bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Enhancing Stability for Elevated Temperature CO2 Electrolysis: Insights from Catalyst Development and Impact of Carbon Protection
Authors: Rossen Alana , Daems Nick , Choukroun Daniel , Breugelmans Tom 
Published: August 2024

While most lab-scale CO2 reduction experiments are conducted at ambient temperatures (20-25°C), maintaining such low temperatures at an industrial scale will become challenging due to joule heating. In our study, we pushed the boundaries further than the already existing systems, opting for a higher temperature of 85°C for CO2 reduction. This deliberate choice was made to accentuate the deviations from ambient conditions and explore their effects on CO2 electrolyzers.
Our current emphasis at elevated temperatures focuses on catalyst development, specifically addressing stability issues induced by the increased temperature. Nevertheless, it was soon discovered that several modifications were required to the system, both in terms of cell materials and operational conditions (e.g. gaskets, pressure arrangements, GDE type, etc.) to allow stable operation at 85°C for extended duration and especially to avoid flooding. Prior research provided valuable insights into the multifaceted impacts of elevated temperatures on the electrochemical reduction of CO2, and proof they go beyond catalyst kinetics. With this in mind, we have synthesized a series of bismuth-related nano catalysts, including oxidized, metallic and carbon containing nanoparticles, and have quantitatively evaluated their activity, selectivity towards formate, and stability at 85°C. Preliminary observations suggest that catalysts without carbon exhibit high initial selectivity, but demonstrate diminished stability over a 24-hour timeframe compared to catalysts with a protective carbon layer. Specifically, we observed an initially high faradaic efficiency toward formate of 85% for commercial bismuth oxide nanoparticles, in contrast to 75% for bismuth nanoparticles with carbon. However, over a 24-hour timeframe, the carbon-free catalyst showed a 20% decrease in FE, while for the carbon-containing catalyst this drop was halved in the same timeframe.
By evaluating the role of carbon additives (e.g. their oxidation state, pore size, surface area, hydrophobicity, etc.) our results yield valuable insights into the impact of carbon additives on stability and overall performance, especially at elevated temperature. These findings uncovered critical aspects for catalyst design, providing essential knowledge for future larger-scale applications. Moreover, we shed light on the required advancements and remaining challenges for elevated temperature CO2 reduction electrolysis, which we believe will become the predominant mode of operation for CO2 electrolysis in the future.

Figure 1
Computational Analysis of Ion Clustering Statistics in Liquid Battery Electrolytes
Authors: Wang Jingyang , Xie Yujun , Kim Sang Cheol , Cohen Orion , Ophus Colin , Ercius Peter , Zheng Haimei , Cui Yi , Persson Kristin A. 
Published: August 2024

The transport properties of liquid battery electrolytes critically depend on molecular-level solvation structures of ions. In contrast to the dilute regime where the majority of counterions are sufficiently separated spatially, in global or localized high-concentrated electrolytes (HCEs) counterions tend to form superstructures such as contact-ion pairs (CIPs) or aggregates (AGGs). The presence and relative population of such superstructures can drastically change the ionic transport behavior in liquid electrolytes. We have developed a computer program [1] that can efficiently perform analysis of ion clustering statistics from molecular dynamics simulations, complementary to experimental measurements. We have successfully applied our method to various systems, including (1) a prototypical concentrated liquid electrolyte (Li:EC:DEC) [2], and (2) a series of newly developed high-entropy liquid electrolytes [3]. In both cases, we find consistent agreements between our prediction and experimentally measured nanostructures and solvation strengths. We envision that our method would be widely applicable to generic structurally disordered systems.
[1] Cohen et al., Journal of Open Source Software 8, 84 (2023)
[2] Xie and Wang et al., Science Advances 9, eadc9721 (2023)
[3] Kim and Wang et al. Nature Energy 8, 814–826 (2023)
(Invited) Smartphone-Based Nanosensors for Environmental, Food Safety, and Health Monitoring
Authors: Du Dan (Annie) 
Published: August 2024

