bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Transition Metal Oxide Catalysts for the Oxygen Evolution Reaction
Authors: Browne Michelle P , Jaśkaniec Sonia , Tyndall Daire , Gannon Lee , McGuinness Cormac , McEvoy Niall , Nicolosi Valeria 
Published: July 2021

Currently, approximately 96% of global H2 production is carried out by fossil fuel based routes such as steam reforming of natural gas or coal gasification;1 while only 4% of H2 is generated by renewable energy routes such as water splitting. To increase the percentage of H2 produced by water splitting, it is necessary to lower the overall cost and, at the same time, to improve the efficiency associated with water splitting technologies, which is, closely related to cost, durability and kinetic issues arising from the catalysts used.
Water splitting, also known as water electrolysis, is the separation of the H2 and O2 from water using an external power source, denoted as the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER), respectively.2 Even though the main goal of water splitting is to produce H2, the opposite reaction, the OER, hinders the overall performance of this process. Hence, to make the overall process of water splitting more efficient, new active and more conductive OER catalysts need to be developed.
In general, layered/2D materials exhibit higher surface area and are more conductive than their bulk counterparts therefore hold great promise as next generation materials for the OER.3 Hence, as Transition Metal Oxide (TMO) based materials are currently the best performing catalysts for the OER, it is logical that few layer and 2D TMO materials are likely candidates to emerge as alternative low cost and active catalysts for this electrochemical energy conversion application.2 In this talk, layered/2D TMO based materials as potential catalysts for the OER will be discussed.4

S. Shiva Kumar and V. Himabindu, Materials Science for Energy Technologies, 2019, 2, 442-454.

M. P. Browne, Z. Sofer and M. Pumera, Energy & Environmental Science, 2019, 12, 41-58.

J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist and V. Nicolosi, Science, 2011, 331, 568-571.

S. Jaśkaniec, C. Hobbs, A. Seral-Ascaso, J. Coelho, M. P. Browne, D. Tyndall, T. Sasaki and V. Nicolosi, Scientific Reports, 2018, 8, 4179.
(Invited) Sustainable and Energy-Efficient (nano)Structured Oxidation Electrocatalysts in Acidic Media from Earth Abundant Metals
Authors: Galan-Mascaros Jose Ramon , Garcés Pineda Felipe , Yu Jiahao , Gelmetti Ilario 
Published: July 2021

The establishment of a sustainable renewable fuels technology will depend on the electrocatalytic reduction of substrates into fuels, but also on the electrocatalytic oxidation of water or other feedstock to extract the needed electrons and protons. The requirements for the oxidation electrocatalysts are typically more demanding regarding long term stability, since these catalysts must be fast, selective and efficient, but also robust to high oxidation potentials, water, oxygen, electrolytes, acids or bases, etc. Several earth abundant metal oxides are excellent electrocatalysts in neutral and basic conditions, with multiple examples from different labs.1 However, most active transition metal oxides are unstable in acidic media, where they just dissolve even in open circuit conditions. Only noble metal oxides, such as IrO2, are able to exhibit competitive electrooxidation activity in aqueous acidic conditions (pH < 3), where reduction electrochemistry is easier and faster, and proton exchange membrane (PEM) technology may facilitate high current density performance in compact electrolyzer architectures.
In this communication we will report our latest results in the search for efficient, low cost oxidation electrocatalysts from earth abundant, non-critical raw materials able to work in aqueous acidic media. We showed how Co-containing polyoxometalates (POMs), are active electrocatalysts for the oxygen evolution reaction (OER) in acidic conditions when stabilized by a partially hydrophobic support.2 Although with some limitations, a hybrid composite of an insoluble salt of the polyoxoanion [Co9(H2O)6(OH)3(PW9O34)3]16– blended with a carbon paste electrode exhibited superior performance and higher current densities than the corresponding IrO2-based electrodes in the low overpotential range. We are extending this same strategy to bulk and nanostructured transition metal oxides to provide fast and robust OER at pH < 1. Furthermore we will show how some of these metal oxides can also catalyze alternative electrochemical oxidation processes of high interest for the chemical industry, such as the selective oxidation of alcohols to aldehydes or carboxylic acids.
[1] J. R. Galan-Mascaros, ChemElectroChem, 2015, 2, 37. [2] M. Blasco-Ahicart, J. Soriano-Lopez, J. J. Carbó, J. M. Poblet, J. R. Galan-Mascaros, Nat. Chem.
2018, 10, 24.
A Mechanistic Understanding of Electrochemical Bistability Induced By the Presence of 1,10-Phenanthroline in the Cathodic Deposition of Copper
Authors: Rospendowiski Julia , Pinto Maria Rodrigues , Hessel Cristian , Sitta Elton , Nagao Raphael 
Published: July 2021

