chemical composition, which can improve the applicability. However, the growth mechanisms of Au-ZnO core-shell nanoparticles are mostly suggested by the post-reaction investigations, and the direct observation of synthesis process is lacking but crucial.
In this work, we utilized liquid cell transmission electron microscopy (LC-TEM) to observe the formation of Au-ZnO core-shell nanoparticles in real-time. The synthesis process of Au-ZnO core-shell nanoparticles was successfully demonstrated via in-situ LC-TEM (Figure 1). The solutions of zinc nitrate hexahydrate ( Zn(NO3)2 · 6H2O), hexamethylenetetramine (HMTA), ascorbic acid (AA) and hexadecyl trimethylammonium bromide (CTAB) were introduced into the liquid cell at the flow rate of 1 µl/min via the microchannels after Au nanoparticles dispersed. The citrate-stabilized Au nanoparticles attracted Zn(OH)4
2‒ complexes with the aid of CTAB and AA, and then Zn(OH)4
2‒ complexes would dehydrate and transform into loose ZnO shells around the Au cores. The morphology of ZnO shells was spherical and smooth, without any granular or crystalline appearance (Figure 2), which was suggested to result from absorbing CTAB molecules. In order to increase the crystallinity of ZnO shells by removing CTAB molecules, the Au-ZnO core-shell nanoparticles were heat-treated at 500°C for 2 h. The crystallization of ZnO shells followed by heat treatment could methodically control the microstructure of heterostructed nanoparticles (Figure 3). The growth behaviors, elements distribution and the statistics about growth has been systematically analyzed. This in-situ experiment casts light on preparation of Au-ZnO core-shell nanoparticles with function of CTAB and AA, extending the study of reaction mechanism and the improvement of controllability of heterostructure synthesis for further device application.

Figure 1
Quantitative Concentration Mapping with AFM-SECM
Authors: Mirabal Alex , Calabrese Barton Scott 
Published: May 2020

Efficient transport of reaction intermediates between active sites can improve the efficiency of multi-site reactions1–3. Experimental detection of these nanometer length scale transport mechanisms is enabled by Scanning Electrochemical Microscopy (SECM). Electrochemical measurements can allow for concentration profile mapping to elucidate the transport processes in experimental systems. SECM can correlate position dependent responses to properties of the system. There is a significant impact on the response profile due to the SECM tip’s presence at the nanoscale. Finite Element Analysis (FEA) has been used to understand and remove these in situ tip effects.
The calculated concentration, using current-flux relations, can be complex near sites generating flux through reactions and/or transport. Additionally, uncertainties such as tip positioning in relation to the interface site can further complicate the response. Quantitative concentration fields can more readily be interpreted through FEA, by matching the experimental tip response.
Electrodeposited platinum nanoparticles were imaged topographically and electrochemically with a Bruker AFM-SECM (Figure 1). The positive response over the nanoparticles vs. the planar HOPG sites allows for kinetic response imaging. The model is parameterized through approach curves and verified though SECM mapping correlation.
We have previously applied FEA to correlate experimental in situ results to in operando conditions. Here, we use this approach to generate corrected concentration profiles. We use Pt nanoparticle catalysts deposited on HOPG, to develop surface property correlations. In this way, a comparison can be drawn between in situ and in operando approaches.

References

(1) Schuhmann, W. Amperometric Enzyme Biosensors Based on Optimised Electron-Transfer Pathways and Non-Manual Immobilisation Procedures. Rev. Mol. Biotechnol.
2002, 82 (4), 425–441.
(2) Wheeldon, I.; Minteer, S. D.; Banta, S.; Barton, S. C.; Atanassov, P.; Sigman, M. Substrate Channelling as an Approach to Cascade Reactions. Nat. Chem.
2016, 8 (4), 299–309.
(3) Liu, Y.; Hickey, D. P.; Guo, J. Y.; Earl, E.; Abdellaoui, S.; Milton, R. D.; Sigman, M. S.; Minteer, S. D.; Calabrese Barton, S. Substrate Channeling in an Artificial Metabolon: A Molecular Dynamics Blueprint for an Experimental Peptide Bridge. ACS Catal.
2017, 7 (4), 2486–2493.

