bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ecofriendly K-Ion Batteries Relying on Abundant Chemical Elements and Water-Based Processes
Authors: Dautain Nicolas , Peralta David , Martin Jean-Frédéric , Sotta Dane , Azaïs Philippe 
Published: August 2024

Current Li-ion batteries are mainly composed of a graphite anode and a cathode based on either NMC (LiNixMnyCozO2) or LFP (LiFePO4) materials. However, the rapid growth of the electric car market will generate significant stress on key chemical elements (nickel, cobalt, copper, lithium). Moreover, the production of NMC and LFP materials turns out to be very energy intensive (multiple calcinations) and uses toxic solvents (NMP, ammonia). Because of that, Li-ion batteries are quite expensive and their ecological footprint is relatively high.
The scope of our work is to develop a potassium-ion battery which does not require any critical element and whose production significantly reduces the ecological footprint of the system. Such a battery technology could find its place either in low-cost electric cars or in large-scale-energy-storage devices.
We focused our efforts on the development of a Prussian White cathode material based on potassium, manganese and iron (K2Mn[Fe(CN)6) showing a theoretical capacity of 155 mAh/g with a potential close to 4 V vs K+/K. The synthesis of this material takes place in water at ambient temperature and it does not involve any calcination. First we optimized the synthesis via a chelating route: tuning the morphology of the Prussian White particles allowed us to come closer to the theoretical capacity of the material. Then we developed water-based coating slurries for our material. We were able to obtain electrodes containing 90 wt% of active material by optimizing both carbon additive and binder. These electrodes showed similar performances compared to electrodes obtained with literature-standard conditions (70 wt% active material, NMP-based slurries). Finally, we tested our Prussian White in full cells versus graphite in coin cells and pouch cells.

Figure 1
Controlled Catalyst Layer Architectures for Fuel Cell Applications
Authors: Ghosh Arpita , Walrand Gilles , Rozière Jacques , Jones Deborah J. , Cavaliere Sara 
Published: August 2024

The catalyst layer composition and architecture play a pivotal role in bridging the gaps between ex situ and in situ catalyst activities in fuel cells.1 The catalyst-support architecture strongly influences the catalyst distribution, ionomer distribution and mass transport losses, occurring at high current density.2 Herein, a novel architecture based on self-standing fiber-network has been fabricated and characterized.3 The resulting porous structure of such catalyst layer is expected to control mass transport limitation across both the interface of catalyst layer by increasing the number of Triple Phase Boundaries. Further platinum catalyst is deposited onto this fibrous support as well as the ionomer. The full electrode is characterized for its morphology and electrochemically verified in both ex situ as well as in situ configurations.

References

(1) Jiantao Fan, Ming Chen, Zhiliang Zhao, Zhen Zhang, Siyu Ye, Shaoyi Xu, Haijiang Wang & Hui Li, “Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells”,
Nature Energy,

6, 475–486, (2021).
(2) Nagappan Ramaswamy, Wenbin Gu, Joseph M. Ziegelbauer and Swami Kumaraguru, “Carbon Support Microstructure Impact on High Current Density Transport Resistances in PEMFC Cathode”,
Journal of The Electrochemical Society
,167, 064515, 2020.
(3) Giorgio Ercolano, Filippo Farina, Sara Cavaliere, Deborah J. Jones and Jacques Rozière, “Towards Ultrathin Pt Films on Nanofibers by Surface-Limited Electrodeposition for Electrocatalytic Applications”,

Journal of Materials Chemistry A

,
5, 3974–3980, 2017.
Long Time Dynamics for Platinum Surface Area Loss in PEM Fuel Cells
Authors: Van-Brunt Alexander John , Beck Victor , Braaten Jonathan , Cheng Lei , Mehrazi Shirin , Stewart Sarah , Stuhmeier Bjorn Marcel , Mojica Felipe 
Published: August 2024

