bluuebunny/crossref_metadata_2025 huggingface dataset:
Ionic Liquid Membraneless Redox Flow Battery
Authors: Chaabene Nesrine , NGO Kieu , Turmine Mireille , Vivier Vincent
Published: July 2022

Today, ionic liquids are more and more present in many fields and more particularly in electrochemistry. Indeed, their physical and chemical properties are appealing and attractive. They are conductive solvents in which organic and inorganic salts can be dissolved depending on the nature of the anion and cation that make up the ionic liquid. However, only very few studies have reported their use in membraneless redox flow batteries (RFBs) for the storage of renewable energy 1, 2. The concept of membraneless redox-flow batteries was first reported by Ferrigno et al.3 in 2002, with the development of a millimeter-scale redox fuel cell based on the vanadium aqueous electrolyte solutions.

In this work, we have developed an ionic liquid membraneless RFB by using 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C2mimTFSI) as supporting electrolyte and Quinone (Q) and iron chloride (FeCl2) as electroactive species in a microfluidic system. Polarization curve and cyclic voltammetry were used to characterize the electrochemical properties as well as the performance of the microbattery. The proof-of-concept of the system has been shown with an open circuit potential of 0.6 V, obtained with both polarization curve and cyclic voltammetry, and with a current density ranging from 0.3 to 0.65 mA cm-2 for total flow rates of 10 to 20 µL min-1. As shown on fig. 1(b), a maximum of power of 40 µW cm-2 has been obtained. Such a technology is promising and performances can be enhanced by using 3D electrodes and optimizing the choice of the redox mediators (concentration, potential, etc.)

Figure 1: (a) Experimental set-up and polarization curves of the cell for a total flow rate of (b) 20 µL.min-1

References

1. Navalpotro, P.; Palma, J.; Anderson, M.; Marcilla, R., A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes. Angew. Chem. Int. Ed. Engl.
2017,
56 (41), 12460-12465.

2. Chen, R.; Bresser, D.; Saraf, M.; Gerlach, P.; Balducci, A.; Kunz, S.; Schroder, D.; Passerini, S.; Chen, J., A Comparative Review of Electrolytes for Organic-Material-Based Energy-Storage Devices Employing Solid Electrodes and Redox Fluids. ChemSusChem
2020,
13 (9), 2205-2219.

3. Ferrigno, R.; Stroock, A. D.; Clark, T. D.; Mayer, M.; Whitesides, G. M., Membraneless vanadium redox fuel cell using laminar flow. Journal of the American Chemical Society
2002,
124 (44), 12930-12931.

Figure 1
Hot Hole Utilization in Au-TiO2 and Au-C3N4-TiO2 Core-Shell Heterojunctions for High Performance Photoelectrochemical Water Splitting
Authors: Chaulagain Narendra , Rajashekhar Harshitha , Kumar Navneet , Vahidzadeh Ehsan , Alam Kazi , Shankar Karthik
Published: July 2022

Gold nanoparticles (Au NPs) coated with TiO2 shells exhibit strong localized surface plasmon resonance (LSPR) peaks at ~550-600 nm. The Au plasmons decay in femtoseconds through both interband and intraband damping processes to produce hot electron-hole pairs. These hot carriers have excess energy at room temperature which can be utilized to generate electricity or drive a chemical reaction. However, the hot carriers experience ultrafast recombination and thermal relaxation in hundreds of femtoseconds to a few picoseconds due to electron-electron scattering and collisions with phonons. A Schottky barrier heterojunction between Au and a n-type semiconductor such as TiO2 is an ideal method to separate the hot carrier pairs. In Au-TiO2 Schottky junctions, hot electrons are injected into TiO2 through thermionic emission and/or field emission before recombination and thermal equilibration, at timescales of roughly 250 fs. However the harvesting of residual hot holes in Au remains problematic partly because of the difficulty in forming Schottky junctions between Au and p-type semiconductors. The harvesting of hot holes is particularly important considering that hot holes in Au are on average, more energetic than hot electrons.

In this work, we use an innovative photoanode architecture to harvest hot holes. Our photoanode architecture consists of Au NPs coated with a thin layer of amorphous TiO2 and deposited on transparent conductive oxide (TCO)-coated glass substrates. Hot electrons are extracted from the Au into the TCO contact through the TiO2 shell. Hot holes tunnel through the TiO2 to reach the alkaline electrolyte whether they oxidize hydroxyl ions and dissolved oxygen species to generate oxygen. Another novelty is the use of a layer of graphitic carbon nitride (g-C3N4) quantum dots to pump the plasmon through exciton-to-plasmon energy transfer and increase the production of hot carriers. g-C3N4 works to enhance the plasmonic light harvesting due to the excellent overlap between the emission of g-C3N4 and the LSPR absorption band of Au. Photocurrent densities as high as 3.7 mA/cm2 were achieved under AM1.5G one sun illumination with concomitant high Faradaic efficiencies. Photoelectrochemical action spectra collected using filtered AM1.5G illumination and monochromatic LEDs revealed the prominent role of visible photons in water-splitting performed using Au-C3N4-TiO2 core-shell ternary heterojunctions. A key goal moving forward is to replace the noble metal (Au) with transition metal nitride plasmonic absorbers while sustaining the high level of photoelectrochemical performance.
ZIF-Based Metal-Organic Frameworks for Cantilever Gas Sensors
Authors: Akbari Masoud , Crivello Chiara , Graniel Octavio , Defort Martial , Basrour Skandar , Musselman Kevin , Muñoz-Rojas David
Published: July 2022