We report herein a precise control of the electrochemical bistability induced by surface area changes during the cathodic deposition of copper. Small additions of 1,10-phenanthroline (Phen) in the reaction media present an inhibiting effect on the global rate mainly due to the adsorption of protonated Phen. The increase of its concentration favors a shrinkage of the bifurcation diagram and shifts it to less negative potentials. The dynamic instability is verified by impedance measurements, and a negative impedance is clearly found. We calculated the apparent molar mass of the adsorbents using in situ gravimetric monitoring in the electrochemical experiments, and the results indicate that mass changes occur mainly due to the reduction of copper from bivalent ions dissolved in the reaction media. Importantly, the adsorption of protonated Phen molecules does not show a considerable contribution in mass variations but prevents the formation of a copper course grained morphology over the surface. Imaging analysis indicates finer nodulations at the lower branch compared to the upper branch in the bistability domain. On the basis of these observations, a kinetic mechanism is proposed and a good agreement is obtained between the apparent molar mass extracted from experiments and the theoretical values. Altogether, our results contribute to a detailed physicochemical description of the nonlinear behavior, bringing new insights about this reaction and pointing out the possibility to design switchable surface electrodes by taking advantage of the bistable behavior.
Rospendowiski, J.; Pinto, M. R.; Hessel, C.; Sitta, E.; Nagao, R. ACS Omega
2018,
3, 13636.
A Numerical Investigation of the Effect of External Resistance and Applied Potential on the Distribution of Periodicity and Chaos in the Anodic Dissolution of Nickel
Authors: Rodrigues Caio Silva , Pereira dos Santos Caio Guilherme , Miranda Renan Carneiro Cavalcante de , Parma Eduardo , Varela Hamilton , Nagao Raphael 
Published: July 2021

In the latest years, the world has witnessed intense research on the synthesis of nanostructured materials. One of the most interesting methodologies recently proposed to this end is the use self-organized electrochemical reactions, on which the structuring emerges spontaneously from the reaction, permanently engraved on the electrodes. To achieve a robust process for a rational synthesis utilizing this technique, however, one must have a detailed description of the reaction’s dynamical properties, as they are closely related to the nanometric patterns formed [ChemElectroChem, 2020, 7, 2979].
One of such self-organized electrochemical reactions is the anodic dissolution of nickel. This reaction has the added benefit of being successfully modelled computationally in the literature, contributing to the dynamical studies on the system [J. Phys. Chem., 1992, 96, 2676]. This work presents a numerical exploration of the system’s dynamics, and its relation to the applied voltage and external resistance, two parameters that can be readily accessed on the experimental counterpart. Dynamical phase diagrams were built by varying these parameters (used in their dimensionless form), using the morphological period and Lyapunov exponents of the time-series to characterize its dynamical behavior.
Magnifications of the diagrams’ chaotic regions revealed the presence of self-similar periodic islands (often referred as shrimps) on them, a feature commonly found on chaotic electrochemical dynamics. Period-doubling, a frequent route to chaos, was found on these shrimps, and a period-adding sequence was successfully identified on a shrimp dispersion, even though the shrimp density on the diagrams were low, when compared to other chaotic electrochemical systems.
The shrimps were deformed as both control parameters were increased, being stretched diagonally when the system moved from potentiostatic to galvanostatic condition. For large values of external resistance and potential applied, this stretching was so extreme that the shrimps gave place to parallel linear diagonal domains of periodicity intertwined by chaotic regions. Period-doubling cascades were also found in these domains, suggesting that some dynamical properties from the shrimps were preserved after the stretching. The hypothesis that the stretching is closely related to the exponential terms on the Butler-Volmer equations that makes up the kinetic model was raised.

Figure 1
Structure and Stability of Small Metal Clusters on Stoichiometric and Defective 2D MoS2
Authors: Nies Cara-Lena , Nolan Michael 
Published: July 2021

Layered materials, such as MoS2, are of great interest to the research community due to their wide range of potential applications. They are of particular interest as supports for low dimensional metal catalysts, as well as for use in the electronics industry as ultra-thin diffusion barriers in semi-conductor device interconnects.
Thus, understanding the interaction between a variety of metal structures and the MoS2 monolayer is of great importance. In previous studies the focus has been largely on the strength of the interaction between a single atom or a nanoparticle of a wide variety of metals, which creates a significant knowledge gap in thin film nucleation on 2D materials. To begin addressing this deficit, we present a density functional theory (DFT) study of the adsorption of small metal structures, with up to four atoms, on a monolayer of MoS2. The metals of interest are Cu, Co and Ru, chosen for their relevance in electronics applications. We show how the metal-substrate interaction changes depending on the particular metal, as well as the mode of adsorption and overall nanocluster structure. Further, we show the effect that the presence of a sulphur vacancy in the monolayer has on the metal-substrate interaction, as this is a commonly observed defect.
The strength of interaction between the metals and MoS2 is in the order Co > Ru > Cu. The effect of adsorption on MoS2 is localised to the metal cluster, however depending on the particular structure, some distortions of the MoS2 lattice can be observed upon adsorption of Ru.
Recycling Diesel Combustion Byproducts As Electrode Material for Lithium-Ion Batteries
Authors: Ketelsleger Cameron , Gregory Darrell , Ozdogru Bertan , Yang Sisi , Cronin Stephen B. , Capraz Omer Ozgur Özgür 
Published: July 2021