Proton exchange membrane (PEM) fuel cells may emerge as a dominant clean energy source for heavy duty transport vehicles. Amongst other considerations, the lifetime performance of the fuel cell cathode catalyst layer is a key component of their future viability and a focus in the development of many proposed membrane electrode assemblies (MEAs). Typical targets of the lifetime of a PEMFC stack are on the order of thousands of hours of operation. However, running degradation tests spanning those long timescales is often impractical; and consequently, extensive work has been done developing and implementing accelerated stress tests (AST's) in order to screen proposed cathode catalyst materials for fuel cells.
Much value is obtained by accurate and robust lifetime prediction models which are able bridge the gap between degradation from AST's in differential cells, and degradation of the catalyst layer in a fuel cell stack under realistic operating conditions. In other words, by parameterizing a model on short-time, subscale ASTs and extrapolating to a stack after tens of thousands of hours of operation. Commonly in such models, the electrochemically active surface area (ECSA) of platinum is used as the primary state-of-health parameter and predicted using either data-driven models or physics-based models. On one hand, data-driven models may be well suited to utilize large sets of stack data, but offer weaker extrapolation potential, conversely fitting physics-based models on global measurements of stack data is rarely a well-conditioned inverse problem.
In this talk we present a scaling law on the long-time behavior of the ECSA obtained from analysis of governing physics equations from the literature. It is assumed that the primary loss mechanism is the coarsening of platinum particles, and the chief technique used is the method of averaging, which allows for the separation of two timescales: the short timescale of platinum oxide formation and dissolution, and the longer timescale over which the particle size distribution changes and a performance loss can be detected. The physics-derived asymptote for the ECSA evolution is then applied to several experiments and found to be in good agreement, allowing for a simple, streamlined lifetime prediction method for PEM fuel cells.
Lunar Electrochemistry Enabling Microgrid Energy Storage on the Moon
Authors: Li Yifan 
Published: August 2024

This talk will cover an atypical paradigm of large scale energy storage technology - the need for scalable energy storage using resources available at the point of use for sustained human presence in space exploration. For Lunar surface power reliability, large scale energy storage enables increased safety factor for power generation downtime, but the launch mass of energy storage makes scalable storage to the level of microgrids or grids unappealing. This is compounded by a central paradox of safe energy storage, that achieving high energy density intrinsically carries greater safety risk in storing greater energy in a smaller mass or volume. In situ resource utilization aims to solve both these problems, enabling safe and scalable energy storage to be deployed for Lunar surface power reliability. However, a long road remains between the nascent field of ISRU energy storage as it exists today and its needed destination to enable future sustained human presence on the Moon and Mars.
This talk will survey applications of electrochemical energy storage technologies and concepts with a focus on how Lunar resources can principally drive the electrochemistry. Brief mention will be given to non-electrochemical technologies such as thermal or mechanical methods, but the emphasis will be on electrochemistry owing to rapid advances in electrochemical state-of-the-art on Earth. Examples will include beyond Li-ion intercalation chemistry, metal-air cells, redox flow batteries, and regenerative fuel cells, using Lunar regolith and water as primary resources. For each technology, the talk will highlight where the study of “Lunar electrochemistry” must deviate from current terrestrial research to enable energy storage optimized for ISRU, rather than a simple transplant of Earth technology to Lunar application.
(Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award) Tailoring Electrode-Electrolyte Interfaces through Non-Covalent Interactions for Electrochemical Energy Storage and Conversion
Authors: Zhang Yirui Arlene , Wang Tao , Fraggedakis Dimitrios , Huang Botao , Stephens Ryan , Bazant Martin Z. , Shao-Horn Yang 
Published: August 2024