Among the different gas sensing platforms, cantilever-based sensors have attracted considerable interest in recent years thanks to their ultra-sensitivity and high-speed response. The gas sensing mechanism in a dynamic cantilever sensor is based on its resonance frequency shift upon adsorption of a gas molecule on the sensor. In order to sensitize the surface of a cantilever, a sensitive receptor material with large surface area is required. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials composed of metal ions coordinated to organic linkers. MOFs are promising for gas sensing applications as they have large surface area, rich porosity with adjustable pore size and excellent selective adsorption capability for various gasses.[1] Zeolite imidazole frameworks (ZIFs) are a class of MOFs where metals with tetrahedral coordination (i.e. Zn, Co, Fe, Cu) are the central node and the ligands are imidazolate-based organic molecules.

In this work, we developed a ZIF-based thin film for dynamic cantilever gas-sensing applications. We employed a novel atmospheric pressure spatial atomic layer deposition (AP-SALD)[2][3] technique to deposit a ZnO sacrificial layer on the silicon cantilevers. This technique allows the deposition of high-quality films at atmospheric pressure, faster than conventional ALD. The ZnO layer was then converted to a particular ZIF film with desired porosity and size, through a MOF-CVD process.[4] A gas-sensing bench setup was developed for the cantilever actuation and read-out. We present the chemical and morphological properties of the ZIF, as well as the frequency response of the sensor to various gases. The device showed reliable sensitivity to humidity, CO2 and several VOCs.

References

[1] X. F. Wang, X. Z. Song, K. M. Sun, L. Cheng, and W. Ma, “MOFs-derived porous nanomaterials for gas sensing,” Polyhedron, vol. 152, pp. 155–163, 2018.

[2] D. Muñoz-Rojas, T. Maindron, A. Esteve, F. Piallat, J. C. S. Kools, and J. M. Decams, “Speeding up the unique assets of atomic layer deposition,” Mater. Today Chem., vol. 12, pp. 96–120, 2019.

[3] K. P. Musselman, C. F. Uzoma, and M. S. Miller, “Nanomanufacturing: High-Throughput, Cost-Effective Deposition of Atomic Scale Thin Films via Atmospheric Pressure Spatial Atomic Layer Deposition,” Chem. Mater., vol. 28, no. 23, pp. 8443–8452, 2016.

[4] I. Stassen et al., “Chemical vapour deposition of zeolitic imidazolate framework thin films,” Nat. Mater., vol. 15, no. 3, pp. 304–310, 2016.
Comparison of Tenax and OV-1 Thin-Films for Microfabricated Preconcentrators
Authors: Struk Daniel , Hesketh Peter J. , Heist Christopher , Navaei Milad
Published: July 2022

Gas chromatography is a common technique for the separation and analysis of mixtures of volatile organic compounds (VOCs). In many applications, such as breath analysis and room air sampling, the concentration of analytes is so low that preconcentration is necessary to selectively trap VOCs over a longer period of time, before analysis. The goal of this project is to develop an energy efficient, compact vapor preconcentrator for air sampling. We present thin-film preconcentrators (PCF) with integrated heaters and temperature sensors that were coated with polydimethylsiloxane (OV-1), poly(2,6-diphenylphenylene oxide) (Tenax-TA) and a mixture of OV-1 and Tenax-TA. The polymer thin-films were fabricated using a dynamic coating method with 20mg/ml OV-1 in a 1:1 mixture of DCM and pentane, 10mg/ml of OV-1 and 5mg/ml of Tenax-TA in chloroform, or 20 mg/ml of Tenax-TA in chloroform.

The OV-1 and OV-1/ Tenax-TA PCFs were initially tested by connecting them to the inlet and FID of a gas chromatograph with 1 m of 50um guard column. A volume of 0.2 µl of an alkane was injected via the heated inlet 175 oC at 1 psi, after any breakthrough had passed, the GC was pressurized to 8 psi and the PCFs were heated using an integrated platinum film heater. The GC was kept at a constant temperature of 40°C during these tests while the PCF was independently heated outside of the GC oven. The adsorption ratio of these experiments is summarized in table 1. Alkanes above decane such as dodecane proved difficult to desorb, even with the integrated heater reaching temperatures of approximately 260°C.

The air sampling experiments for each PCF were performed for decane and benzene using a dynamic headspace sampling method with a constant flow of nitrogen induced by a mass flow controller at a rate of 0.3 ml/min. at a pressure of 5psi. A six-way valve connected the PCF to the GC for desorption at a pressure of 15psi, after a set period of time. Analysis with Agilent 5890GC using a 20 m Rxi-1ms column, temperature ramp from 40°C to 180°C at a rate of 20°C/min, and FID detector. The results for the headspace sampling are summarized in figure 1. For benzene the thin-films with Tenax-TA saturate much more quickly than the OV-1 film and the pure Tenax-TA film which has the lowest capacity. For decane, the thin films with Tenax-TA still saturate faster but the largest capacity was observed for the mix of OV-1 and Tenax-TA over this limited range of sampling times.

The authors would like to thank the Georgia Tech Research Institute for funding this research out of Independent Research and Development (IRAD) funds.