Lithium-ion (Li-ion) batteries are the most widely commercialized mode of portable, rechargeable energy storage in the twenty-first century. These batteries were introduced in the early 1990s and since have been massively produced to power personal electronics, store renewable energy, and more recently power electric automobiles. As demand for lithium-based batteries increases, it is important to recycle materials pertinent to the battery set up as frequently as possible. In this study, we examine the electrochemical performance of diesel exhaust soot particles as a conductive carbon in cathode composite electrodes and as active anode particles in anode composite electrodes. Diesel soot is a toxic byproduct of diesel combustion which contributes to an estimated 3,500 premature respiratory-related deaths per year in California alone [1]. By removing contaminates in the soot via annealing or tunnel process, we can adjust the electrochemical performance such that it is suitable for batteries.
Electrochemically active diesel particulate matter is obtained from particulate scrubbers attached to diesel-powered engines. Diesel soot powders were annealed at 250 oC for one hour. The material was tested as conductive carbon in cathode electrodes and as an anode in Li-ion batteries. For testing conductive carbon for cathode electrodes, we used lithium iron phosphate (LFP) as the active material and prepared composite electrodes by mixing LFP, conductive carbon, and carboxymethyl cellulose in 8: 1: 1 weight ratio. We compare the performance of the soot as a conductive material with the commercially available Super P carbon (Figure 1A). In the second part of the study, we investigated the ability to store lithium ions as an anode material (Figure 1B). To do this, we prepared composite electrodes made with 80% soot, 10% binder, 10% Super P carbon. The electrochemical performance of these electrodes was tested with cyclic voltammetry, galvanostatic testing, and impedance spectroscopy at various rates.
We find that both diesel soot materials perform closely to Super P as a conductive carbon in LFP composite cathodes (Figure 1A). We find that the electrochemical performance of the recycled carbon waste as a conductive carbon is close to that of the standard, Super P, in composite cathode electrodes. Figure 1B shows that the capacity - voltage profiles of diesel soot anode electrode cycled at different C-rates. Considering performance in both electrodes, this is a novel development which shows hope for making an industrial waste and toxic byproduct useful in electrochemical energy storage.
Acknowledgement: Cameron Ketelsleger and this work were supported by the Lew Wentz Foundation.

Figure 1
Different Redox Mediators Applied to Elastin-like Polymer Surfaces
Authors: Austin Katherine , Feeney Stanley , Balog Eva Rose M , Halpern Jeffrey M 
Published: July 2021

Previous investigation of elastin-like polymer (ELP) modified surfaces showed successful modification followed by a reversible extension and collapse, as measured by electrochemical impedance spectroscopy (EIS). This work indicated successful modification of an electrode with ELP corresponds with a charge transfer resistance of 10-20 kOhms in 10 mM ferri/ferrocyanide (FFC).1 The EIS charge transfer resistance value can be seen to increase with a stimulus predicted to cause ELP collapse and then decrease again with a re-extension of the ELP. We investigated the effects of the FFC concentration and other solution conditions on the interpretation of EIS signals in monitoring ELP response.
For these experiments, ELP was attached to the surface of a gold electrode by binding a cysteine thiol from the ELP to the gold surface in the presence of the reducing agent TCEP. This was followed by EIS experiments to measure the electrochemical impedance of the same ELP-modified surface under three different electrochemical mediator conditions: (1) 5 mM FFC in water, (2) 10 mM FFC in water, and (3) 5 mM FFC in 0.5 M KCl aqueous solution. Before the exchange of electrochemical mediator, the electrode was washed. We observed an increased charge transfer resistance in the presence of 5 mM FFC and a decrease in charge transfer resistance in the presence of 5 mM FFC 0.5 M KCl relative to experiments performed in 10 mM FFC. We predict that the type of electrochemical mediator and supporting electrolyte used in conjunction with ELP modified surfaces will impact the interpretation of data. We will present our progress on the interpretation of ELP-modified surfaces using different electrochemical mediator concentrations, and what we learned from these results.
Acknowledgments: This work was supported by NIH P20 GM113131
References

M. A. Morales, W. A. Paiva, L. Marvin, E. R. M. Balog, and J. M. Halpern, Soft Matter, 15, 9640–9646 (2019).
A Model for Sonochemistry in a Thin Layer Sonochemical Cell: What Constructive Interference Yields
Authors: Parr Daniel , Leddy Johna 
Published: July 2021