Li-ion batteries and fuel cells play essential roles in electrifying transportation. Central to the electrochemical systems is the electrode-electrolyte interface, where (electro)chemical surface reactions or intercalation occur, and its thermodynamic and kinetic properties determine the energy density, power density, and lifetime of the electrochemical devices. However, the molecular structures at the electrical double layer and reaction mechanisms remain poorly understood, hindering the rational material design for more efficient electrochemical devices. This talk focuses on the mechanisms of (electro)chemical reactions and charges transfer kinetics at the electrode-electrolyte interface, providing design principles based on non-covalent interactions in electrolytes.
First, an in situ Fourier-transform infrared spectroscopy (FTIR) method was developed for Li-ion batteries, which revealed unique evidence for dehydrogenation of carbonate electrolytes on Ni-rich lithium nickel, manganese and cobalt oxides (NMC), accounting for interface impedance build-up and battery capacity fading. Based on the proposed mechanism, strategies on suppressing electrode and electrolyte reactivity were demonstrated to improve battery cycling. Next, the kinetic mechanism for ion intercalation at the electrode-electrolyte interface will be discussed. Li-ion concentration-dependent intercalation kinetics was demonstrated from charge-adjusted electrochemical experiments and fit into a coupled ion-electron transfer mechanism, which governed the current-dependent maximum capacity and power density of intercalation batteries. Finally, for electrocatalytic reactions central to fuel cell technologies, we demonstrated tuning interfacial hydrogen bonding through protic ionic liquids with different acid dissociation constants and organic solvents with different donor numbers to tailor oxygen-reduction reaction (ORR) and hydrogen evolution reaction (HER). Strengthening hydrogen bonding between ORR products and ionic liquids, or between interfacial water molecules facilitated proton-coupled electron transfer kinetics, revealed by in situ surface-enhanced infrared absorption spectroscopy and density functional theory (DFT) calculations. The study can pave the way for the electrolyte and electrode design of electrochemical storage devices with improved energy and power density and cycle life.
(Invited) Tailored Electrochemical Interfaces for Renewable Fuels Production
Authors: Escudero-Escribano Maria 
Published: August 2024

Tailoring the structure of the electrified interface and the electrocatalytically active sites at the atomic and molecular levels is key to elucidating the design principles to develop advanced materials for sustainable energy conversion and storage. This talk will focus on recent strategies to tune the structure-activity-selectivity relationships for oxygen, carbon dioxide/carbon monoxide and methane electrocatalysis to produce renewable fuels.
First, I will present our work toward understanding and tuning the structure-property relations for oxygen evolution for the production of green hydrogen in proton exchange membrane water electrolysers. Then, I will show our model studies on well-defined Cu-based surfaces to understand structure-properties relations for the electrochemcial CO2 reduction reaction. We have investigated the effect of electrolyte, pH, and potential dependence for CO reduction on Cu single crystals as well as methods to evaluate the facet distribution on Cu-based catalysts. Finally, I will discuss some strategies for selective oxidation reactions such as partial oxidation of methane to produce liquid fuels such as methanol.
(Energy Technology Division Supramaniam Srinivasan Young Investigator Award) CO2 as a Building Block for Electrosynthetic Coupling to N- and S- Based Reactants
Authors: Kornienko Nikolay 
Published: August 2024

Energy-intensive thermochemical processes within chemical manufacturing are a major contributor to global CO2 emissions. With the increasing push for sustainability, the scientific community is striving to develop renewable energy-powered electrochemical technologies in lieu of CO2-emitting fossil-fuel-driven methods. However, to fully electrify chemical manufacturing, it is imperative to expand the scope of electrosynthetic technologies, particularly through the innovation of reactions involving nitrogen- and sulfur- based reactants as products from water/CO2 electrolysis do not cover the full scope of industrial needs.
To this end, this talk focuses on my lab’s efforts not only in CO2 conversion in the use of this molecule as a building block. This entails the co-electrolysis of CO2 with additional small molecule reactants (N2, NO3
-, SO3
2-...) in generating products with C-N and C-S bonds like amides, urea, and sulfonates that are important as commodity and fine chemicals in the chemical industry. In particular, I will discuss several new reaction pathways discovered towards several of the above-mentioned products and the application of operando techniques to understand the key C-N/C-S coupling steps in the reaction process.

Figure 1
A Strategy to Enhance Photo-Algal Hydrogen Production Using External H+ Ions in a Dual Photobioreactor
Authors: Hwang Jae-Hoon , Lee Woo Hyoung 
Published: August 2024

