bluuebunny/crossref_metadata_2025_split huggingface dataset:
Role of Electrolyte-Adsorbates Interaction in Determining CO2 Reduction Reaction Pathways
Authors: Morinaga Asuka , Itoine Ryota , Kondo Yasuyuki , Yamada Yuki , Katayama Yu 
Published: September 2023

Electrochemical CO2 reduction reaction (CO2RR) is a promising strategy to convert atmospheric CO2 into valuable fuels and chemicals. Although the optimization of the catalyst-adsorbates interaction via tuning the binding energies of electrocatalysts has been extensively studied, activity and product selectivity remain a challenge. Recently, there has been a growing recognition that cations in electrolytes influence the activity of surface electrocatalytic reactions.1 A recent density functional theory study suggested that partially desolvated metal cations stabilize CO2RR intermediates via electrostatic interactions.2 Therefore, an experimental understanding of how the cations (and surrounding water molecules) control the intermediates present on the surface and govern the reaction pathway is critical to establish further insights into the design of electrolytes for CO2RR.
In this talk, the role of alkali metal cations and water molecules on the CO2RR is revealed by tracking the surface-bound intermediates using operando attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). We will also integrate the operando surface analysis with final product selectivity, further strengthening the understanding of the reaction mechanism. It will also be demonstrated that the holistic information about the electrolyte-adsorbates interaction can provide additional knobs to tune the energetics of key reaction intermediates, leading to further improvements in electrocatalytic activity for the CO2RR.
[Reference]
1 Ringe, S. et al., Energy Environ. Sci.
2019, 12, 3001–3014.
2 Monteiro, MCO. et al., Nat. Catal.
2021, 4, 654–662.
The effect of strong electric fields in acetonitrile-water mixtures
Authors: Sourpis Anastasios , Forero-Marinez Nancy , Schmid Friederike 
Published: September 2023

Electrolyte-free electrolysis fuel cells are central to a sustainable future
with clean water. With growing industrial development, for example, toxic heavy
metals, radioactive ions, and inorganic compounds are increasingly discharged into
the environment and our sources of drinking water. In novel cutting-edge developed
electrolysis fuel cells [1] the case of electrolyte-free electrolysis has been observed for
mixtures of water and acetonitrile. These high modular flow cells of electro organic
synthesis are very promising for the production of fine chemicals and pharmaceutically
active agents. The purpose of this study is to qualitatively and quantitatively evaluate
the effect of electric fields on electrolysis cells. Especially in the case of acetonitrile
and water mixtures, we have focused on understanding by atomistic simulations the
existence of the electrical conductance and how this can be described on larger scales.
References
[1] Highly Modular Flow Cell for Electroorganic Synthesis Christoph Gütz, Andreas
Stenglein, and Siegfried R. Waldvogel Organic Process Research Development 2017 21
(5), 771-778 DOI: 10.1021/acs.oprd.7b00123
(Digital Presentation) Operando x-Ray Emission/Absorption Spectroscopy to Characterize Electronic Structure Changes of Transition Metals in Lithium-Ion Batteries
Authors: Krishnan Abiram , Lee Dong-Chan , Read Ethan , Ahsan Sumaiyatul , Slagle Ian , Alamgir Faisal M. 
Published: September 2023

Demand for high-performance rechargeable batteries has driven the development of novel electrodes with high reversibility and energy density. Tracking the change in electronic and local structure is crucial to investigate and improve the stability and performance of these batteries. Advanced characterization techniques allow the user to monitor electronic and local atomic structure changes to better understand the role and behavior of different elements during cycling of electrode material for rechargeable batteries.
X-ray Absorption and Emission Spectroscopy allow us to explore such changes in 3d transition metal elements through the process of generation and quenching of core holes in the sample. Operando measurements enable real-time monitoring of electronic structure changes in electrode materials which enable us to capture phenomena which are only kinetically accessible.
In this study, the change in electronic structure of transition metals present in electrode materials is explored as a function of lithium removal through XES Kβ1,3feature along with K-edge XAFS using a lab-scale instrument. The choice of electrodes explored in this study considers the degree of oxidation, structure, and mechanism for ion storage. Change in peak and edge positions of Kβ1,3and K-edge feature is utilized to monitor oxidation/spin changes in electrode materials during charge/discharge. Further the magnetic behavior for ex-situ samples prepared by electrochemical delithiation of LCO in the range of 2-10% delithiation is investigated using Kα and Kβ fluorescence (spin sensitive) followed by K-edge XAFS for Cobalt and Oxygen.