Figure 1
High Electrochemical Signal Amplification Using a Propagating Cascade Reaction and a Redox Cycling Reaction
Authors: Yang Haesik , Park Kiryeon 
Published: May 2020

Propagating cascade reactions based on two enzymes have been used to achieve high signal amplification in biosensors wherein one enzyme continually triggers the activation of the other enzyme that produces signaling species. However, in many cases, biosensors that use cascade reactions are not sensitive enough to allow low detection limits because of the inherent slowness of proteolytic reactions. This paper reports a sensitive electrochemical immunosensor using a high-signal-amplification method that combines a propagating cascade reaction and a redox cycling reaction. The cascade reaction uses ecarin and prothrombin: the ecarin label proteolytically converts inactive prothrombin into active thrombin, which then proteolytically liberates electroactive p-aminophenol (AP) from an AP-conjugated peptide. The liberated AP is electrochemically oxidized to p-benzoquinone imine (QI), regenerated by the reduction of QI by NADH, and then electrochemically reoxidized. This electrochemical−chemical (EC) redox cycling reaction significantly increases the electrochemical signal. The developed immunosensor is also compared with an immunosensor that uses only a propagating cascade reaction and an immunosensor that uses a single proteolytic reaction and an EC redox cycling reaction. The detection limits for thyroid-stimulating hormone (TSH) obtained using the three immunosensors are 3 pg/mL, 2 ng/mL, and 4 ng/mL, respectively, indicating that the newly developed immunosensor is more sensitive than the others. The measured concentrations of TSH in clinical serum were found to agree well with those determined using a commercial instrument, indicating that the immunosensor is highly promising for sensitive detection of biomolecules.
Keyword: Electrochemical biosensor, Cascade reaction, Redox cycling, Proteolytic reaction
Designing and Fabrication of Low Cost Microfluidic Electrochemical Paper Analytical Device (ePAD) for Sensing
Authors: Kariate Sudhakaraprasad , Sonia Joseph 
Published: May 2020

The development of electrochemical sensors as miniaturized and low-cost platforms for the rapid and sensitive detection of biomolecules demands for the requirement of disposable economically viable and easy manufacturable devices. Moreover, it should ASSURES (Affordable, Sensitive, Specific, User-friendly, Robust, Electrode for Sensing) the simple DIY (Do It Yourself) strategy. This could be achievable only if the substrate for the electrodes are inexpensive, easily manufacturable and should be from renewable and reusable resources. Simple paper offers unique advantages such as, easily printable, impregnable, and because of its innate cellulose structures, paper is protein and biomolecules friendly. In addition, porous structure acts as a good filter, and facilitates lateral flow. On the other hand, papers also have been used to make paper analytical devices (PAD), which have the advantages to incorporate microfluidic channels and reagent prestorage zones with mixing opportunities for colorimetric and electrochemical sensing units. Recently, these PADs have been recognized as low-cost and disposable sensing platforms.
Considering the aforementioned properties, herein paper has been explored as a substrate for the fabrication of microfluidic ePAD. Using simple photo-lithography technique, we could achieve the hydrophobic and hydrophilic regions for making a 3 in 1 electrode patterns consists of working, counter and reference electrodes along with the reservoirs for analyte of interests (sample inlet) and reagents (prestorage zones). The designed and fabricated ePAD with colorimetric detection zones (Fig.1) was further characterized by surface morphological and electrochemical studies. As a proof-of-concept, we were able to use ePAD as an electrochemical sensor for trolox (analogue of Vitamin E, an antioxidant), and a probe for selective detection of dopamine in the presence of ascorbic acid. On the other hand, the electrochemical investigations further revealed the interplay between edge plane sites, oxygen functionalities, and the carbon structures π-π interactions with pyrene conjugates towards biomolecules detection. The calibration plot for the trolox sensor showed linear range from 5 µM to 400 µM with a detection limit of (S/N=3) of 1.17 µM. The modified ePAD were able to detect dopamine in real sample with satisfactory results. Aforementioned observations indicated that ePAD have great potential to establish point-of-care testing platform for clinical applications. The findings also demonstrated simple fabrication of microfluidic ePAD is possible, unlike the widely used wax printing technique, and laser scribing or screen printing, or inkjet printing of electrodes onto different substrates, which requires sophisticated instrumentation and skilled personal.