Figure 1
TiO2 Nanotube Integrated Microwave Resonator UV Sensor
Authors: Alijani Mahnaz , Wiltshire Ben D. , Zarifi Mohammad H. , Macak Jan M.
Published: July 2022

Ultraviolet (UV) irradiation is extensively utilized in numerous applications such as outer space communication, biological disinfection, memory storage, optoelectronic circuits, and biological analysis [1]. Excessive exposure to UV irradiation is deleterious and causes adverse health effects, for instance, premature aging and skin cancer. A rapid and highly sensitive device for the detection of UV is in great demand in various applications. Recently, planar microwave resonator sensors have demonstrated attractive and robust performance providing high sensitivity, real-time response, and low-cost fabrication process [2]. The planar microwave resonators can easily be integrated with nanostructured materials to make them sensitive to UV radiation via absorption and subsequent charge generation [3]. Among various wide bandgap metal oxides such as TiO2, ZnO, SnO2, one-dimensional TiO2 nanotubes (TNTs) are favorable in UV photodetectors as they possess, except intrinsic TiO2 properties high active surface area and their unique hollow geometry enables increased charge trapping and, a direct pathway for rapid transport of photogenerated carriers [4-6]. Therefore, the use of high aspect ratio (HAR) TNTs might offers superior sensing performance in the UV region.

In this presentation, the impact of TNT thicknesses on the UV sensitivity of the planar microwave resonator’s response will be investigated. We will demonstrate the use of a high frequency microwave resonator integrated with different thicknesses (50, 80, 100 µm) of TNT membranes. The presented work will aid in selecting an optimized thickness of TNT membranes with a large active surface-to-volume ratio to provide the highest sensitivity to UV irradiation. We expect this investigation to act as basis for expanding the use of HAR TNTs to effectively develop low-cost, easy to use and robust microwave UV sensors in a wide range of applications. Experimental details and recent results will be presented and discussed.
Identifying Hypocalcemia in Dairy Cattle By Combining 3D Printing and Paper Diagnostics
Authors: Mamaril Art Matthew , Glasco Dalton Lee , Sheelam Anjaiah , Leal Yepes Francisco A , Bell Jeffrey Gordon
Published: July 2022

Electrochemistry is a powerful technique for advancing point-of-care (POC) diagnostics due largely to its ease of use and compatibility with electronic readers that can be controlled by ubiquitous technology such as smartphones or tablets. Specifically, potentiometry, (i.e., the use of ion-selective electrodes) is well-suited for incorporation into POC devices for the following reasons: (i) it possesses high selectivity (through the incorporation of ionophores), (ii) it is multiplexable, and (iii) provides a fast response time. This talk will focus on the development of a paper-based diagnostic device for the identification of hypocalcemia in dairy cattle at the point-of-care. Hypocalcemia is a metabolic disorder resulting from a lower-than-normal concentration of calcium in the bloodstream and can lead to deleterious outcomes such as early herd removal or death. Diagnosis and treatment of hypocalcemia lead to increased expenses on dairy operations, where low-cost and rapid testing solutions are currently not commercially available. Our approach utilizes the highly reproducible and mass-production capabilities of 3D printing to fabricate sensors that can be incorporated into paper substrates, resulting in low-cost and reliable diagnostics devices.
(Digital Presentation) Super Ultra-Fast and Highly-Sensitive Non-Enzymatic Electrochemical Sensor to Detect Uric Acid By Electronic Waste to MoS2 and Functionalised MWCNT/MoS2 Coated High-Performance Aluminium Electrode
Authors: Sundeep Dola , K Varadharaj Eswaramoorthy
Published: July 2022

Electronic waste also known as (E-waste) includes used computers, televisions, refrigerators, mobile phones, laptops, electric and electronic cables and so on possess a severe threat to the society and the environment. Among the Sustainable Development Goals (SDGs) about six goals are interlinked to tackle the e-waste management stress to understand and focus on the challenge. In the present work, we report the utilization of waste aluminum cables as high-performance modified electrode to detect the uric acid in human urine. The obtained waste PVC wrapped 2mm diameter aluminum cable is peeled off, cleaned and cut in to 7 cm rod to be use as an electrode. MoS2 and Multiwalled Carbon Nanotubes (MWCNTs) doped MoS2 are separately grown on the Al rod through hydrothermal synthesis. The XRD patterns reveal that both the MoS2 and MWCNTs/MoS2 are in 1T phase structures, but the doping of MWCNTs promoted a minor phase shift and transformed to accurate 1T structure. The fundamental modes of vibration and qualitative chemical analysis are obtained from FTIR and Raman analysis. The interlaced nanosheets underlying in flower like morphology of MoS2 and MoS2/MWCNTs are clearly seen from the FESEM images which offered the high sensing ability of the sensor with a detection limit of 1.13 µM and sensitivity of 97.6 nA µM-1 with linear response (R2=0.99) within 2 seconds. The stability and reproducibility of the electrodes were determined by 15 repeated cyclic voltammetry response to 0.1M uric acid. All the detection parameters were studied in comparison with MoS2 and MWCNTs/MoS2 electrode and the later offered the superior results as mentioned. Though there are many publications on uric acid detections through nanomaterials modified standard electrodes, the present work initiates to report the non-enzymatic detection of uric acid in human urine samples by modifying the Al electrode for the e-waste. This work may pave the way towards decreasing the usage of conventional fossil carbon electrodes. The developed MWCNTs/MoS2 electrode offers a super ultra-fast and highly-Sensitive electrode that can be employed in biomedical sensing applications.