Figure 1
Reversible Intercalation of Protons in Tungsten Oxide Films for Multi-Transduction Sensor Applications
Authors: Schwellberger Barbosa Martin , da Silva Ranilson Angelo , Orlandi Marcelo O. 
Published: September 2023

Tungsten oxide films under electrochemical bias, can form tungsten oxide bronzes (MxWO3 with M being small cations such as H+ or Li+) featuring high electronic conductivity and change in coloration to deep blue1. This doping process occurs through the reduction of W6+, as described by the following equation:
WO3 + x H+ + xe- -> HxWO3
The bronze phase can also be formed through exposure of tungsten oxide to H2 at high temperatures (> 200 oC) or in presence of catalysts2, as described by the following equation:
WO3 + x/2 H2 -> HxWO3

Because of the significant changes in both optical and electrical proprieties of the films, electrochemical control of proton doping can be used as a strategy for the development of ion-gated transistors3,4, hydrogen sensors and smart windows5.
In this work, we report the use of thin films prepared by sol-gel synthesis using polyperoxotungstic acid (PPTA) as a precursor. We used three different types of substrates (conductive transparent fluorine-doped tin oxide (FTO) glass, Si/SiO2 patterned with Au source-drain electrodes and Interdigitated electrodes patterned on transparent glass) to study the changes of color and conductivity following the formation of the bronze in both electrochemical and dry environments. In electrochemical environment, we show that gating by ionic liquid in transistor configuration can be used to propose an iontronic sensor to detect H2 and H2O6. In dry environment, we show that simultaneous monitoring of visible light transmittance and electrical conductivity can be used a double transducer for H2 sensors6.
1 M. S. Whittingham, in Solid State Ionics, 2004, vol. 168, pp. 255–263.
2 C. C. Chan, W. C. Hsu, C. C. Chang and C. S. Hsu, Sensors and Actuators, B: Chemical, 2011, 157, 504–509.
3 M. Barbosa, X. Meng, F. Soavi, C. Santato and M. O. Orlandi, J Mater Chem C Mater, 2018, 6, 1980–1987.
4 G. V. de Oliveira Silva, A. Subramanian, X. Meng, S. Zhang, M. S. Barbosa, B. Baloukas, D. Chartrand, J. C. Gonzáles, M. O. Orlandi, F. Soavi, F. Cicoira and C. Santato, J Phys D Appl Phys,
5 G. Cai, J. Wang and P. S. Lee, Acc Chem Res, 2016, 49, 1469–1476.
6 M. S. Barbosa, R. A. da Silva, C. Santato and M. O. Orlandi, Journal of Vacuum Science & Technology A, 2022, 40, 013202.
Cu-Based Nanoneedle Array for Electrochemical Detection of Nitrate
Authors: Yang Zhengyang , Che Fanglin , Gu Zhiyong 
Published: September 2023

