bluuebunny/crossref_metadata_2025_split huggingface dataset:
Utilizing Advanced Bipolar Membranes in Next Generation Electrodialysis Systems
Authors: Vulpin Olivia T. , Boettcher Shannon W. 
Published: August 2024

Bipolar membranes (BPMs) have experienced a renaissance, owing to their proposed use in membrane electrode assembly (MEA) systems. MEA systems encompass technologies such as fuel cells and electrolyzers, where the BPM allows for fine pH control at the electrodes and helps to prevent ion-crossover that may lead to lower system efficiencies and fouling of the system. The exploration of MEA systems has significantly expanded our fundamental understanding of BPM functionality and limits, setting the stage for future advancements in BPM applications.
Beyond MEA systems, BPMs have been seen in a wide array of technologies such as CO2 sequestration systems, electrodialysis, brine remediation, organic acid/base production, and more. These applications all present unique stressor to the BPM that prevent the direct translation of advanced, MEA optimized BPM to these non-MEA systems. Initial investigations into transferring advanced BPM to non-MEA applications have found issues with membrane delamination at scale and a need for system specific catalyst optimization. However, the fundamentals learned from MEA systems translate well and can be used to inform advancements of BPM in these non-MEA systems. Here we present initial findings and proposed solutions for durability issues when optimizing advanced BPM for application in BPM electrodialysis.
Effect of Temperature on Faradaic Efficiency and SEI Formation in Lithium Mediated Nitrogen Reduction
Authors: O'Rafferty Alden , Benedek Peter , Niemann Valerie Anne , Lee Sang-Won , Nielander Adam C. , Jaramillo Thomas F. 
Published: August 2024

Lithium-mediated nitrogen reduction (Li-N2R) can be distributed and powered by renewable energy, making it a sustainable ammonia production alternative to the Haber Bosch process. While Haber Bosch is responsible for 1.3% of CO2 emissions yearly and requires centralized facilities with high temperatures and pressures, Li-N2R works at near-ambient conditions and therefore allows for decentralized production.1 First, lithium (Li+) ions electroplate as lithium metal on the working electrode. Second, the deposited lithium reacts with N2 gas to form lithium nitride (Li3N). Lastly, Li3N reacts with a proton source to form ammonia (NH3) (Figure Right).
During Li-N2R, the NH3 selectivity is controlled through the mass transport of N2, Li+, and protons to the working electrode electrode (WE). The transport of these species is limited by the solid electrolyte interface (SEI), a passivation layer formed on top of the WE.2 The thickness and ratio of organic and inorganic species in the SEI change at different cycling temperatures, thus affecting the rates of transport between charge and uncharged species traveling to and from the electrode. Here, we study the impacts of temperature on FE and SEI composition in 1M LiBF4 in both diglyme (DG) and tetrahydrofuran (THF) with a 1v% ethanol (EtOH) proton source (Figure Left). Using ion chromatography (IC), nuclear magnetic resonance (NMR), and inductively coupled plasma mass spectrometry (ICP-MS) on the SEI dissolved in D2O, we quantify the SEI species formed at different cycling temperatures. Our correlation of temperature and SEI compositions to FE provide opportunities to engineer the SEI for improved Li-N2R FE and stability.

1J. W. Erisman et al., Nat. Geosci 2008. 1, 636–639

2K. Steinberg et al., Nat. Energy 2022, 8 (2), 138

Figure 1
A Novel Electrochemical Method to Detect HIV in Saliva
Authors: Saha Dipu , Botte Gerardine G 
Published: August 2024