The use of microalgae for direct biohydrogen energy generation exhibits significant promise as an alternative to traditional bio-energy production due to zero-emission of CO2. It is known that during photolysis, algae are capable of producing hydrogen (H2) gas instead of oxygen (O2) under enriched acetate conditions by algal fermentative metabolisms [1]. The utilization of acetate as a practical oxygen regulator in photosystem II (PSII), but the algal hydrogen production was relatively low due to the insufficient H+ ions available in the photobioreactor (PBR) [2]. Therefore, given that hydrogen ions from acetate contribute to H2 production, it is still unclear whether supplying additional external H+ ions can enhance H2 production.
Here, we demonstrate a feasibility study on improving algal H2 production using a dual PBR system. This system enables the continuous transfer of H+ ions generated from photolysis to an algal H2 PBR through a proton exchange membrane (PEM), thereby enhancing photo-algal hydrogen production. The maximum H2 production of 108 µmol L-1 was obtained for Chlamydomonas reinhardtii in a single PBR for 15 days at a light intensity of 100 µmol m-2 s-1 [3]. However, by leveraging the external H+ ions supply, the dual PBR system increased photo-algal hydrogen production from 108 up to 760 µmol L-1 for the same period, which is 7 times greater compared to single chamber operation. This indicates that supplying external H+ ions in the operation of the dual PBR is one of the important parameters for improving biohydrogen production. Our findings contribute to the ongoing development of high-performance algal H2 production, offering valuable insights into optimizing the amount of H+ ions for enhanced hydrogen production.
[1] Clemens KL, Force DA, Britt RD. Acetate binding at the photosystem II oxygen evolving complex: an S2-state multiline signal ESEEM study. J Am Chem Soc. 2002;124(36):10921-33.
[2] Hwang J-H, Church J, Lim J, Lee WH. Photosynthetic biohydrogen production in a wastewater environment and its potential as renewable energy. Energy. 2018;149:222-9.
[3] Hwang J-H, Lee WH. Continuous photosynthetic biohydrogen production from acetate-rich wastewater: Influence of light intensity. Int J Hydrogen Energy. 2021;46(42):21812-21.
Concepts for Sustainable Organic Electrosynthesis
Authors: Francke Robert 
Published: August 2024

Organic electrosynthesis is frequently presented as an intrinsically sustainable, safe, and efficient method [1]. While this is indeed often the case, this assessment cannot be easily generalized, since several challenges need to be addressed on the way to more efficient and truly sustainable processes. These challenges comprise the necessity for employing large amounts of supporting electrolyte additives along with concomitant separation and waste issues [2]. Another separation problem arises when mediators have to be employed for controlling the selectivity [3]. In addition, highly flammable and toxic solvents are often used.
The present contribution will provide an overview of our recent work on the development of new approaches toward improving the practicality and sustainability of electro-organic reactions. Several concepts will be discussed, including polymediator-guided electrosynthesis [4], multi-functional supporting electrolytes [5], and electrolysis in sustainable solvents [6].
References:

a) M. Yan, Y. Kawamata, P. S. Baran, Chem.
Rev.
2017, 117, 13230. b) A. Wiebe, T. Gieshoff, S. Möhle, E. Rodrigo, M. Zirbes, S. R. Waldvogel, Angew.
Chem.
2018, 57, 5594.

a) R. Francke, Chimia
2020, 74, 49. b) R. Francke, Curr. Opin. Electrochem.
2022, 36, 101111.

a) R. Francke, R. D. Little, Chem. Soc. Rev.
2014, 43, 2492. b) R. Francke, B. Schille, M. Roemelt, Chem. Rev.
2018, 118, 4631.

A. Prudlik, N. Mohebbati, L. Hildebrandt, A. Heck, L. Nuhn, R. Francke, Chem. Eur. J.
2023, 29, e202202730. b) N. Mohebbati, A. Prudlik, A. Scherkus, A. Gudkova, R. Francke, ChemElectroChem
2021, 8, 3837. c) B. Schille, N. O. Giltzau, R. Francke, Angew. Chem. Int. Ed.
2018, 57, 422.

a) A. F. Roesel, T. Broese, M. Májek, R. Francke, ChemElectroChem.
2019, 6, 4229. b) O. Koleda, T. Broese, J. Noetzel, M. Roemelt, E. Suna, R. Francke, J. Org. Chem.
2017, 82, 11669. c) T. Broese, R. Francke, Org.
Lett.
2016, 18, 5896.