The extensive usage of nitrogen-based fertilizers, food preservatives and explosive chemicals in various industries has led to the accumulation of nitrate in the ecosystems, especially in soil and water bodies. Several severe environmental and human health issues, including eutrophication, diseases related to N-nitroso compounds (such as Cancer, Parkinson and Gastritis) and blue-baby syndrome (methemoglobinemia), have arisen from the excessive nitrate concentration in the environment. Consequently, various government and regulatory agencies, such as the U.S. Environmental Protection Agency (EPA), have established the maximum nitrate ion concentration in drinkable water at 44 mg/L (0.71 mM). In this context, an accurate monitoring of the level of nitrate becomes important in environmental pollution control, food, clinical analysis, and other industries. While the spectroscopy techniques are of the most use due to its high precision and low limit of detection (LOD), these methods frequently require skilled workforces and specific instrumentations to operate. The electrochemical sensors benefit from recent developments of new nanomaterials to detect nitrate with a quick response, ability of continuously monitoring, small and simple instrumentation as well as easy to use. Several studies have utilized different strategies to fabricate Cu-based nanostructures (such as nanoparticles, nanoclusters, nanowires, and single-crystals) to achieve a low LOD. However, the sensitivity that has been achieved so far is still relatively low compared to the requirements for the real sampling applications.
In this work, we utilized a one-step electrodeposition method to prepare Cu-based nano-array electrodes with high active surface sites, aiming for a fast and sensitive electrochemical detection of nitrate. The morphology of the array can be fine-tuned between nanoneedle and nanowire structures (Figure 1a and 1b). The x-ray diffraction (XRD) measurements indicate that the Cu-based nanoneedle array exhibited an abundant Cu(220) facet than the nanowire systems, which is usually associated with the active edge sites on copper (Figure 1c). The nanoneedle array was used for nitrate sensing via Cyclic Voltammetry methods which showed a sensitivity of 2.8 μA/μM*cm2, about 5-fold higher than the Cu foil control electrode (Figure 1d). The main reason of the sensitivity enhancement is that the nanoneedle structure resulted in a 30 times enrichment in the surface area compared to the Cu foil as shown in the electrochemical surface area (ECSA) measurement. Overall, our study provides a novel and convenient design of highly ordered Cu nanoneedle array structure for the sensitive electrochemical detection of nitrate.

Figure 1
Reveal the Electrical Double Layer (EDL) in Zinc Battery Electrolytes with Electrocapillarity
Authors: Shi Feifei 
Published: September 2023

The electrified interface between electrodes and electrolytes, aka, electrical double layer (EDL), resides at the heart of electrochemistry and exists universally in all electrochemical devices. It governs the kinetics and reversibility of all electrochemical processes, and predicts the interphase chemistries in advanced batteries. However, despite such importance, its understanding remains insufficient. While many theoretical models have been developed to predict EDL structure and to correlate key properties to the structures, so far there have been very rare direct experimental characterization, due to the limitations of existing techniques and the extreme elusiveness and sensitivity of the electrified interfaces.
In this talk, I will discuss a modernized high-resolution electrocapillarity method, developed in my group. Applying this reborn electrocapillarity on a bivalent electrolyte of ZnCl2 and ZnSO4, we reveal the interfacial structure of Zn ion battery electrolytes in the absence and presence of anion specific adsorption and established the abnormal potential distribution across the interface due to anion adsorption and its effect on the kinetics of Zn ion deposition chemistry.
(Invited) Next-Generation Enabling Technologies for Disease Diagnosis and Therapeutic Monitoring
Authors: Poudineh Mahla 
Published: September 2023

To enable personalized and precision medicine, it is crucial to monitor patient health status and bring information on disease-related agents and therapeutic drug molecules into the clinic. This requires new technologies to interrogate different body fluids that are rich sources of biomarkers, such as whole blood and interstitial fluid (ISF). Such technologies enable rapid, sensitive and - ultimately - real-time and continuous analysis of the clinically important biomarkers. Micro and nanofabrication and nanomaterials as well as materials chemistry and polymer and molecular engineering are crucial tools in this endeavor.
At IDEATION Lab, we apply innovative engineering solutions to advance patient health monitoring using two main technologies: Microneedles and Microfluidics. Our new transdermal biosensing technologies powered by engineered hydrogel microneedles (HMNs), aptamer probes, and in-situ metallic nanoparticle synthesis enable minimally invasive, on-needle, and real-time measurement of clinically important biomarkers in ISF. Our HMN assays expect to pave the way for the next-generation of polymeric-based wearable biosensors. We developed a real-time biosensor driven by microfluidic techniques that continuously updates specific biomolecules’ fluctuating concentration levels with picomolar sensitivity directly in whole blood. For the first time, our microfluidic assay enables measuring the dynamic changes in blood insulin which is an important knowledge gap in diabetes management. Another microfluidic technology integrated with electrochemical biosensor has been recently developed in our lab that enables cervical cancer screening at point-of-care setting.
These new advances enrich the level of information that can be collected from different body fluids and provide new means and potentials for highly accurate patient health status monitoring, thus transforming the field of personalized and precision medicine.