Human Immunodeficiency Virus (HIV) is a global epidemic that causes acquired immunodeficiency syndrome (AIDS) with time. Approximately 14% (one in seven) of HIV-infected people do not know their HIV status till 2022 [1]. These people have a higher chance of spreading HIV without knowing its consequences. So, there is an unmet need for more HIV testing techniques to isolate and identify all HIV-infected people as soon as after their infection. Till now, there are no available techniques to detect HIV in saliva due to HIV’s low concentrations and the inhibition properties of saliva. We developed a nickel-based electrochemical method to detect HIV in saliva for the first time. This method does not require any biorecognition element for the detection, thus making it label-free. The difference in current responses during the chronoamperometry helps to distinguish HIV from saliva. It happens due to the blocking of the formation of NiOOH in the presence of HIV on the nickel surface. This method has high sensitivity and exhibits a linear current trend with increasing concentrations of HIV culture fluid. Also, it has a lower detection limit of around 50 copies/mL and a high selectivity of HIV over Epstein-Barr Virus (EBV), which is the most common co-infection for HIV patients. Also, the most common route to transmit EBV is through saliva. So, this novel method will create a new opportunity for the commercialization of non-invasive HIV testing techniques that minimize the spreading rate of HIV by fastening HIV testing.
[1] “Global HIV & AIDS statistics — Fact sheet.” Accessed: Nov. 26, 2023. [Online]. Available: https://www.unaids.org/en/resources/fact-sheet
Iron Production By Molten Sulfide Electrolysis
Authors: Suryarao Kimaya Prasad , Daehn Katrin Ellen , Allanore Antoine 
Published: August 2024

With urgency and incentives to cut CO2 emissions, alongside increasing demand for steel, there is a need for technologies that use solely electricity for iron ore reduction, eliminating the role of carbon as a reductant. Herein, we propose the electrolytic production of liquid cast iron using a novel sulfide route, molten sulfide electrolysis (MSE). The process operates using sulfide chemistry and an inert anode. Sulfides are well known from non-ferrous metallurgy1 and the exclusion of oxygen supports a virtual elimination of green-house gases(GHG) emissions from the reduction step. The electrolytic decomposition of iron sulfide into iron and elemental sulfur gas operates in a multi-component molten sulfide electrolyte. The underlying thermodynamics suggests the absence of trivalent iron species (Fe3+) in such conditions, supporting the reduction of only divalent iron (Fe2+) and reducing the energy need proportionally, as compared to other oxide-based routes. Iron sulfide deposits or tailings, as well as conventional iron oxide ores after sulfidation2 are some of the suitable feedstocks for MSE.
Both thermal only, and galvanostatic electrochemical experiments were carried out on electrolyte droplets (~200mg) in a thermal imaging furnace, to confirm the electrolytic deposition of Fe and the evolution of sulfur in a 2-electrode set-up. Faradaic efficiency estimates based on mass-loss measurements – i.e. with respect to gaseous sulfur anodic evolution – are of the order of 90%. Key electrochemical attributes of MSE to be reported include impedance measurement at various fixed DC potentials, measurements at various current densities up to 2A/cm2, and the role of the total charge passed, to highlight the potential limitations observed in such an experimental set up. Characterization of the electrochemical deposits are also presented.
References:

Daehn, Katrin & Stinn, Caspar & Rush, Lucas & Benderly-Kremen, Ethan & Wagner, Mary Elizabeth & Boury, Charles & Chmielowiec, Brian & Gutierrez, Carolina & Allanore, Antoine. (2022). Liquid Copper and Iron Production from Chalcopyrite, in the Absence of Oxygen. Metals. 12. 1440. 10.3390/met12091440.

Allanore, Antoine, and Caspar R. Stinn. "Selective sulfidation and desulfidation." U.S. Patent Application 17/134,429, filed September 9, 2021.
Lithium-Ion Battery Recycling: Ternary Deep Eutectic Solvents Enable Efficient and Selective Electrochemical Recovery of Critical Component Metals
Authors: Ashoka Sahadevan Suchithra , Usen Nazreen Mohamed Shahid , Sankarasubramanian Shrihari , Ramani Vijay K 
Published: August 2024