Traditional sonochemistry (TS) in bulk solution is violent and expensive. Typically, a high power (> 60 W) ultrasonic horn is directed at a planar working electrode. Compression and rarefaction oscillations elicit cavitation bubble formation. Upon bubble collapse, high temperature (> 5000 K) and pressure (> 1000 atm) are produced locally, which enhances rates of chemical reactions. Bubble collapse near the electrode causes solvent jets directed at the surface to effect the surface cleaning and mass transport enhancements attributed to TS.
While productive, TS obscures quantitative measurement of electron transfer kinetics and mass transport and requires a large laboratory footprint. An alternative and efficient sonochemistry is needed. Thin Layer Sonochemistry (TLS) exploits natural acoustics in a thin layer electrochemical cell. Low power transducers (e.g., quartz crystal oscillators) are appropriate because TLS achieves resonance in the cell to amplify input sound to the limit set by the solvent. TLS is more efficient and allows finer control of experimental and acoustic parameters. The footprint of TLS is minimal, and so TLS is appropriate for energy production applications (e.g., fuel cells) in portable devices.
Experience suggests a subtle relationship between acoustic parameters and resonance. Here, a model is presented for calculation and explanation of resonance in a thin layer sonochemical cell. Background physics are explained and a step-by-step assembly guide is presented.
References:

Suslick, K. S.; Didenko, Y.; Fang, M. M.; Hyeon, T.; Kolbeck, K. J.; McNamara, W. B. III; Mdleleni, M. M.; Wong, M. "Acoustic Cavitation and Its Chemical Consequences" Phil. Trans. Roy. Soc. London A, 1999, 357, 335-353.

Johna Leddy, Chester G. Duda, Jacob Lyon, and William J. Leddy III, US Patent 10,300,453 B2, "Thin Layer Sonoelectrochemistry and Sonoelectrochemistry Devices and Methods," 28 May 2019.

D.L. Parr IV and J. Leddy, "Sonoelectrochemistry - A Sketch of Thin Layer Advantages," ECS Trans. (2019) 92(10), 65-73; Open Access, DOI:10.1149/09210.0065ecst
Deep Learning Combined with Surface-Enhanced Raman Spectroscopy for Chemical Sensing and Recognition
Authors: Bertz Morten , Yanagisawa Masahiro , Homma Takayuki 
Published: July 2021

Surface-enhanced Raman spectroscopy (SERS) combines the unique advantages of Raman spectroscopy – namely detection of specific molecular fingerprints without requiring prior labelling – with enhanced sensitivity. SERS takes advantage of the amplification of the incident electric field by localized surface plasmons on noble metal nanoparticle surfaces, which allows the rapid, non-destructive detection of a wide variety of analytes ranging from small molecules to entire microorganisms.
The data obtained from SERS experiments, however, can be difficult to interpret. Spectra are dominated by the chemical species in closest contact with the plasmonic field, and consequently spectra recorded at different points in time from the same sample can exhibit considerable differences. The rich chemical information contained in the spectral data therefore is often not utilized to its full potential or lost altogether.
Here, we combine deep convolutional neural networks (CNNs) with SERS to classify series of spectra obtained from mixtures of different sample species (1). We find that CNNs outperform standard chemometric methods, such as principal component analysis, but also support-vector machine classifiers, shallow artificial neural networks, or even trained human experts while requiring minimal data preprocessing, such as background subtraction or smoothing. We discuss optimizing the classifier with regards to network topology, learning strategy, and data augmentation.
In addition, we show that we can extract useful information from trained networks. In simple cases, activation maximization spectra, which represent the spectral features that are most relevant to discriminate between different sample classes, can provide a good approximation of the spectra in the original sample. We also train generative adversarial networks (GANs) (2) to generate / extract characteristic spectra from large, more heterogeneous datasets. These spectra can provide additional insight into the composition of the sample and might thus be relevant to guide further experiments.
Deep learning and SERS are two powerful techniques that complement each other. The high sensitivity of SERS quickly generates large, but often highly complex spectral datasets, which are in turn well-suited to the analysis by CNNs. Most importantly, deep learning not only excels at classification but can be used as a more general tool to facilitate the interpretation of heterogeneous, seemingly intractable datasets. Given the tremendous attention deep learning has attracted over the past decade, we anticipate that it will play an increasingly prominent role in spectral analysis as well.

Yang, J. et al., 2019. Deep learning for vibrational spectral analysis: Recent progress and a practical guide. Analytica chimica acta, 1081, pp.6–17.

Odena, A., Olah, C. & Shlens, J., 2016. Conditional Image Synthesis With Auxiliary Classifier GANs. arXiv:1610.09585 [stat.ML]

Figure 1