Figure 1
Broadband Microwave Microfluidic Spectroscopy to Capture Product Evolution in Electrosynthesis Reactions
Authors: Pawlik Jacob , Miller Samantha , Evans Sarah , Schwarz Kathleen , Orloff Nathan , Long Christian , Booth James C. , Stelson Angela 
Published: September 2023

Electrosynthesis plays an important role in chemical manufacturing with over 2 billion dollars in annual sales worldwide of products such as chlor-alkali and aluminum. Synthesis with an electrochemical driving force can afford unique chemical products that are difficult to achieve with conventional synthesis techniques. Electrosynthesis can also provide a more sustainable alternative to energy-intensive processes. For example, the most profitable electro-organic synthesis in industry is adiponitrile production, a precursor to Nylon 6,6, and the electrochemical route consumes less energy than conventional thermochemical methods. However, electrosynthesis reaction mechanisms are often complex and involve multiple biproducts that are difficult to distinguish, limiting product yield and cost efficiency. Prior work involves characterization with techniques such as NMR spectroscopy, mass spectrometry, and optical spectroscopy to understand product evolution during the reaction. These methods tend not to capture intermolecular interactions between substances, which is important for understanding the influence of the dielectric environment on reaction outcomes.
Here, we propose to analyze the dielectric environment of electrosynthesis reaction mixtures with on-chip broadband microwave microfluidic spectroscopy (MMS) from 40 kHz – 110 GHz (see attached figure). MMS has been implemented previously for capturing broadband fluid effects such as electric double layer formation, ionic conduction, ion pairing, and dipole relaxations in a single measurement. We want to use MMS to diagnose the interactions between species during an electrolysis reaction and correlate these interactions with specific electrochemical mechanisms. We plan to test our idea by analyzing a model reaction, namely the Shono oxidation of N-Boc pyrrolidine, which is a well-studied electrosynthesis reaction. The goal is to validate our method with a known electrosynthesis reaction mechanism, then extend the technique to systems with an unknown mechanism.
We performed broadband MMS of the reaction mixture at different time points to capture product evolution during the electrolysis. Then, we calibrated the resulting S-parameters and fit the data to equivalent circuit models. The equivalent circuit parameters were correlated to signatures from specific entities in the product mixture and used to develop a picture of the evolving dielectric environment. After validating our models with known literature about the Shono oxidation mechanism, we plan to extend our technique to other electrolysis reactions with unknown mechanisms. The goal is to provide a high-throughput technique for identifying key species and interactions that influence the outcome of electrolysis reactions.

Figure 1
Scenarios for Hydrogen Production from a Full-Scale Reversible Solid Oxide System with Electrolyte-Supported Stacks
Authors: Parashar Aadarsh , Braun Rob J 
Published: September 2023