The growing demand for lithium-ion batteries (LIBs) in electric vehicles and energy storage systems has led to a rise in LIB waste. Efficient metal recovery from LIB waste is critical to meet the growing demand sustainably. However, traditional recycling methods, such as pyrometallurgy and hydrometallurgy, have limitations regarding energy consumption, efficiency, and environmental impact. In this work, we address these challenges by exploring the potential of Deep Eutectic Solvents (DESes) as an alternative. DESes are compounds formed by mixing hydrogen bond donors and acceptors and exhibit a high capability for metal dissolution. DES has a wide electrochemical stability window (1-2 V vs Ag), making it ideal for electrodeposition. While DES holds promise for sustainable LIB recycling, current applications are hindered by high leaching temperatures (140-220°C) and prolonged durations, extending even to days.
In this study, we investigate the physical properties of a novel ternary DES and assess its leaching capabilities alongside electrodeposition studies. The leaching efficiency (LE) of metals using ternary DES is compared to the binary DES, composed of choline chloride and ethylene glycol (1:2 ChCl: EG). For the same leaching conditions (900C, 24 hr), the leaching efficiency (LE) of metals using binary DES, is 20%, whereas the LE of metals from ternary DES is nearly 100%. We optimized the leaching conditions and investigated the leaching kinetics. The electrochemical properties of the tailored, ternary DES are explored, revealing an electrochemical window of 2-3 V vs Ag. We analyze current density–time transients using the Scharifker–Hills model for instantaneous and progressive nucleation to study the early nucleation and growth mechanism of electrodeposition. Furthermore, we perform potentiostatic electrodeposition of metals from the leach liquor on different substrates, such as copper sheet and carbon at various constant potentials (-0.7 V to -1 V vs Ag). The effect of applied potential, stability of working and counter electrodes, and growth mechanism of deposited metals are studied. The electrodeposited metals are characterized using scanning electron microscopy with energy-dispersive X-ray spectroscopy and X-ray diffraction techniques. Our findings indicate that the proposed ternary DES holds significant promise for efficient and environmentally friendly metal recovery from LIB waste, paving the way for advancements in sustainable battery recycling technologies.

Figure 1
(Invited) Electrochemical Engineering Approaches for High-Performing Electrosynthesis of Polymer Precursors
Authors: Modestino Miguel A 
Published: August 2024

The chemical industry accounts for ~5% of the US energy utilization and >30% of the US energy-derived industrial CO2 emissions. Amongst these processes, the production of organic chemical commodities, many of which are used as polymer precursors, account for the majority of the energy utilization (>1200 TBTU/y). The electrification of these processes via the implementation of electro-organic reactions could accelerate the decarbonization of the chemical industry, and bring additional sustainability advantages over their thermo-chemical counterparts. Currently, however, two major challenges prevent the deployment of electro-organic reactions: their low selectivity and their low production rates. To circumvent these barriers, our group deploys electrochemical reaction engineering principles to engineer electrode/electrolyte interfaces and design high-performing electro-organic processes. In this presentation, I will discuss how we implement this approach to understand and improve the performance of electro-organic reactions for the production of large-scale precursors for the production of Nylon 6,6 and polyethylene.
The production of Nylon 6,6 involves the step-growth polymerization of 1,6-hexanediamine (HMDA) with adipic acid. HMDA is currently produced by the hydrogenation of adiponitrile (ADN). Here, I will present our insights into the electrohydrodimerization of acrylonitrile (AN) to adiponitrile (ADN). This is one of the largest electro-organic reaction deployed in industry and serves as a model process for the development of practical organic electrochemical processes. Our investigations on ADN uncovered relationships between the microenvironment at and near the electrical double layer (EDL) and reaction performance metrics (i.e., selectivity, efficiency, and productivity). I will discuss general guidelines for electrolyte formulation, dynamic electrochemical operation, the implementation of convective forces to mitigate transport limitations, ultimately leading in the conversion of AN to ADN at Faradaic efficiencies >80% and current densities of 100’s mA/cm2. Our learnings on ADN electrosynthesis helped us to engineer the electrocatalytic hydrogenation of ADN to HMDA, achieving the highest reported selectivity to date for this reaction (>95%). I will also show how similar electrochemical engineering approaches allowed us to elucidate factors that control performance in the electrochemical production of ADN from glutamic acid, an abundant and inexpensive bio-based feedstock, and of ethylene from bio-derived propionic acid. Through our studies, we aim to electrify and bring sustainability to chemical manufacturing, one reaction at a time.
Electrocatalytic Reduction of Oxygen to Peroxide on a Microporous Carbon Layer in a Gas Diffusion Electrode: Implications for Scale-up
Authors: Bashir Shahid M. , Gyenge Elod L. 
Published: August 2024

