bluuebunny/crossref_metadata_2025_split huggingface dataset:
Unraveling Electrochemical Lignin Degradation in Organic Solvent for Production of Valuable Fuels and Chemicals
Authors: Hasan Mahmudul , Greenlee Lauren F 
Published: September 2023

Lignin is the second most abundant biopolymer in nature after cellulose. Due to its distinctive aromatic backbone, it is also one of the most unique biopolymers. The aromatic components in lignin provide structural support to plants and comprises about 30% of the plant material. These aromatic groups can be used to produce renewable aromatic compounds. Also, these aromatic compounds can be used to produce biofuels which can be promising alternative to fossil-based fuels and chemicals. Besides, from previous studies it is found that about 40 to 60 million tons of lignin are generated from pulp and paper industry, mostly as wastes. So, developing novel and attractive strategies for fragmentation of lignin is gaining increased interest among scientific community for valorizing this underexploited material. Also, by valorizing lignin the sustainability of biorefinery and paper industry can be enhanced. However, the present technologies used for degradation of lignin generally requires the use of metallic catalysts at high temperatures and harsh reaction conditions. As a result, catalyst recovery and decomposition often become difficult under such harsh conditions and the process becomes impractical. Also, these technologies suffer from poor selectivity and usually produce the desired fragmentation products in low yields. Compared to the thermocatalytic transformation of lignin, electrocatalytic approaches have several advantages like it is environmentally friendly, have mild reaction conditions and the cost is low. Besides, there is a lack of studies incorporating electrocatalytic oxidation and reduction of lignin in organic solvent. In this project, the main goal was to overcome the challenge of using isolated lignin from various industrial processes by electrochemical depolymerization of lignin in organic solvent like tetrahydrofuran. Tetrahydrofuran is mainly used in Co-solvent Enhanced Lignocellulosic Fractionation (CELF) process. So, electrocatalytic degradation of lignin in this solvent is beneficial because the product from CELF process can be directly used here and thus it can work as a secondary treatment process for CELF process. Cyclic voltammetry (CV) and Chronoamperometry (CA) which are important tools for identifying redox reactions happening in the system is used here. In this presentation, for varying concentrations of Lignin, Tetrahydrofuran and sulfuric acid the results found from CV and CA will be discussed with practical significance.
Keywords: Recalcitrant biopolymer, Lignin in organic solvent, controlled electrocatalysis, secondary treatment for CELF process, Cyclic Voltammetry
Transport in Ion-Exchange Membranes with Ternary Solutions of Salt, Water and Alcohol Relevant for (Reverse) Electrodialysis
Authors: Solberg Simon Birger Byremo , Burheim Odne Stokke , Grieg Joachim Willumsen 
Published: September 2023

Leaching of Li-ion battery components in sulfuric acid followed by precipitation with ethanol has been proposed as a route for material recycling [1]. Cobalt, copper and lithium were then recovered as sulphate salts. The final mixture of dilute salts, water and ethanol may be further processed using ion-exchange membranes and electrodialysis to separate salts and water from ethanol, with the aim of increasing salt recovery and allowing for the re-use of the spent ethanol. We investigate the effect of alcohol on the transport numbers, resistance and the thermodynamic properties of the membrane and the aqueous solutions of alcohol, water and salt. This has implications for the electrodialysis of alcohol-containing mixtures, as well as for the application of this working fluid to a power-producing reverse electrodialysis system.
[1] S. Aktas, D. J. Fray, O. Burheim, J. Fenstad & E. Açma, Recovery of metallic values from spent Li ion secondary batteries.
Different Approaches to Teaching Electrochemistry and Equilibria II - Updates and Aftermath®
Authors: Coduto Joshua Richard , Lazicki Andy Peter , Paschkewitz Timothy , Leddy Johna 
Published: September 2023

Instruction in electrochemistry and equilibria was once algebraically intensive. But the skills of contemporary undergraduates have changed. Instruction has shifted to spreadsheets, web searching, and mathematical manipulators (e.g., Wolfram Widgets®). Emphasis on methods of problem solving requires full access to web tools, open book/ open computer exams, and new ways to present data.
For electrochemistry and equilibria, tools include systematic treatment of equilibria + Wolfram Widgets to complete the algebra once the system is specified; potential axes to identify spontaneous reactions and pH dependence; and spreadsheets tailored to various classes of titrations that are developed by the students with video supplements.
Here, several newly deployed tools for undergraduate instruction are briefly introduced. The commercial tools are available at little or no cost.