Reversible solid oxide cell technology is of increasing interest and is emerging as a promising grid-flexible support system [1] with storage [2]. Among the types of cell architecture available, electrolyte-supported cells have proven to be better in terms of long-term stability and degradation of the cell, albeit sacrificing on performance as compared to anode-supported cells [3]. This makes electrolyte-supported cells better suited architecture to be used in reversible systems where higher stability is required due to the changing operating conditions in each mode. In the present work, validated cell and stack models of Nexceris electrolyte-supported cells are used to model a full-scale reversible solid oxide system designed for hydrogen production.
EIS data from symmetric button cells and polarization curves from 5cm×5cm full cells are used to validate the stack model. A net 100 kWe system in fuel cell mode is modelled with electrolyte-supported stacks from Nexceris operating at a nominal temperature of 800 oC. The system is run at thermoneutral conditions in electrolysis mode and at 0.5 A/cm2 in fuel cell mode to balance between efficiency and hydrogen production. The levelized cost of hydrogen production is calculated using a price-taker model with the system pumping the produced hydrogen into a natural gas/hydrogen pipeline. The effect of various parameters, such as the capacity factor of the system, the operating pressure, grid-electricity pricing, etc. - are investigated on the levelized cost of hydrogen.
[1] Guenther Glenk and Stefan Reichelstein, “Reversible Power-to-Gas systems for energy conversion and storage”, Nature Communications
13, 2010 (2022).
[2] Evan Reznicek and Robert J. Braun, “Techno-economic and off-design analysis of stand-alone, distributed-scale reversible solid oxide cell energy storage systems”, Energy Conversion and Management
175, 2018.
[3] Marco A. Buccheri, Anand Singh, and Josephine M. Hill, “Anode- versus electrolyte-supported Ni-YSZ/YSZ/Pt SOFCs: Effect of cell design on OCV, performance and carbon formation for the direct utilization of dry methane”, Journal of Power Sources 196, 2011.

Figure 1
Analysis of Interfacial Capacitance of Ni-YSZ Anode By Transient Simulation
Authors: Yashiro Keiji , Watanabe Kota , Budiman Riyan Achmad , Sato Masami , Muramatsu Mayu , Kawada Tatsuya 
Published: September 2023

An electrochemical impedance and equivalent circuit analysis are frequently used for electrochemical evaluation of SOFC cells. The impedance analysis enables to obtain the resistance and the capacitance components of the electrode reaction. The electrode resistance is directly related to the cell performance. The electrode capacitance can be sometimes give information about the active electrode reaction site. As to Ni-YSZ electrode, we've tried to elucidate the physical meaning of the capacitance [1]. However, it is not easy to clarify the physical origin of the electrode capacitance. Thus, the capacitance has not been used to evaluate the active reaction zone so far. In this study, the capacitance of Ni-YSZ interface will be simulated by calculating the chemical capacitance derived from YSZ. Then, the origin of the capacitance will be discussed through comparison with the previous studies [1].
The structural model to simulate the Ni-YSZ model cell [1] are shown in Fig. 1., which shows simplified model according to symmetry of the cell. In order to limit the electrochemical reaction zone (triple phase boundary), a virtual reaction zone was introduced. Cell conditions for the calculation are following: temperature: 765ºC; oxygen partial pressure of the air electrode: 0.21 bar;hydrogen partial pressure: 1.00 bar, and water vapor partial pressure: 0.03 bar for fuel electrode. Transient simulation was performed to obtain the chemical capacitance by an in-house code, SIMUDEL, where mixed ionic electronic conduction and oxygen nonstoichiometry were taken into consideration [2,3] using the reported conductivity data of YSZ [4].
The measured capacitance of the model cell [1] was 5×10-4 Fcm-2. On the other hand, the calculated chemical capacitance of YSZ was 2×10-3 Fcm-2. Even though the oxygen nonstoichiometry of YSZ was small, calculated chemical capacitance was much larger than the observed interfacial capacitance. These difference implies there was unknown factors to promote the response of electron in the actual Ni-YSZ interface. If a thin resistive layer was inserted between Ni and YSZ interface, the calculated chemical capacitance became smaller than that of observed. Sasaki et al. observed an incoherent interface between Ni and YSZ by TEM [5]. This kind of interface structure may be the potential cause of the complicated capacitance.
This study was partially supported by NEDO, Japan.
[1] M. Takeda, et. al., submitted to J. Electrochem. Soc.
[2] K. Terada, et. al., ECS Trans. 35(1), 923 (2011).
[3] M. Sato, et. al., Trans. Jpn. Soc. Comp. Eng. Sci. 2017, 14 (2017).
[4] J.H. Park, et. al., J. Am. Ceram.Soc.,72[8],1485-87(1989).
[5] T. Sasaki, et. al., Mater. Trans. 45(7), 2137 (2004).
Fig. 1 Schematic diagrams of the structural model to simulate the chemical capacitance of Ni-YSZ.

Figure 1