When coupled with renewables, the two-electron oxygen reduction reaction(O2RR) could be a valuable process to generate hydrogen peroxide (H2O2), a versatile and environmentally friendly oxidant[1]. While the electrocatalyst's nature determines the catalytic activity and selectivity (2e- vs. 4e- reduction), the O2 gas mass transport, electrolyte type (e.g., alkaline, neutral, or acidic) and its flow rate, and the electrode configuration (e.g., trickle-bed or gas diffusion (GDE) electrode) are also essential factors for scale-up[2-4]. Typically, operational current densities for O2RR are limited to less than 100 mA cm-2, which is inadequate for industrial applications. The porous gas diffusion electrode (GDE) assembly provides continuous O2 gas delivery at the catalyst/electrolyte interface by overcoming O2 mass transport limitations encountered in trickle-bed or dissolved gas (single-phase) configurations. While the GDE could enable the operation under industrially relevant current densities (i.e., > 100 mA cm-2), for two-phase flow processes, flooding imposes severe challenges in the GDE scale-up and the durability of the process. Here, we present that a microporous carbon-coated gas diffusion electrode could enable very high current density (> 500 mA cm-2) synthesis of alkaline peroxide in a flow reactor with more than 90% faradaic efficiency. The microporous carbon layer provides dual functionality, namely the catalytically active sites for the reaction and controlling the GDE flooding. In addition to the electrode design, the two-phase fluid flow dynamics and electrolyzer operation conditions are significant factors for long-term stability. Although the fluid flow effect on the trickle bed type electrolyzer has been studied [3], no study exists on the systematic investigation of the two-phase mass transfer effect in the GDE-based electrolyzer for peroxide generation with a catholyte layer. The experimental findings and mass transfer modeling highlight further improvements concerning the process scale-up.

References

[1] N. Wang, S. Ma, P.Zuo, J. Duan and B. Hou, Adv. Sci., 2021, 8(15), e2100076-e2100076
[2] E. L. Gyenge and C. W. Oloman, J. Electrochem. Soc., 2005, 152(3), D42-D53
[3] I. Hodgson and C. Oloman, Chem. Eng. Sci., 1999, 54(23), 5777-5786
[4] Q. Zhang, M. Zhou, G. Ren, Y. Li and X. Du, Nat. Commun., 2020, 11(1), 1731
Enhancing Efficiency and Selectivity of Electrochemical Regeneration of NADH By Dynamic Operation
Authors: Al-Shaibani Mohammed Ali Saif , Sakoleva Thaleia , Zivkovic Luka A. , Dörr Mark , Bornscheuer Uwe , Vidakovic-Koch Tanja 
Published: August 2024

The demand for the reduced nicotinamide adenine dinucleotide (1,4-NADH) and reduced nicotinamide adenine dinucleotide phosphate 1,4-NAD(P)H in industrial processes, particularly in the pharmaceutical sector, necessitates their continuous regeneration to mitigate cost implications [1]. In this respect, direct electrochemical cofactor regeneration is a promising alternative, but challenges in achieving optimal selectivity have hindered its widespread industrial integration.
This study focuses on advancing the efficiency and selectivity of electrochemical NADH regeneration through dynamic potential inputs, inspired by recent findings demonstrating improved selectivity using dynamic potential inputs instead of steady-state conditions [2]. Various dynamic, pulsed potential profiles are tested and compared with steady-state conditions, revealing distinct advantages in selectivity. Nicotinamide adenine dinucleotide reduction reaction is then coupled with the enzymatic conversion of a substrate (cyclohexenone) to a product (cyclohexanone). In this electroenzymatic biotransformation, 1,4-NADH formed electrochemically is utilized as a second substrate of enzyme enoate reductase. The success of this coupling is evident in the observed formation of the desired product. This research not only contributes to the fundamental understanding of electrochemical co-factor regeneration but also demonstrates its practical application. By combining the advantages of electrochemical and enzymatic reactions, we pave the way for more sustainable and economically viable industrial processes. The presented results mark a significant step towards harnessing the full potential of electrochemical regeneration in facilitating enzymatic transformations with enhanced efficiency and selectivity through a pulsed dynamic operation.
References
1. Wu, S., et al., Biocatalysis: Enzymatic Synthesis for Industrial Applications. Angewandte Chemie International Edition, 2021. 60(1): p. 88–119.
2. Miličić, T., et al., Pulsed electrolysis – explained. Faraday Discussions, 2023. 246(0): p. 179–197.
Re-Functionalization of Aged Lithium Iron Phosphate Cathode Materials
Authors: Gee Carol-Lynn , Amador Carolyn , Nesvaderani Farhang , Hadidi Lida , Gates Byron D. 
Published: August 2024