Figure 1
Chemo-Mechanical Model for Internal Stress Impact on Lithium Dendrite Growth
Authors: Meyer Julia Mae , Mukherjee Partha P. , Harrison Katharine Lee , Roberts Scott A. 
Published: May 2020

Lithium-ion batteries have the potential for greater efficiency and lifetime than current commercial options. However, there are operational and safety concerns that must be addressed before expanding their applications. During charge-discharge cycles lithium dendrites form within the battery due to plating on Li-electrolyte surface inhomogeneities. Full penetration through the electrolyte to the cathode leads to a short-circuit, resulting in battery failure and sometimes fire. Thus, controlling the rate of lithium dendrite growth is imperative for creating safer and longer-lasting batteries. Dendrite growth occurs when the lithium deposition rate exceeds the stripping rate and increases when the current density at the peak of a surface inhomogeneity is greater than at the valley. Addition of mechanical stress due to both internal and external pressures can decrease the propensity for dendrite growth; for various system conditions, a critical pressure exists above which formation is suppressed. However, mechanical pressure also leads to other complications, including inhomogeneous transport through the separator caused by nonuniform contact of a rough Li surface. Pressure-driven creep of the Li surface additionally evolves the contact and mechanical landscape. In this work, we present a mesoscale model and parametrically study the effect of internal stress and material properties on dendrite growth. The model couples mechanical deformation in both Li and the separator with the electrochemical response during the charging phase. Both the effects of mechanical and transport properties of the liquid electrolyte are investigated. Phase maps of the conditions for which dendrite formation is encouraged or suppressed are created and can be used to inform battery manufacturing and material choices.
This work was supported by the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia National Laboratories is a multi-program laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525.
Impact of Water on the Properties of Litfsi-Acetonitrile Superconcentrated Electrolytes
Authors: Généreux Simon , Gariépy Valérie , Rochefort Dominic 
Published: May 2020

Superconcentrated electrolytes are a new class of electrolyte that is of interest to the scientific community for battery applications. These electrolytes consist of an amount of salt greater than the amount of solvent, while remaining liquid. It is currently accepted that the reduction of the solvation sphere under these conditions results in a greater electrochemical stability of the solvent and a higher Li+ transport number. These properties are widely used in the literature For instance, superconcentrated electrolytes employing acetonitrile as the solvent have been applied in lithium metal batteries while acetonitrile with moderate salt concentration decomposes on lithium. Despite the attractiveness of the field to these electrolytes, their properties are still poorly understood, and the methods of analysis used vary between different studies. There is no standard protocol for their use and it becomes difficult to establish correlations between different studies. Our goal is to establish the required methods to standardize the methodology and fill the gaps in the field.
To do so, we firstly studied superconcentrated electrolytes based on LiTFSI and acetonitrile. The approach taken highlights the factors that have a significant impact on the properties of electrolytes. One of these factors is the water content. The results demonstrate that the presence of water in the solutions has a limited impact on the physical properties of viscosity and density of the mixtures as long at the concentration remains at and below 1000 ppm. The water content has a significant impact on the electrochemical window of stability of the electrolyte, reducing it to less than 2 V at 1000 ppm. The solvating structure of superconcentrated electrolytes is also studied via the electrochemistry of the Ferrocene/Ferrocenium couple to probe the impact of the electrolyte properties on electron transfer reactions. These results highlight the importance of structure and composition in the development of superconcentrated electrolytes.
Using Experiment and First-Principles to Assess Electrochemical Windows of Common Solid Electrolytes for Their Application in All Solid-State Lithium Batteries.
Authors: Benabed Yasmine , Rioux Maxime , Rousselot Steeve , Hautier Geoffroy , Dollé Mickael 
Published: May 2020