Wolfram Widgets®

“Walk the Duck”

Voltammetry i vs E and Ohm’s law

Merge Cubes® for display of 3D data

AfterMath cyclic voltammetric simulations (Pine Research)

ProWriting Aid® and BibCitation®

Tools are provided to allow students to “See the Beaker” and to encourage the students to speculate about chemical systems and test their ideas.
Acknowledgments: Work supported by the Carver Foundation and Innovations in Teaching with Technology Awards (ITTA) at the University of Iowa
In Situ Synthesis of Co-WO3 Anodic Layers for Enhanced Photoelectrochemical Water Splitting
Authors: Syrek Karolina , Zycha Marta , Kotarba Sebastian , Sulka Grzegorz 
Published: September 2023

Photoelectrochemical water splitting under solar radiation is one of the most studied areas of science. However, there are still many problems connected with this topic such as the low efficiency of systems or their usability only in the region of ultraviolet radiation. Anodic metal oxides are used as working electrodes in PEC cells due to their unique geometry, relatively high surface area, simple preparation, and their unique properties. Nanostructured tungsten oxide is characterized by strong photocorrosion stability in aqueous solutions and stable physicochemical properties. The main advantage of this material is its bang gap energy (2.6 eV), which is much lower than that of the commonly used titanium dioxide (3.2 eV). In consequence, absorption in the visible light region is significantly increased (up to 12% of the solar spectrum). The main objective of this project is to develop and optimize the single-step fabrication method of cobalt-doped nanostructured anodic tungsten oxide with enhanced photoelectrochemical properties under solar radiation. Particular attention will be paid to finding the correlation between the concentration of Co2+ ions in the electrolyte and their amount embedded in the anodic layer. A complex characterization (SEM/EDS, XRD, XPS, UV-Vis DRS) of nanostructured Co-WO3 layers will be performed to establish correlations between material morphology, composition, structure, and its optical, semiconducting, spectro-, photo- and electrochemical properties.
Acknowledgements
This research was partially funded within the budget of the "Excellence Initiative - Research University" program at the Jagiellonian University in Krakow.
Operando Microscopy of Model Electrocatalysts during Oxygen Evolution Reaction
Authors: Akbashev Andrew 
Published: September 2023

In situ characterization of electrochemical processes in model materials are central to fundamental electrochemistry as they provide precise potential-dependent quantities that can be used to accurately assess theoretical models and predictions. As such, structural evolution of materials under highly oxidizing conditions represents a particular challenge. To gain the necessary insight into the surface and bulk behavior, one should combine advanced in situ characterization techniques with well-defined materials that are essential for modeling.
In this talk, I will discuss how a combination of in situ microscopy techniques can provide insight into the surface and bulk behavior of electrocatalysts during electrocatalytic water splitting (OER). Specifically, I will show how operando electrochemical atomic force microscopy (EC-AFM) can be used to record nanoscale changes in the surface morphology during anodic corrosion of the perovskite SrIrO3 surface. I will also discuss how operando EC-AFM can be combined with operando transmission X-ray microscopy and scanning electrochemical cell technique to probe the evolution and reactivity of single particles of Co(OH)2.
(Invited) Using Molecular Dynamics Simulations to Relate Morphology to Water and Ion Dynamics in Hydrated Ion-Conducting Polymers
Authors: Frischknecht Amalie L. 
Published: September 2023