Abstract: Biosensors are a modern engineering marvel with widespread applications across diverse areas, including healthcare, environmental monitoring, microbiology, and food safety and security. The integration of nanotechnology with biosensor technology has led to novel sensing mechanisms, significantly enhancing performance and sensing capabilities beyond the constraints of traditional methods. In our laboratory, several nanotechnology-enabled biosensors have been developed to overcome the limitations of current bioanalytical methods, particularly in terms of sensitivity, throughput, ease-of-use, and miniaturization. We have synthesized various innovative nanomaterials, such as protein cages, single-atom nanozymes, and mesoporous bimetal nanoparticles. These materials have been crucial in the fabrication of 3D printed nano-immunosensors, which are effective in detecting pesticides, food pathogens, and exposure biomarkers.
My research specifically focuses on the development of nanotechnology-enhanced biosensors that leverage these novel nanomaterials. This endeavor aims to revolutionize biosensor fabrication, with a particular emphasis on creating new, handheld devices. These devices are designed for rapid, on-site detection of molecules, offering immense potential for point-of-care diagnostics. The integration of these biosensors with smartphone technology has further opened avenues for real-time data analysis and sharing, making them invaluable tools for environmental, food safety, and health monitoring. This talk will delve into the specifics of these developments, highlighting the innovative approaches and potential impacts of smartphone-based nanosensors in various sectors.
Development of Dual-Gel System for Wearable Electrochemical Sensors
Authors: Fan Ruolan , Andrew Trisha L. 
Published: August 2024

With the innovation of materials and rapid development of wearable technology, wearable electronics—particularly textile-based systems—have broadened perspectives in health monitoring, therapy, and disease diagnosis.
Bioelectronics interpret analyte information into real-time electrical signals with high sensitivity. Realizing the selective detection of analytes in biofluids often requires bioreceptors, such as enzymes, antibodies, and DNA, along with corresponding electrochemical detection techniques.
Enzymatic sensors have relatively complex sensing structures among others. Enzymes function as biocatalysts at the sensing interface, facilitating electron transfer from analytes to the electrode surface. To enhance overall data acquisition, redox mediators are typically incorporated into these systems.
Wearable bioelectronics are currently fabricated by depositing functional materials onto conformal flexible substrates using techniques such as spin coating, spray coating, printing, etching, and other technologies. However, seamlessly integrating multi-layer textile-based biosensors necessitates specific screen mesh and inkjet angles that ultimately limit the manufacturing process.
Here, we propose a dual-gel system consisting of a base gel embedding functional materials (redox mediators and bioreceptors) and an encapsulation gel to stabilize the base gel while offering antifouling properties. The thin dual-gel film is fabricated through blade-casting followed by photo-initiated Chemical Vapor Deposition (piCVD) and can seamlessly adhere to various rough fabric surfaces. Moreover, this solvent-free process largely prevents bioreceptor degradation, promising better manufacturing sustainability.
Glucose detection on flexible electrodes utilizing such a dual-gel system is exemplified as a proof-of-concept. This unique dual-gel system is expected to contribute to the development of textile-based electronics with greater versatility and improved sensing performance.
Gas Phase Aldehydes Detection in Exhaled Breath in Screening of Barrett's Esophagus
Authors: Rafiee Mohammad , Hejazi Reza , Nikzad Nastaran 
Published: August 2024