During the last decades, lithium batteries have been developed to power a growing number of portable applications and to meet the needs of an increasingly mobile society. Their industrial and commercial application has always occurred in two successive steps of equal importance: the discovery of new electrode materials and/or electrolytes, followed by their extensive optimisation. A new generation of lithium batteries has been recently developed to meet high expectations in terms of safety, stability and capacity: All-Solid-State Lithium Batteries (ASSLB), where the conventional liquid electrolyte (LiPF6 + EC/DEC) is replaced by a safer and more stable ceramic, polymer or glass solid electrolyte (SE). ASSLB are partly developed with the prospect of using high potential materials as positive electrode and lithium metal as negative electrode. This is only possible through SE stated large electrochemical windows. Nevertheless, values for these electrochemical windows are very divergent in the literature published through the last decades. Recently, several studies have come to specifically decry the frequent overestimation of SE electrochemical stabilities 1,2. Establishing a robust procedure to determine SE real electrochemical windows has become detrimental. Our work is focused on developing a combined theoretical and experimental approach to better assess the electrochemical stability of widely used SE such as Li1.3Al0.3Ti1.7(PO4)3, Li1.5Al0.5Ti1.5(PO4)3 and LiLaTi2O6. In this presentation, we shed light on the importance of selecting the right experimental setup and explore the link between experimental and interpreted thermodynamic results.
1) Y. Tian, T. Shi, W. Richards, J. Li, J. Kim, S-H. Bo, G. Ceder. Energy Environ. Sci., 2017, 10, 1150
2)Z. Zhang, Y. Shao, B. Lotsch, Y-S. Hu, H. Li, J. Janek, L. Nazar, C-W. Nan, J. Maier, M. Armand, L. Chen. Energy Environ. Sci. 2018,11, 1945-1976.
Acetate-Based Water-in-Salt Electrolyte for Aqueous Sodium-Ion Batteries
Authors: Han Jin , Mariani Alessandro , Zarrabeitiaa Maider , Varzi Alberto , Passerini Stefano 
Published: May 2020

Aqueous rechargeable alkali-ion batteries have attracted considerable interest in recent years due to reduced cost, lower environmental impact and, most importantly, and improved safety.1 Unfortunately, the narrow electrochemical stability window of water (1.23 V) limits the maximum output voltage of aqueous batteries, thus leading to intrinsically low energy density. Water-in-salt electrolytes (WiSE) constituted of, for example, highly concentrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solutions, has promoted the development of aqueous LIBs.2 However, these highly concentrated electrolytes based on fluorinated salts spoil the two major advantages of aqueous batteries, which are the low cost and reduced environmental impact.
Here we study alternative “Water-in-Salt” electrolytes (WiSE) based on highly concentrated sodium acetate and potassium acetate solutions. This kind of halide-free WiSE are studied by classical Molecular Dynamics (MD), evidencing the overall molecular arrangement to approach the “sponge-like” structure observed in certain ionic liquids and it offers wide electrochemical stability window and compatibility with stainless steel current collector. This is then employed as electrolyte in aqueous sodium-ion batteries featuring polyanionic compounds as active material. In-situ X-ray diffraction (XRD) experiments evidence the structural evolution during the reversible sodium de/intercalation. The X-ray photoemission spectroscopy (XPS) confirms the formation of a solid-electrolyte interphase (SEI) layer on the negative electrode. The cells show stable cycle performance and high coulombic efficiency above 99 % at 1C and 99.9% at 10C over 500 cycles.
Keywords: Acetate-based, Water-in-Salt electrolyte, aqueous sodium-ion batteries, high coulombic efficiency
References:
1. W. Li, J. R. Dahn, & D. S. Wainwright, Rechargeable lithium batteries with aqueous electrolytes, Science, 264((1994)1115-1118.
2. L. Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. Fan, C. Luo, C. Wang, K. Xu, "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries, Science, 350 (2015) 938-943.