Hydrated ion-containing polymer membranes are used as electrolytes in a variety of applications, including in fuel cells and in alkaline batteries. Achieving high conductivity in hydrated, ion-conducting polymers typically requires the hydrophobic backbone of the polymers to be nano-phase separated from the hydrophilic domains so that the ions (protons or hydroxide ions) have well-defined water domains for efficient transport. The ion transport thus depends strongly on the hydration level and on the detailed morphology of the hydrophilic domains. It is often difficult to determine the morphology of these domains experimentally. I will present results from atomistic molecular dynamics (MD) simulations that reveal the domain morphology in various ionic polymers. Increasing water content generally leads to an increase in the characteristic spacing between hydrophilic domains. However, this swelling can be obscured in X-ray scattering due to a loss of scattering contrast between the hydrophobic and hydrophilic domains. The MD simulations reveal that the systems are nano-phase separated, even when X-ray scattering appears to indicate otherwise. Calculated and measured scattering profiles are in good qualitative agreement. I will discuss several methods to characterize the water domain morphology in more detail, including various measures of pore size distributions, surface areas, and fractal dimension. Water and ion diffusivities calculated from the MD simulations follow the experimentally-measured trends in conductivity and are consistent with changes in the nanoscale morphology with changing water content. I will discuss the implications of the results for the future design of ion-conducting polymers for use as membranes in electrochemical devices.
This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. DOE’s National Nuclear Security Administration under contract DE-NA-0003525.

Figure 1
Investigation of Electrocatalytic CO2 Reduction Reaction Mechanism: Role of H2s and Exsolved Metal Nanoparticle at Perovskite Oxides Electrodes
Authors: Aydogdu Irfan , Martinez Rios Franz Michel , Birss Viola Ingrid , Ponnurangam Sathish 
Published: September 2023

ABSTRACT
Affordable and sustainable energy demands from post-modern society as well as the need to lower the CO2 emissions require alternative approaches rather than business-as-usual [1]. Solid oxide fuel cells (SOFC) and solid oxide electrolysis cells (SOEC) are one of the promising technologies that are being developed to meet these needs. The working principle of an SOEC is based on heterogeneous electrocatalysis to produce syngas (CO and H2) by splitting CO2 and H2O at high temperatures. The stability and electrochemical performance of the components, including the solid-state electrolyte and the electrode materials, are vital to making this technology mature enough to enhance its economic competitiveness [2]. Therefore, the physical and chemical features of the components need to be understood fundamentally. Due to its high electrocatalytic activity, Ni-YSZ cermets are still the most commonly used electrode materials in SOECs. However, the poisoning of these catalysts by sulfur deposition and coke formation is a problem. As a result, there has been growing interest in using mixed conducting perovskites oxides (MIECS) as electrode materials, which are more resistant to these challenges and as their chemical and physical properties can be easily tailored [3].
Here, we investigate a family of MIECS that can be used in many fuel environments and is also highly active in air, namely LCFCr (La0.3Ca0.7Fe0.7Cr0.3O3-δ). One specific objective of the current study is to elucidate the CO2 reduction mechanism based on varying the composition of LCFCr [4,5] as well as by alterations of the operating conditions, such as temperature, reactant gas mixture, and applied potential. Importantly, the effect of the presence of H2S in the gas phase [6] and ex-solved metal nanoparticles on the surface [7] during exposure to CO2 at open circuit and under CO2 reduction conditions is being investigated. This work involves the use of reactive molecular dynamics (ReaxFF MD), electrochemical perturbations, and thermo-catalytic methods, with our initial ReaxFF MD results showing good agreement with the experimental results [8].
ACKNOWLEDGMENTS
This computational research was supported by the Canada First Research Excellence Fund (CFREF), while the platforms for this computational work were provided by Westgrid (https://www.westgrid.ca) and Compute Canada (https://www.computecanada.ca). Thanks are also extended to Dr. Haris Ansari, Oliver Calderon, Michael Pidburtnyi, Dr. Scott Paulson, Dr. Anand Singh, Sara Bouzidi and Adam Bass for helpful discussions.
Cu Surface Chemistry in Acid Media: Vibrational Spectroscopy, Mass Spectrometry and ECSTM Measurements
Authors: Raciti David , Hight Walker Angela , Moffat Thomas P 
Published: September 2023