As lithium-ion batteries continue to be implemented in everyday technologies, it is imperative to repurpose these battery materials upon their degradation. Carbon-coated lithium iron phosphate (LFP/C) is considered one of the most stable cathode materials for application in lithium-ion batteries. Due to this stability, LFP/C possesses a remarkably long cycle life of greater than 3000 cycles.1 Extended cycling of these cathode materials may result in multiple modes of degradation, including degradation of the carbon coating, and loss of contact between the cathode and the current collector.2,3 In this work, a suitable process and reagents have been selected to isolate and purify the LFP/C from the cathodes of cycled batteries. Isolating and purifying aged LFP/C materials enables the diagnosis of the mode(s) of degradation of these materials and their coatings using a variety of techniques including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy methods.
Furthermore, additional work was pursued to give new life to these isolated, spent cathode materials. The addition of a coating with a relatively high lithium conductivity to the aged LFP/C particles was sought to provide a second life to these electrochemically aged materials. Half-cells were fabricated using the coated, aged LFP/C cathode materials to compare their performance to both pristine LFP/C nanoparticles and aged LFP/C nanoparticles without the addition of this custom coating. Electrochemical testing techniques such as galvanostatic cycling, cyclic voltammetry, and electrochemical impendence spectroscopy were used to probe the performance of each type of LFP/C nanoparticle as cathode materials in lithium-ion batteries. The coated, aged LFP/C particles were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy techniques. The techniques developed herein can be used to isolate, purify, and re-functionalize other cathode materials from lithium-ion batteries.

Lewerenz, M.; Munnix, J.; Schmalstieg, J.; Kabitz, S.; Knips, M.; Sauer, D. U. Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging. Power Sources.
2017, 345, 254-263.

Wang, L.; Qiu, J.; Wang, X.; Chen, L.; Cao, G.; Wang, J.; Zhang, H.; He, X. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience
2022, 2(2), 125-137.
KxFeO2 As Electrode Material for K-Ion Batteries
Authors: Sagot Armance , Kovrugin Vadim , Stievano Lorenzo , Pralong Valerie 
Published: August 2024

To meet future energy demands, developing beyond-lithium energy storage technologies have become a major part of global research activities. Potassium-ion batteries (KIBs) represent a promising technology thanks to their chemical and economic advantages1–3. The majority of the work on layered transition oxide was done on the KxMnO2 family4,5 due to their safety and price advantage.
Interestingly, KFeO2 structure is not a layered structure as for LiFeO2 or NaFeO2; this structure is defined as FeO4 tetrahedral linked by their corners. In electrochemistry, a reversible capacity of 60 mAh/g (for 0.3K+) was delivers6.
In our presentation, we will detail the electrochemical behaviour of KFeO2 and discuss the structure/properties relationship of this family of materials, showing the interest in the exploration of such a system.

Xu, Y. et al. 2023 roadmap for potassium-ion batteries. J. Phys. Energy
5, 021502 (2023).

Tian, Y. et al. Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev.
121, 1623–1669 (2021).

Zhang, W., Liu, Y. & Guo, Z. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering. Sci. Adv.
5, eaav7412 (2019).

Kim, H. et al. Investigation of Potassium Storage in Layered P3-Type K0.5MnO2 Cathode. Adv. Mater.
29, 1702480 (2017).

Liu, C., Luo, S., Huang, H., Zhai, Y. & Wang, Z. Layered potassium-deficient P2- and P3-type cathode materials KxMnO2 for K-ion batteries. Chem. Eng. J.
356, 53–59 (2019).

Han, S. C., Park, W. B., Sohn, K.-S. & Pyo, M. KFeO2 with corner-shared FeO4 frameworks as a new type of cathode material in potassium-ion batteries. J. Solid State Electrochem.
23, 3135–3143 (2019).