Keywords: E-waste, Aluminum rod, Modified Electrode, MoS2, MWCNTs doped MoS2

Figure 1
(Invited) Textile-based Electronic/fluidic Platforms Towards Wearable Diagnostic Sensor Systems
Authors: Gray Bonnie
Published: July 2022

The fields of flexible electronics and microfluidic-based labs-on-a-chip continue to advance, with new devices and systems-level technologies reported on a daily basis. However, much of this advancement is limited to each of these fields separately, rather than development of platforms for combining flexible electronics and microfluidics together to realize wearable sensors and sensor systems. We present new approaches for combining electronics and microfluidic devices together on wearable textile-based substrates, resulting in combined systems that are highly portable, mechanically flexible, and can be easily integrated with clothing. We develop polymer materials traditionally used for artistic designs on clothing for use as engineering materials, i.e., as the base polymer for conductive electronics that can be integrated with polymer microfluidic channels printed in the same materials. Unlike other techniques, our technologies and materials are highly compatible with clothing-based textiles, and result in non-polarizable electrodes for improved frequency response. Our platforms can be laundered, facilitating rugged wearable devices and systems for biomedical and environmental monitoring. Application areas for our flexible and wearable platforms include health care, worker safety, food safety, consumer devices, personalized medicine and biomedical and environmental monitoring. We present technologies for specific applications that include: lighting and health monitors for safety vests; heart and perspiration (pH, lactate) monitors for athletic clothing; and wearable bioelectric and biochemical monitoring.
(Digital Presentation) Fabrication and Characterization of C-MEMS Based 3-Dimensional Microelectrode Arrays for Cardiac Electrophysiological Studies
Authors: Biswas Shatavisha , Datta Arkaprava , Bhattacharyya Tarun Kanti
Published: July 2022

In-vitro examination of the electrical conduction characteristics and the beating of cardiomyocytes can be done using Microelectrode arrays(MEAs). The microelectrodes continuously monitor the electrical activity of the active cardiac cells on a microsecond timescale and presents a precise data based on that. Since the introduction of MEAs, many efforts have been made by scientists to evolve this technology by means of microfabrication. Previously, planar metallic electrodes were mostly used for this study but they could not penetrate the dead cells and reach the active cell layers. To overcome this, protruding 3-D microelectrodes were introduced that could puncture the dead tissues and reach the active cells for effective recording of cardiac electrical potentials.

The characteristics of an electrode are defined by the characteristics of the material used to develop it. In this paper, we focus on the fabrication of cylindrical 3-dimensional Glassy Carbon microelectrode arrays (MEAs) for analyzing cell preparations from cardiac tissues. In order to improve the electrical properties of the commercially available electrodes, we have used a highly conductive material for fabrication. Glassy Carbon microelectrodes were fabricated by the pyrolysis of SU-8 microelectrodes which were developed by a standard lithographic process on Silicon wafer. The ohmic nature and high conductivity of Glassy Carbon makes it a suitable material to be implemented in electrophysiological studies. Further in our work, we have performed the theoretical and structural analysis using Comsol Multiphysics 5.2 considering different geometries of microelectrodes. The skin insertion force is calculated to be 0.012N, which is much lesser than the comprehensive force (15.38N), the maximum bending force (0.885N) and the maximum buckling force (3.28N) per cylindrical microelectrode. The maximum Von Mises stress (as shown in the figure) acting at the base where it is attached to the substrate is found out to be 6.56x106 N/m2 for each cylindrical microneedle. Among all the considered geometries, it can be concluded that the fabricated cylindrical microelectrodes penetrate successfully without breaking or bending and causing minimal damage to the cardiac tissues. The slanted tip microelectrode was also favored as it’s design makes it able to easily pierce the cardiac cell layers. However, the Maximum Von Mises stress distribution showed that the stress at the tip was much higher than the Yield strength of Glassy Carbon (4Gpa) making it evident that the tip might break while penetrating. With the theoretical and simulation analysis performed we were thus able to optimize the geometry and establish that Glassy Carbon proves to be a good material for fabrication of 3D microelectrode arrays.

Figure 1
Low-Cost ITO Microelectrodes for Bio-Sensing and Impedance Based Cellular Assays
Authors: Kappalakandy Valapil Karthika , Szymon Filipiak Marcin , Rekiel Weronika , Jönsson-Niedziółka Martin , Witkowska Nery Emilia
Published: July 2022

Excellent electronic and optical properties make Indium tin oxide (ITO) an attractive electrode substrate.1 It is an alloy of indium oxide (In2O3) and tin oxide (SnO2) in a weight ratio of 90:10. It is transparent as thin film, so, it is also good to be viewed under different types of microscopes used in cell-culture studies. Despite the commercial availability of finest quality ITO and some low-cost methods for direct deposition being in use by now, definition of patterns on them is still a concern. Placing its popularity and extensive usage aside, the manufacturing of ITO electrodes so far lacks a rapid, proficient, highly reproducible, flexible, cost-effective, easy patterning process that could surpass non-trivial, time consuming techniques as lithography. A promising advancement towards achieving these limitations was the use of lasers for the fabrication of the ITO electrodes and related structure. Even though several laser techniques are explored, with the exception of CO2 lasers, none of the others provides the benefit of being widely available and comparatively inexpensive means for fabrication of microelectrode sensors. Presently, these are the highest-power continuous wave lasers available. With their high efficiency, they are usually employed in laser cutting, welding, drilling and surface treatment.2