Copper electrodeposition is a central process in the metallization of microelectronics and more recently copper has also found use as an important electrocatalyst in the conversion of CO2 to hydrocarbons. Gaining mechanistic insight into the reactivity of Cu surfaces requires in situ and better still in operando measurements. Herein the utility of the combination of vibrational spectroscopy (SEIRAS, SHINERS), electrochemical mass spectrometry (EC-MS) and scanning tunneling microscopy (ECSTM) to examine the competitive and co-adsorption interactions between potential dependent halide adsorption, molecular adsorption, underpotential metal deposition and hydride formation on low index Cu single crystals surface will be detailed. Further still, the emergent opportunity to study the impact of such interaction on metal deposition reactions will also be explored.
1.Raciti and T.P. Moffat, “Quantification of Hydride Coverage on Cu(111) by Electrochemical Mass Spectrometry,” J. Phys. Chem., 126, 18734-18743 (2022).
2.Raciti, A.R. Hight Walker, T. P. Moffat, “Mapping Surface Chemistry During Superfilling with Shell- Isolated Nanoparticle Enhanced Raman Spectroscopy and X-ray Photoelectron Spectroscopy,” J. Electrochem. Soc., 169, 082506 (2022).
3.B.M. Tackett, D. Raciti, A.R. Hight Walker, T.P. Moffat, “Surface Hydride Formation on Cu (111) and its Decomposition to Form H2 in Acid Electrolytes,” J. Phys. Chem. Lett., 12, 10936-10941 (2021).
4. G.Liu, S. Zou, D. Josell, L.J. Richter and T.P. Moffat, “SEIRAS Study of Chloride Mediated Polyether Adsorption on Cu,” J. Phys. Chem. C., 122, 21933-21951, (2018).
(Invited) Towards a Mechanistic Understanding of the Oxygen Evolution Reaction on Hematite: Operando Characterization of Band Bending and Interfacial Chemical Speciation Using Sum Frequency Generation Spectroscopy
Authors: Yang Yuke , Tong Yujin , Campen R. Kramer 
Published: September 2023

Hematite is an attractive photoanode for the oxygen evolution reaction (OER) due to its cheap price, relatively small band gap, stability in alkaline solution and a valence band energy suitable for OER catalysis. However, insight into the OER mechanism, and thus the capability to rationally modify this material to optimize performance, is limited by the challenge in relating band bending, surface state population and chemical reactivity operando. Conventionally these issues are addressed by some combination of electrochemical impedance spectroscopy (EIS), photocurrent/voltage kinetics, and linear optical spectroscopies in the visible. While important, all of these approaches suffer from significant limitations: e.g. EIS and related techniques integrate over all charge transfer processes in the device while only those at the hematite/water interface are of interest (and thus require a challenging to validate model to quantify) and UV/Vis absorption measurements (whether steady-state or time resolved) are bulk-sensitive and probe spectrally broad features that are challenging to relate to surface structure.
Sum Frequency Generation (SFG) spectroscopy is interface-specific by its symmetry selection rules, can straightforwardly probe interfacial chemical speciation if one of the two incident fields is in the infrared, and is sensitive to the amplitude of interfacial electric fields. These attributes make the technique particularly suitable for characterization of interfacial chemical speciation, double layer and space charge layer structure at the working electrode/electrolyte interface within thin-film spectroelectrochemical cells. Here I describe our recent efforts to characterize chemical speciation and interfacial field at a hematite/electrolyte interface, in the presence and absence of external illumination, as one moves from the Hematite flat band potential through the onset of the OER. Using vibrationally resonant SFG spectroscopy, at infrared wavelengths > 10 micron, we quantify the population of surface holes, i.e. Fe(IV)=0 groups, as the OER turns on. Concurrently we quantify the development of the space charge potential using non-resonant SFG. Recent work has argued, largely from current or optical transients in the visible under chopped illumination, that the OER on Hematite proceeds by a multi-hole mechanism. Because our approach allows for the simultaneous quantification of interfacial field and chemical speciation we directly address this mechanism and the circumstances under which it is expected to apply. More generally, the role of interfacial field in oxidation catalysis has been an object of much current interest. The approach described here – in which interfacial speciation and field can be quantified operando – offers an ability to explore this relationship not possible via any other combination of experimental approaches.
Spectroelectrochemical Detection of Acetaldehyde in Wines
Authors: Williams Kia , Ibáñez David , González-García María Begoña , Hernández-Santos David , Fanjul Pablo 
Published: September 2023