A. Prudlik, A. Matei, S. Beil, R. Francke, 2024, manuscript in preparation.
Reusable Cyclodextrin-Mediated Electrochemical Sensor in Automated Flow Cell for Cortisol Detection
Authors: Sajedi Ferdows , Halpern Jeffrey M. 
Published: August 2024

Our focus is on using beta cyclodextrin (βCD) to electrochemically detect cortisol; cortisol is a hydrophobic molecule that is a vital hormone, and cortisol is involved in the immune system, metabolism, heart health, and overall body balance. Cyclodextrins, characterized by a hydrophobic inner cavity and a hydrophilic outer surface, emerge as promising molecular receptors for detecting hydrophobic molecules. Notably, βCD and cortisol can form host/guest inclusion complexes. Building on our success in detecting cortisol with βCD in previous static cell experiments [1], herein we introduce innovations to further improve our methodology by employing an automated flow cell system. The transition to automation offers advantages such as repeated runs for obtaining more reproducible data and the elimination of human interactions and considerations, leading to an increased number of experiments. Our efforts, including the utilization of a ten-way multi-position valve and a pump for solution transfer, were crucial for enhancing the accuracy, stability, and reproducibility of cyclodextrin-mediated biosensors in automated flow cell systems. The automation process did encounter challenges, particularly with pump control, necessitating manual pauses before electrochemical measurements. Additionally, issues related to bubbles arose, prompting the search for the optimal flow rate and the utilization of a degasser. The ultimate goal is to optimize sensor stability, sensitivity, and reproducibility, contributing to the advancement of cortisol detection with the automated cyclodextrin-mediated biosensors.
Research supported by New Hampshire- INBRE through an Institutional Development Award (IDeA), P20GM103506, from the National Institute of General Medical Sciences of the NIH. Support was also provided by a National Science Foundation EPSCoR award (#2119237), BIO-SENS.
[1] Z. Panahi, T. Ren, and J. M. Halpern, “Nanostructured Cyclodextrin-Mediated Surface for Capacitive Determination of Cortisol in Multiple Biofluids,” ACS Appl. Mater. Interfaces, vol. 14, no. 37, pp. 42374–42387, Sep. 2022, doi: 10.1021/acsami.2c07701.
Synthetic Chemistry and Microelectrode Arrays for Point of Care Diagnostics
Authors: Moeller Kevin D , Chang Yu-Chia , Huang Albert 
Published: August 2024

Molecular diagnostics typically require a molecular interaction that identifies a specific target, a device that detects, quantifies, and records that interaction, and an interface between those two elements. Each feature is critical for the success of the device. Yet while the first two are matters of intense interest an research, the surface itself is often ignored. This is problematic because it provides the platform for the whole "experiment". For a "point-of-care" diagnostic, the surface on the device must be stable both in terms of chemistry and time while still allowing the signal from the molecular interaction to be sensed and recorded.
With this in mind, we have been focusing on the use of diblock copolymers as molecular surfaces for the construction of "point-of-care" diagnostics. We have developed a toolbox of chemical reactions that can be used site-selectively on such surfaces, and we have recently demonstrated that the approach taken is compatible with the use of DNA-aptamers to do multiplex sensing on a high density microelectrode array using a surface that is stable for a year. We have also illustrated how the quality of the signaling study conducted on an array is dependent on optimization of the chemical reaction.
But exactly how good are the chemical reactions employed on the arrays to build a surface in a site-selective manner? One can tell with the use of fluorescence based studies that reactions happen where you want then to happen, but are there background reactions that can be problematic for a multiplex sensing experiment, do the reactions happen in high yield, and how much of an expensive, difficult to obtain biological reagent might be lost due to the confinement strategy? Are some reactions better than others in this regard? In short, if we are to optimize the surfaces constructed on a diagnostic device, then we need not only have tools in place for conducting synthetic chemistry on the device, but also the tools in place necessary to analyze those reactions. Understanding the chemistry that can and/or does occur at any electrode in a high density array requires more than looking at pretty pictures of fluorescent spots. In the talk to be given, we will utilize a combination of a "Kenner-safety-catch" linker strategy and molecular biology techniques to answer key questions about the synthetic chemistry used to construct the DNA-aptamer based multiplex sensor mentioned above.