A cost-effective method based on CO2 laser irradiation for the preparation of ITO microelectrodes to find applications in the bio-sensing, impedance-based analysis, and more, is presented. Electrodes of different sizes and shapes were examined to identify the performance of the samples. They were later optimized to suit our applications for studies in three dimensional cell-cultures. For rectangular shaped electrodes, the smallest sizes optimized were 25, 50 and 100 µm wide. The figure attached shows cyclic voltammetry results illustrating the reproducibility of 100 µm electrodes with ferrocenedimethanol as the redox probe in potassium nitrate. However, smaller electrodes are not always desirable. For the cell-culture work, electrodes with area 1.75mm2 were fabricated and characterized to get reproducible results. Initial measurements of impedance based cellular assays have been conducted first in DMEM medium and then in the cell culture medium to understand the parameters and study the adhesion of the cells on to the electrodes. Analysis of glucose sensing properties of the system have also been attempted. Further modifications of the electrode structure and characterizations for validation will be discussed.

References

Stadler A. et al. J.Materials,
2012, 5, 661-683

Wang Y. et al. J Energy Chem. 2021, 59, 642-665

Figure 1
(Invited) Nanomaterial-Based Electrochemical Sensors for the Detection of Pharmaceutical Compounds
Authors: Chen Aicheng , Qian Lanting , Tavana Babak , Durairaj Sharmila
Published: July 2022

The surging growth of the pharmaceutical industry is a result of the rapidly increasing human population, which has inevitably led to new biomedical and environmental issues. Aside from the quality control of pharmaceutical production and drug delivery, there is an urgent need for precise, sensitive, portable, and cost-effective technologies to track patient overdosing and to monitor ambient water sources and wastewater for pharmaceutical pollutants. The development of advanced nanomaterial-based electrochemical sensors for the detection of pharmaceutical compounds has garnered immense attention due to their advantages, such as high sensitivity and selectivity, real-time monitoring, and ease of use. Recently, my research team has designed and fabricated a variety of functional nanomaterials and nanocomposites. In this talk, the synthesis of nanoporous gold and the development of graphene-based nanomaterials as well as their promising applications in electrochemical sensing of different pharmaceutical compounds (e.g., acetaminophen, naproxen and isoniazid) are presented. The design rationale and the performance of the proposed electrochemical sensors are highlighted.
SAW-Based Differential Sensor Exploiting Metallocorroles Properties for Selective CO Measurement
Authors: Vanotti Meddy , Poisson Sacha , André Laurie , Brandès Stéphane , Desbois Nicolas , Gros Claude , Blondeau-Patissier Virginie
Published: July 2022

During the last decades, the potential impact of indoor air quality on human health has stimulated an interest in hazardous compounds survey, such as carbon monoxide (CO). The detection of these compounds has consequently become a vital need. To address this issue, we propose a Surface Acoustic Wave (SAW) device functionalized with metallocorroles used for the selective detection of CO.

Here, we insist on the necessity to detect CO in the presence of interferents, such as O2 that is obviously present in the air, carbon dioxide (CO2) present in significant quantity in urban area (400 ppm) and humidity (H2O) which is a well-known interferent in the case of SAW-based gas sensors.

We will report on the interest of a differential configuration of the sensor that takes advantage of accurate organic layers, to improve the stability of the sensor’s signal and lower the sensitivity to interferents.

Acknowledgments: this work was supported by the PIA-Excellence ISITE-BFC (CoMICS program 2019-2022: Chemistry of Molecular Interactions - Catalysis and Sensors) and the ISITE CO2DECIN.

REFERENCES: [1] Di Natale, C.; Gros, C. P.; Paolesse, R., Chem. Soc. Rev.
2022, 000;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans.
2004, 1208-1214; [3] Vanotti, M.; Poisson, S.; Soumann, V.; Quesneau, V.; Brandes, S.; Desbois, N.; Yang, J.; Andre, L.; Gros, C. P.; Blondeau-Patissier, V., Sensors and Actuators B: Chemical
2021, (332), 129507. [4] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans. 2019, 48, 11651-11662 (Front Cover).

Fig. 1.Double delay line SAW-based CO sensor (left) and Open-loop phase measurement (Right)

Figure 1
Solubility Trends in Pyridinium Salts for Non-Aqueous Organic Redox Flow Batteries
Authors: Samaroo Sharmila , Hengesbach Charley , Bruggeman Chase , Mtemeri Lincoln , Guarr Thomas F. , Hickey David
Published: July 2022