Aldehydes, e.g., acetaldehyde, have been classified as toxic and carcinogenic volatile organic compounds (VOCs) and are recognized as one determinant of upper aerodigestive tract cancer like Barrett's esophagus. Measuring aldehyde levels in breath provides information about the aldehydes released by abnormal cells, the level of aldehyde dehydrogenase (ALDH2) activity, and risks and diseases associated with high levels of acetaldehyde, which include liver disease and lung and upper digestive cancers. Devices currently available for breath analysis are state-of-the-art, high-resolution mass spectrometry instruments. These instruments have some drawbacks such as size, initial cost, and operational expense. Electrochemical sensors are capable of miniaturization and are available as portable and handheld breathalyzers. The non-invasive nature of breath analysis and its easy sampling makes smaller devices a more attractive alternative, particularly for continuous monitoring and point-of-care (POC) testing.1 However, the lack of an exchangeable/disposable sensing element, the resulting memory effect, and the need for frequent recalibration is the main drawback of currently available electrochemical breathalyzers.
Herein we examine the feasibility of a POC testing device for aldehyde in exhaled breath to assess the medical application of such a device in noninvasive diagnostic testing for Barrett’s esophagus. To improve the selectivity of the method we harness the unique catalytic activity of the aminoxyl radical/oxoammonium redox couple toward aldehyde oxidation. The highly selective/sensitive device offers the capability for use in the detection of Barrett's esophagus, ideally at early stages, without the need for a high-cost screening test. Our functional sensing element consists of a screen-printed electrode (SPE) in which the graphene oxide-based is the working electrode. Exposing this electrode to simulated breath that contains aldehyde, while applying the required potential for oxidation of the aminoxyl radical (4-acetamido-TEMPO known as ACT), generates an electrocatalytic current proportional to the aldehyde concentration in the breath. These simple, sensitive, durable, and inexpensive electrodes may contribute to the development of a single-use reliable aldehyde sensor for personal or law enforcement applications.
1. M. Mayer, M. Rafiee, Electrocatalytic Detection of Ethanol and Acetaldehyde by Aminoxyl Radicals: Utilizing Molecular Catalysis for Breath Analysis. Analyst 147, 2022, 3420 – 3423.
Development of an Electrochemical Biosensor for GFAP with Carbon-Based Substrate for Traumatic Brain Injury
Authors: Santana Alicea Dasairy L , Vazquez Yolimar , Cunci Lisandro 
Published: August 2024

This study concentrates on creating an electrochemical biosensor designed for the real-time identification and monitoring of biomarkers, specifically Glial Fibrillary Acidis Protein (GFAP). The intended applications involve the diagnosis and prognosis of Traumatic Brain Injury (TBI). TBIs pose a significant global health challenge, impacting millions each year, and existing diagnostic methods, such as neuroimaging, face constraints related to cost, radiation exposure and a greater delay in providing a diagnosis. The suggested biosensor exploits electrochemical techniques, offering benefits such as non-invasiveness and swift results. The primary objective is to advance wearable microelectrodes for TBI detection, with an emphasis on utilizing bodily fluids like sweat as practical samples. Moreover, the biosensor's versatility makes it well-suited for various environments, including extreme conditions.
The objective of this research is to enhance the precision of TBI diagnosis and prognosis, thereby ultimately improving the efficacy of point-of-care treatment. Our methodology involves the utilization of the Capture Systematic Evolution of Ligands by Exponential Enrichment (Capture-SELEX) technique to create a highly specific aptamer designed for the detection of Glial Fibrillary Acidic Protein. The biosensor we are developing will feature electrodes modified with aptamers and a carbon-based substrate, enabling continuous real-time monitoring of the target substance. The primary objective of our biosensor is to identify GFAP, thereby reducing risks associated with exposure to radiation, and healthcare costs. To ensure the long-term stability of our biosensor, our design centers around a carbon-based substrate. Carbon-based nanomaterials have garnered significant attention in biosensor applications due to their diverse range of properties, encompassing chemical stability, biocompatibility, functionalization, and biodegradability.
Bismuth Oxychloride Nanoflakes Based Wearable Colorimetric Sensors for Efficient Monitoring of UV Exposure
Authors: Ramaiyan Kannan , Troche Kyle , Boyle Timothy J , Garzon Fernando H. 
Published: August 2024