The combination of electrochemical sensors and spectroscopy has been scarcely used due to the traditional instrumental limitations of spectroelectrochemical techniques. However, the development of new setups and commercial instruments enables the spectroelectrochemical detection of a variety of analytes [1]. In that way, UV-Vis spectroelectrochemistry joins the advantages of electrochemistry and UV-Vis spectroscopy, improving the analytical features that both techniques have separately.
In this work, a new spectroelectrochemical two-enzyme sensor system has been developed for the detection of acetaldehyde in wine. Spectroelectrochemical detection is achieved by the analysis of the optical properties of the ferri/ferrocyanide redox couple involved in the enzymatic process: aldehyde dehydrogenase catalyzes the aldehyde oxidation using NAD+ as a cofactor and, simultaneously, diaphorase reoxidizes the NADH formed in the first enzymatic process due to the presence of ferricyanide. The analysis of the characteristic UV-Vis bands of ferricyanide at 310 and 420 nm allows the detection of acetaldehyde, since absorption bands are only related to the oxidation of this substrate and avoids the contribution of other interferents [2]. Two different wines have been evaluated in this work, obtaining excellent results that agree with the literature as well as with those obtained with a commercial fluorogenic kit.
References
[1] C. Navarro, M.B. González-García; D. Hernández-Santos; M.A. Heras, A. Colina, P. Fanjul-Bolado, Electrochem. Commun. 2016, 64, 65–68.
[2] D. Ibáñez, M. B. González-García, D. Hernández-Santos, P. Fanjul-Bolado, Biosensors 2022, 12, 1032.
Using Ambient Pressure Photoelectron Spectroscopy to Investigate the Time Dependence of Electrostatic Potential Difference over the Interphase between an Electrode and an Electrolyte
Authors: Krizan Alenka , Ericson Tove , Kallquist Ida , Chen Heyin , Temperton Robert , Dominko Robert , Gaberscek Miran , Hahlin Maria 
Published: September 2023

Ambient pressure photoelectron spectroscopy (APPES) is a method well-suited for measuring the change ∆φ in electrostatic potential difference φ over an interphase between an electronic conductor and an insulator. APPES had previously been used to compare ∆φ over an interphase between an electrode and an electrolyte with the change in electrochemical potential difference ∆UWE-RE
between the working and the reference electrode UWE-RE
.[1] The relationship between ∆φ and ∆UWE-RE
at low current-transient had been shown to follow two distinct trends depending on whether charge transfer of Li+ ions between an electrode and an electrolyte occurs or not.[1,2] In this work, APPES was used to investigate the time dependence of ∆φ after changing UWE-RE
. The studied electrochemical system consisted of Au (working electrode), Li4Ti5O12 (reference electrode) and a second Li4Ti5O12 (counter electrode) with 0.008 M LiClO4 in propylene carbonate (PC) as the electrolyte. Pressure in the sample compartment was equal to the saturated PC pressure. APPES experiments were performed at HIPPIE beamline at MAX IV in Lund and were conducted as follows. After applying a potential step ∆UWE-RE
, a C 1s spectrum was measured every 7 s. Incident photon energy was 1800 eV. Each spectrum was fitted using a Python code written especially for the obtained C 1s spectra. Time dependence of ∆φ was extracted from the shift in the kinetic energy ∆KE of the C=O peak (∆φ = ∆KE). Experiments were performed in both regimes, i.e. when the working electrode behaves as an ideal polarizable electrode and when it behaves as an ideal non-polarizable electrode, and have shown the time dependence of ∆φ to differ for the two regimes. Behaviour of ∆φ(t) as well as the experimental setup and spectral fitting using the Python code will be discussed.
Figure 1: a) Schematic depiction of the electronic electrostatic potential φ between a working (WE) and a reference electrode (RE). Electrostatic potential profile is not to scale. b) An example of the experimentally obtained time dependence of the C=O peak kinetic energy KE(t). KE(t) is related to φ(t) as ∆φ(t) = ∆KE(t).
References:
[1] Källquist, I. et al. Probing Electrochemical Potential Differences over the Solid/Liquid Interface in Li-Ion Battery Model Systems. ACS applied materials & interfaces
13, 32989–32996 (2021).
[2] Källquist, I. et al. Potentials in Li-Ion Batteries Probed by Operando Ambient Pressure Photoelectron Spectroscopy. ACS Applied Materials & Interfaces
14, 6465-6475 (2021).

Figure 1