Redox flow batteries (RFBs) are a strong candidate for grid-scale energy storage applications. Recent pursuits for chemical systems involve focus on organic species, due to their chemical abundance, and non-aqueous solvent systems, due to an expanded electrochemical stability window. Currently, RFBs suffer from limitations that prevent them from being economically competitive when scaled. Among the critical properties hindering RFB expansion, one limitation is low system energy densities. The energy density of a RFB system is dependent on voltage, electrons transferred, and concentration of the anolyte and catholyte. Electrolyte advancements have focused on optimizing energy density by targeting species that maximize divergence of anolyte/catholyte redox potentials, increase species solubility, and feature reversible multi-electron transfer. Strategic structural engineering of redox-active materials is necessary to tune these distinct qualities. Understanding the relationship between molecular design and these variables, and then developing strategies to predict structures with optimal characteristics could help identify promising electrolyte candidates. Our work is focused on understanding and predicting the solubility trends of pyridinium anolyte materials. The pyridiniums in this series all feature low reduction potentials and a broad range of solubility in acetonitrile. By carefully aligning experimental data to DFT and other modeled parameters we are investigating the predictive parameters involved in controlling electrolyte solubility.
Towards a Mechanistic Explanation for Solid Electrolyte Interphase Formation in Lithium-Ion Batteries
Authors: Spotte-Smith Evan Walter Clark , Kam Ronald L , Barter Daniel , Self Julian , Xie Xiaowei , Hou Tingzheng , Dwaraknath Shyam , Blau Samuel M , Persson Kristin A.
Published: July 2022

The solid electrolyte interphase (SEI), a nanoscale passivation film formed by reductive electrolyte decomposition during initial battery charging, is a key component of lithium-ion batteries (LIBs). When properly formed, an SEI layer allows ion mobility and prevents further degradation of the battery anode and electrolyte. Despite the essential protective role of the SEI and its importance in promoting reversible cycling in LIBs, the mechanisms underlying SEI formation remain poorly understood. In this work, we use first-principles quantum chemical calculations and stochastic methods to directly model mechanistic reactive competition during SEI formation for the first time. Our simulations, which are general to any LIB with an ethylene carbonate (EC)-based electrolyte, suggest that the separation of the SEI into primarily inorganic and primarily organic layers arises due to reductive decomposition of major organic products near the electrode interface. By varying the initial quantities of water and carbon dioxide, we also explore the role of impurity species in SEI formation. We validate that water is critical to the formation of lithium ethylene monocarbonate (LEMC) and could promote the formation of the postulated dilithium ethylene monocarbonate (DLEMC). Further, we observe that carbon dioxide reduction can compete with EC reduction, leading to downstream competition between organic carbonates, inorganic carbonates, and lithium oxalate. In addition to furnishing fundamental insights into the complex chemistry of the SEI, these findings provide a roadmap for future mechanistic studies of SEI formation in LIBs as well as next-generation batteries.
Development of Reversible Ni-Fe Metal Supported Solid Oxide Cells
Authors: Park Dayoung , Kang Dahee , Myung Jaeha
Published: July 2022

Reversible Solid Oxide Cells (RSOCs) are bi-functional energy conversion devices for generating electricity and producing fuels (H2 and CO) with high efficiency and fuel flexibility. Conventional ceramic supported RSOCs have limitations in commercialization due to mechanical issue, so a metal support with thermomechanical stability has been proposed. Thermal expansion coefficient (TEC), conductivity and diffusion behavior of metal support can be simply adjusted by composition control. Herein, we maximized the electrical, chemical and contact properties of the Ni-Fe metal support by controlling the Fe2O3 contents to 10-90 wt% (10 NiFe, 50 NiFe, and 90 NiFe). 50NiFe showed high electrical conductivity and low Fe diffusion into the functional layer based on high alloy content. In addition, good contact was obtained without structural defects due to the appropriate TEC difference with the other components. 50 NiFe | Ni-YSZ | ScSZ | LSM-ScSZ single cell showed excellent performance with maximum power density of 2.4 W cm-2 in 3%H2O/H2 in fuel cell mode and a current density of 2 A cm-2 at 1.4 V in 50%H2O/H2 in electrolysis cell mode at 800oC. The electrochemical performance of the cell shows stable operation during 30 cycles electrolysis cell/fuel cell for 5 hours. The results demonstrate the potential for commercialization of long-lasting high performance and cost-efficient RSOCs in a broad range of fields.
Electrochemically Deposited Tin on High Surface Area Copper Foam for Enhanced Electrochemical Reduction of CO2 to Formic Acid
Authors: Yadavalli SIVA RAM PRASAD , Chandiran Aravind Kumar , Chetty Raghuram
Published: July 2022

Conversion of CO2 into valuable chemicals and fuels has received widespread attention as a way to tackle the increased CO2 emissions (Gattrell, Gupta and Co, 2006) and this also resulted in a reduction of dependence on fossil fuels . There are different techniques for CO2 conversion to value-added products, where electrochemical reduction (ECR) of carbon dioxide into chemical fuels is identified as a promising way since energy efficiency is high and the products, especially the chemical fuels can be readily stored. Among the variety of metallic electrodes, especially transition metals investigated for activity towards ECR of CO2, tin (Sn), bismuth (Bi), Indium (In) were found to be selective towards formic acid production. However, it was found that these metals show a low catalytic activity.

To enhance the performance of CO2 reduction, three dimensional (3D) porous foam structured catalysts can be employed by increasing the active surface area. These 3D porous foam structures of metallic catalyst can be achieved by electrodeposition process by tuning the deposition parameters such that the evolving hydrogen during deposition can act as a dynamic template to fabricate 3D metal deposit structures with high surface areas (Shin, Dong and Liu, 2003).