Ultraviolet radiation from sunlight is essential for human health in many ways such as facilitating vitamin D synthesis while excessive exposure can cause adverse effects such as premature aging, sunburn, and skin cancers. In the USA, between 2007 and 2011, nearly five million adults were treated for skin cancer annually with average treatment costs of $8.1 billion each year. Hence, monitoring daily exposure to sunlight is essential to avoid developing health risks. Colorimetric UV sensors change color as a function of UV exposure, provide onsite information about the level of exposure, and can act as a personal wearable device to assist in making informed decisions on sunlight exposure. These sensors utilize radiation-induced reactions on a dye to produce a color change. We developed a BiOCl based wearable UV sensor for monitoring UV exposure where a white-to-black color transformation is induced due to the creation of oxygen vacancies in BiOCl. This color transformation is not quantifiable in bulk BiOCl; hence BiOCl was purposely dispersed on filter paper to form petal-like nanostructures that help quantify the color change. Four different dye molecules, 6-carboxyfluorescein, 5-carboxyfluorescein, rhodamine-B, and Prussian blue were evaluated, where 6-carboxyfluorescein gave the best color contrast. The sensor responds to UVA, UVB, and UVC and with proper UV filters can be made selective for specific UV radiations. This unique colorimetric UV sensor can help manage personal UV exposure and reduce the risk of sun exposure ailments.
Reference:

Kyle Troche, Kannan Ramaiyan, Timothy J. Boyle, Fernando H. Garzon, “Bismuth Oxychloride Nanoflakes Enabled High Sensitivity Colorimetric UV Dosimetry” ACS Appl. Nano. Mater. 2023, 6, 7.
(Invited) Empowering Clean Energy Manufacturers with Low-Temperature Plasma: A Novel Approach to Real-Time Thin Film Metrology
Authors: O'Leary Jared 
Published: August 2024

Thin films, or micro- and nano-scale materials with unique functional properties, enable many clean energy industries, such as lithium-ion batteries, solar cells, and carbon conversion. Minimal-waste manufacturing of high-performance thin films will be vital for achieving society’s net-zero carbon emission goals. Because existing thin film sensors cannot operate within most sections of manufacturing lines, manufacturers often complete hundreds of processing steps before they can test (a small portion of) their products and detect problems. Current thin-film manufacturing thus often yields many low-quality products, or off-spec products that must be discarded. A real-time, in-situ metrology strategy can create unprecedented opportunities for implementation of smart manufacturing practices and advanced process control solutions to realize higher thin film throughput and performance.
SirenOpt has developed a real-time low-temperature plasma-based thin film metrology sensor. The sensor is compact, can be integrated within existing manufacturing lines, and can collect multiple thin film property measurements (such as thickness with a precision of 1/10th of a nanometer, density, resistivity, chemical composition, and contaminate identification) in parallel and in real-time, thus allowing for the collection of critical manufacturing data that is otherwise unobtainable. SirenOpt is currently applying the sensor to industrial thin film coating processes such as Lithium-ion battery electrodes, where this flexible sensor can be used to accelerate R&D and process optimization, improve quality control, and enable real-time process control.
(Invited) Probing Local Ion Insertion through Operando AFM
Authors: Tsai Wan-Yu , Balke Nina 
Published: August 2024

Electrode volume change during ion insertion or intercalation has been one of the main failure mechanisms for several energy storage devices, especially Li-based batteries. Fundamental understanding of the relationship between the amount of the ions/charge stored and the induced volume changes of the hosting electrodes, and how this relationship impact the materials’ performance are necessary to develop the next generation batteries. However, most of the studies on the volume change were based on bulk techniques, which study the entire electrode including binders and additives. Here, we use operando atomic force microscopy (AFM), which allows tracking local volume changes and other mechanical responses with sub-nanometer spatial resolution under the conditions close to the device operation.
In this work, we monitored electrode volume change via operando AFM and demonstrated the electro-chemo-mechanical coupling behaviors during proton insertion into WO3 materials. The concept of mechanical cyclic voltammetry (mCV) curves was developed, and the relationship between electrochemical current and strain was investigated with simplified models. The results revealed multiple ion-intercalation processes with different mechanical responses are involved during electrode cycling. Local heterogeneity was investigated via mCV mapping, confirming that the charging mechanisms varied across the electrode. These local variations could be further correlated to local morphology, crystal orientations, or chemical compositions. We further demonstrate that the mCV approach is applicable to a variety of energy storage materials (e.g., birnessite, MXene and metal nitrides) with the increasing complexity of current-deformation relationships.
Numerical Modelling of Nanopores
Authors: Gyasi Agyemang Eugene 
Published: August 2024