In this work, a 3D foam of copper is electrochemically deposited onto Cu foil (f-Cu) and Cu mesh (f-Cu mesh). Further, the deposition parameters for the electrodeposition of Sn on 3D Cu foam (Sn/f-Cu) were optimized to investigate the activity towards the ECR of CO2. SEM and EDX technique were employed for the physical characterization of the electrodes, while the produced formic acid from the reactions was quantified using ion chromatography. The results indicated that Sn/f-Cu mesh electrode showed better performance for ECR of CO2 to formic acid compared to Sn deposited copper foil (Sn/Cu) and bare copper foam. It was observed that Sn/f-Cu mesh achieved 83 % maximum faradaic efficiency at -1.6 V vs Ag/AgCl. However, a highest rate of formic acid production of 350 µmol/hr.cm2 was achieved at -1.8 V vs Ag/AgCl which is nearly seven times higher than Sn/Cu at the same potential. A similar analysis is going to be performed with the other formic acid selective catalysts like Bi/f-Cu mesh and In/f-Cu mesh. Based on the above analysis on faradaic efficiency against various electrodes, an optimized electrode will be identified and used in scaled-up electrolyser for CO2 reduction.

References

Gattrell, M., Gupta, N. and Co, A. (2006) ‘A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper’, Journal of Electroanalytical Chemistry, pp. 1–19. doi: 10.1016/j.jelechem.2006.05.013.

Shin, H. C., Dong, J. and Liu, M. (2003) ‘Nanoporous Structures Prepared by an Electrochemical Deposition Process’, Advanced Materials, 15(19), pp. 1610–1614. doi: 10.1002/adma.200305160.
Alginate/Polyethyleneimine-Based Nitric Oxide-Releasing Hydrogel As a Potential Platform to Study the Effects of NO on Carcinogenesis
Authors: Maher Shaimaa , Kalil Haitham , Bayachou Mekki
Published: July 2022

Numerous biological functions are affected by the functions of nitric oxide (NO), such as cell proliferation and programmed cell death. NOis a ubiquitous free radical gas that exerts a wide range of biological effects and acts as a signaling molecule in the body. Recent studies have indicated that nitric oxide regulates multiple cancer-related processes, such as angiogenesis, apoptosis, cell cycle, invasion, and metastasis. Alternatively, it is also emerging as a potential anti-oncogenic agent under other conditions. Nitric oxide is synthesized by a complex family of nitric oxide synthase (NOS) enzymes. There is encouraging interest in developing NO-releasing materials as potent tumoricidal agents in which high and localized concentrations of NO may be directly released in a sustained manner to the tumor site. The goal of this project is to develop a hydrogel that incorporates inducible nitric oxide synthase (iNOS) using a layer-by-layer building strategy to form layers of polyethyleneimine (PEI) and iNOSoxy as NO-releasing coatings on alginate hydrogel. When the hydrogel coated with PEI/iNOSoxy films are exposed to arginine, a source of reducing equivalents, and other required ingredients, nitric oxide is formed and released. In this work, FTIR spectroscopy was employed to characterize the functional groups of pristine sodium alginate (SA), polyethyleneimine (PEI) and SA/PEI composite hydrogels. We also used scanning electron microscopy (SEM) for surface characterization. Cyclic voltammetry was used to determine the amount of electroactive heme-enzyme adsorbed on the modified surfaces. We examine how the electroactive heme enzyme in the thin films correlates with the enzymatic NOS activity in terms of NO release fluxes from PEI/NOS-coated hydrogels. After the structural characterization of the NOS/hydrogel films using spectroscopy, we examined their function in terms of NO release profiles. We observed an initial “burst” of NO release during the first 4 hours of activity, followed by a decline and then stable NO release for up to 144 hours possibility to interrogate the role of NO on the balance of cell proliferation and cell death in these cell lines. The measured fluxes are higher than what have been reported in the literature for other inorganic NO-releasing systems. This data will allow us to build NOS-alginate hydrogels with defined NO release profiles for application in cell biology to test the effect of sustained NO release on cell proliferation and cell death on specific cancer cell lines.
(Invited, Digital Presentation) Sustainable Recycling of Spent Lithium Ion Batteries
Authors: Li Li , Fan Ersha , Wu Feng , Chen Renjie
Published: July 2022

As attractive energy storage technologies to integrate renewable resources and electric transportation, lithium-ion batteries are undergoing unprecedented rapid development. However, the intrinsic toxicity of rechargeable batteries arising from their use of toxic materials is potentially environmentally hazardous. Here, we provide a systematic overview of lithium-ion batteries recycling from a sustainable perspective. New challenges and future prospects for battery sustainability are also highlighted.We present state-of-the-art fundamental research and industrial technologies related to battery recycling, with a special focus on lithium-ion battery recycling. Finally, 4H strategy for battery recycling with the aims of high efficiency, high economic return, high environmental benefit, and high safety are proposed.
Electrochemical Processes Role in the Drive for Industrial Decarbonization
Authors: Palou-Rivera Ignasi , Grieco William
Published: July 2022

Manufacturers are increasingly focused on meeting sustainability targets by decarbonizing their processes. Process electrification, exploiting the increasing amount of renewable power, is emerging as a viable tool for decarbonizing the chemical process industries (CPI). Electrochemical processing, together with process heating, and supported by electrical energy storage represent the key opportunities for innovation in process electrification.