Nanopores are used for resistive pulse sensing of single analytes and as nanopipette probes for electrochemical scanned probe microscopy. The current-voltage responses of nanopores display a rich range of behaviors, which arise due to interactions between the electric fields (applied potential and surface charges), ion concentrations, and fluid flows.1 To understand these behaviors and interpret experimental results, numerical simulation of the coupled physics are typically performed.2 Yet despite simulations of conical nanopores being commonplace, they remain challenging. As the electric double layer requires resolution of concentrations and electric fields at sub-nm length scales, while concentration enhancements and depletions occur 10s of μm inside the pore simulations must resolve differences over length scales that vary by ~5 orders of magnitude. While various strategies have been employed to make these simulations more manageable including simulating a small portion of the pore, ignoring surface charge beyond a certain distance [others]. However, no consensus exists as to best practices or the impact of these simplifications.
In this work we assess the impact of commonly made simplifications and describe best practices for efficient modelling of conical nanopores to ensure accurate results are readily obtained. Suggestions include effective choices of mesh, initial conditions, and the handling of semi-infinite boundaries.
(1) Lan, W.-J.; Holden, D. A.; White, H. S. Pressure-Dependent Ion Current Rectification in Conical-Shaped Glass Nanopores. J. Am. Chem. Soc. 2011, 133 (34), 13300–13303. https://doi.org/10.1021/ja205773a.
(2) White, H. S.; Bund, A. Ion Current Rectification at Nanopores in Glass Membranes. Langmuir 2008, 24 (5), 2212–2218. https://doi.org/10.1021/la702955k.
(General Student Poster Award Winner, 3rd Place)
Lithium Niobate Coatings on Lithium Iron Phosphate Cathode Materials for Applications in Lithium-Ion Batteries
Authors: Gee Carol-Lynn , Dunn Devon , Gates Byron D. 
Published: August 2024

Lithium-ion batteries have become a crucial tool in countering global fossil fuel reliance; when paired with electric motors, they provide an alternative to petroleum-based energy storage for internal combustion engines. Typical cathode materials used in lithium-ion batteries present a unique set of challenges. Some of the electrochemical materials that have a relatively high performance also have serious impacts on the environment and human health.1 Other materials that lack these specific drawbacks, such as lithium iron phosphate (LFP), face other issues. For example, LFP suffers from a relatively low electrical conductivity and a relatively slow lithium-ion diffusion, both of which affect the general electrochemical performance of this material. These weaknesses can be addressed using coatings applied to LFP nanoparticles. Carbon coatings have already been shown to improve the performance of LFP nanoparticles, but materials with higher ionic conductivities have remained relatively undeveloped.2 By synthesizing a composite coating of both carbon and lithium niobate, further improvements to LFP nanoparticles were sought to enable a wider range of applications for this cathode material.
In this work, lithium niobate coatings on carbon coated LFP nanoparticles were synthesized using a low temperature solvothermal method. Lithium niobate coatings have been shown to improve the specific capacity, rate capability, and durability of other cathode materials for lithium-ion batteries.3 Half-cells were fabricated to examine the effect of adding a lithium niobate coating to the carbon coated LFP cathode materials. Electrochemical testing techniques such as galvanostatic cycling and cyclic voltammetry were used to compare the properties and performance of the composite coated LFP relative to the carbon coated LFP. The composite coatings were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. This coating method has resulted in the successful synthesis of lithium niobate coatings on carbon coated LFP nanoparticles with an observed improvement in durability.

Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Mater.
2010, 22 (3), 587–603.

Wang, J.; Sun, X. Understanding and Recent Development of Carbon Coating on LiFePO4 Cathode Materials for Lithium-Ion Batteries. Energy Environ. Sci.
2012, 5 (1), 5163–5185.

Kim, J. H.; Kim, H.; Choi, W.; Park, M.-S. Bifunctional Surface Coating of LiNbO3 on High-Ni Layered Cathode Materials for Lithium-Ion Batteries. ACS Appl. Mater. Interfaces
2020, 12 (31), 35098–35104.