Electrochemical processing, using electrochemistry in place of or alongside traditional thermochemical or biochemical production methods, is already commonly used to produce aluminum, adiponitrile, chlorine, and caustic soda. Electrolysis is also used to produce hydrogen as a more sustainable alternative to steam methane reforming. Despite these commercial applications, electrochemical processing has not been applied broadly across the CPI due in part to slow development of electrodes, complex requirements for electrochemical cell fabrication and operation, and high capital and operating costs. However, spending on research and development in this area is increasing. Electrochemical reduction of carbon dioxide to C1 compounds (e.g., carbon monoxide, formic acid, and methanol) is demonstrated and scalable, and applied research on cell development for the production of C2 and higher compounds (e.g, ethylene, propylene, dimethyl ether, etc.) is accelerating. Development efforts must focus on demonstration of these process technologies at scale and over a range of operating conditions and feedstock qualities.

Options for the future should include factory-produced, standardized modular platforms that enable cost-effective electrolysis. These platforms could become a mainstream process for distributed hydrogen production, a key requirement for carbon dioxide utilization. Similarly, electrochemical processing modules with various cell configurations could enable distributed carbon dioxide upgrading to C1 and higher compounds. Each of these cases will require development and demonstration of more efficient electromagnetic power sources and more robust electrode and membrane materials.
Developing New Quinone Based Electrodes for Electrochemical Carbon Capture
Authors: Hartley Niamh A , Pugh Suzi M , Jaffe Adam , Forse Alexander C.
Published: July 2022

The need for cost-effective carbon capture technology is rapidly increasing. To limit the global temperature increase to 1.5 degrees within the next century, the level of CO2 mitigation needs to be increased drastically [1]. Current technology, i.e., amine scrubbing, provides several challenges which limit their deployment: high regeneration energy, high operational costs and degradation at high temperatures [2]. An electrochemical approach avoids large energy losses and can selectively uptake CO2 by utilizing redox-active organic molecules. To compete with conventional chemical scrubbing, the electrochemical cell needs high power density, high CO2 uptake and long cycle stability. Redox-active molecules such as quinone-based molecules have been utilized in this area however suffer from low cycling stability due to organic molecules leaking into the electrolyte [3,4]. Quinone-polymer electrodes have shown a high efficiency for CO2 capture however are prone to quinone degradation and low active-material mass [5]. Here we present our work on a new class of quinone-based electrodes for electrochemical CO2 capture, and explore their electrochemistry in the presence and absence of CO2 and quantify their CO2 uptake capacities. This work paves the way for the design and discovery of improved electrode materials for electrochemical CO2 capture.

The Intergovernmental Panel on Climate Change (2018), Global Warming of 1.5 degrees. Available at: https://www.ipcc.ch/sr15/ (Accessed: 10 December 2021)

Rahimi, M., Zucchelli, F., Puccini, M. and Alan Hatton, T., 2020. Improved CO2 Capture Performance of Electrochemically Mediated Amine Regeneration Processes with Ionic Surfactant Additives. ACS Applied Energy Materials, 3(11), pp.10823-10830.

Apaydin, D., Głowacki, E., Portenkirchner, E. and Sariciftci, N., 2014. Direct Electrochemical Capture and Release of Carbon Dioxide Using an Industrial Organic Pigment: Quinacridone. Angewandte Chemie International Edition, 53(26), pp.6819-6822.

Ranjan, R., Olson, J., Singh, P., Lorance, E., Buttry, D. and Gould, I., 2015. Reversible Electrochemical Trapping of Carbon Dioxide Using 4,4′-Bipyridine That Does Not Require Thermal Activation. The Journal of Physical Chemistry Letters, 6(24), pp.4943-4946.

Voskian, S and Hatton, T., 2019. Faradaic Electro-swing Reactive Adsorption for CO2 Capture. Energy and Environmental Science, 12(12), pp.3530-3547
(Invited) Process Intensification of Electrochemical Systems for CO2 and Biomass Valorization
Authors: Perez-Gallent Elena
Published: July 2022

Valorization of CO2 and biomass waste streams via electrochemical conversions is a sustainable alternative for the production of fine chemicals and commodity chemicals. This topic has gained a lot of attention in the past decades and major research efforts have been put into it. Key advances has been achieved in the field of material development, where, novel catalysts have been synthesized, developed and have demonstrated to increase the efficiency and selectivity towards the targeted products. Relatively to the large number of studies focused on material development, limited studies are focused on process development, reactor optimization and product separation. Although material development is of paramount importance to achieve an adequate electrochemical reaction performance, it is only the first step needed in order to develop a competitive technology. Process development offers the possibility of enhancing the overall performance of the technology by looking not only at the reaction level, but finding engineering solutions to overcome critical limitations. Process development is essential in order to accelerate the technology towards its envisioned application and advance towards commercial realization. In this talk, we will present several optimization strategies (beyond material development) that helped increase the overall performance of several electrochemical conversion processes, as well as the economic profitability of the complete system.

In addition, in order to advance the technology on the TRL scale and have a positive market potential, the technology needs to be evaluated in several aspects such as the scaling-up challenges, its cost competitiveness and its climate benefits. For this, it is crucial to consider the complete value chain, and evaluate not only the electrochemical reaction but also the upstream and the downstream processes. A complete system approach is paramount for the development of competitive technologies. In this talk we will also show several examples on different process intensification strategies and its benefits on the economic potential of them.
Electrochemical Manufacturing of Hydrogen Peroixde
Authors: Wang Haotian
Published: July 2022

Electrochemcial synthesis of H2O2 from air and water represents a green and sustainable alternative to traditional chemical engineering process. Here I would like to introduce both catalytic materials design and reactor engineering in both cathodic oxygen reduction reaction and anodic water oxidation reaction for efficient generation of H2O2.