bluuebunny/crossref_metadata_2025 huggingface dataset:
Beast DB: A Computational Electrocatalysis Database with Solvation, Grand-Canonical Applied Potential, and Beyond-DFT Reaction Energetics
Authors: Vigil-Fowler Derek , Sutton Christopher , Musgrave Charles , del Ben Mauro , Sundararaman Ravishankar
Published: August 2024

Electrocatalytic reactions are key to decarbonizing the world economy, but progress in understanding electrocatalytic systems is often hindered by the diversity of conditions under which experiments are run and calculations are performed. This diversity is most often a result of experimental innovation to achieve better electrocatalyst performance, but nonetheless makes it difficult to establish clear baselines for electrocatalytic performance and to understand the fundamental factors that govern changes in performance. In order to make clear comparisons between different electrochemical configurations routine, we have constructed BEAST DB: the Beyond-DFT Electrochemistry with Accelerated and Solvated Techniques database. BEAST DB contains the most promising electrocatalysts for CO2reduction (CO2RR), the oxygen reduction reaction (ORR), the oxygen evolution reaction (OER), the hydrogen evolution reaction (HER), and nitrogen reduction reaction (NRR). For each electrocatalyst and chemistry, we have computed the adsorption energies, 𝛥Gads, and electronic properties for the most relevant catalyst facets and applied potentials. In this talk, we discuss general trends observed from this high-throughput database approach, and examine a few catalysts and chemistries in detail. Additionally, we describe our delta learning approach to learn high-fidelity reaction energetics from less expensive, lower-fidelity DFT calculations and applications of it to electrocatalytic systems. We illustrate how calculations of potential-dependent reaction energetics, as well as observables such as oxidation state and vibrational frequencies, allows for detailed comparisons to experiments such as X-ray absorption spectroscopy (XAS), Surface-enhanced infrared absorption spectroscopy (SEIRAS), and cyclic voltammetry. BEAST DB provides a wealth of information for both computationalists and experimentalists in the field of electrocatalysis, and provides a foundation for exploration of the underlying factors that govern electrocatalytic performance across a wide range of catalysts and chemistries.
Rate-Dependent Formation Processes in Li-O2 Batteries: Phase-Field Modeling with the Marcus Kinetics
Authors: Zhang Penghao , Bai Peng
Published: August 2024

Lithium-oxygen batteries (Li-O2) present a compelling prospect for the next generation of batteries owing to their exceptionally high theoretical energy density.[1] Yet, the performance of Li-O2 batteries is significantly limited by the current-dependent morphology of insulating oxides.[2-3] Existing mathematical models using Butler-Volmer kinetics exhibit uncertainties and inaccuracies.[4-5] In this study, we propose the integration of Marcus kinetics with the existing phase-field model to resolve a few outstanding inconsistencies between theoretical predictions and experimental discoveries. Notably, utilizing the Marcus kinetics enables a quantitative assessment of the role of solvation energy in current-dependet particle growth as opposed to film growth. Experimental results further verify the new theoretical predictions. This research offers valuable insights for the future design of Li-O2 batteries.

[1] Bruce, P. G., Freunberger, S. A., Hardwick, L. J., & Tarascon, J.-M. (2012). Nucleation and growth of lithium peroxide in the Li-O2 battery. Nature Materials, 11, 19–29.

[2] Read, J. (2002). Characterization of the Lithium/Oxygen Organic Electrolyte Battery. Journal of The Electrochemical Society, 149, A1190-A1195.

[3] Kraytsberg, A., & Ein-Eli, Y. (2011). Review on Li–air batteries—Opportunities, limitations and perspective. Journal of Power Sources, 196, 886-893.

[4] Lau, S., & Archer, L. A. (2015). Nucleation and growth of lithium peroxide in the Li-O2 battery. Nano Letters, 15(9), 6108–6114.

[5] Horstmann, B., Gallant, B., Mitchell, R., Bessler, W. G., Shao-Horn, Y., & Bazant, M. Z. (2013). Rate-dependent morphology of Li2O2 growth in Li-O2 batteries. Journal of Physical Chemistry Letters, 4(24), 4227–4232.
(Invited) Operando Visualization of the Electrolyte Distribution in Vanadium Redox Flow Electrodes
Authors: Zeis Roswitha
Published: August 2024

Electrolyte transport losses are among the main factors that limit the performance of Vanadium Redox Flow Batteries (VRFBs)1. The electrolyte must percolate into the electrode and reach the reaction sites with minimum resistance to reduce such losses. The optimized electrolyte flow ensures that the reactants and products are transported to and away from the reaction sites freely and decreases the pumping losses of the electrochemical cell, increasing the overall efficiency of the battery system.

The electrolyte distribution in a porous electrode is crucial for the stability and performance of the electrode. The presence of gas bubbles in the electrode reduces the electrochemically active surface, resulting in cell potential fluctuations. In addition, the gas bubbles cause poor contact between the electrolyte and the electrode, and the ionic conductivity could be locally blocked2. These effects lead to inhomogeneous potential distribution (spikes), accelerating the electrode material's corrosion. Gas bubbles are very common in VRFBs, and they result from parasitic side reactions, such as carbon corrosion, hydrogen evolution (HER), or incomplete electrode wetting3.

Synchrotron X-ray imaging is a powerful tool for tracking these bubbles in porous carbon materials. We have designed an experimental setup resembling an operating VRFB cell to image the flow through the porous carbon electrode. With its modular structure, the setup offers excellent flexibility to evaluate different designs and operational aspects of VRFBs4, 5. The findings of our investigations over the years will be discussed in this presentation.

References

J. Kim and H. Park, Journal of Power Sources, 2022, 545, 231904.

K. Krause, C. Lee, J. K. Lee, K. F. Fahy, H. W. Shafaque, P. J. Kim, P. Shrestha and A. Bazylak, ACS Sustainable Chemistry & Engineering, 2021, 9, 5570-5579.

M.-A. Goulet, M. Skyllas-Kazacos and E. Kjeang, Carbon, 2016, 101, 390-398.

L. Eifert, N. Bevilacqua, K. Köble, K. Fahy, L. Xiao, M. Li, K. Duan, A. Bazylak, P.-C. Sui and R. Zeis, ChemSusChem, 2020, 13, 3154-3165.

K. Köble, L. Eifert, N. Bevilacqua, K. F. Fahy, A. Bazylak and R. Zeis, Journal of Power Sources, 2021, 492, 229660.

Figure 1
Toward High-Throughput Surface-Sensitive X-Ray Scattering Studies of Electrochemical Interfaces
Authors: Matar Toka , Corts Wieland , Steinruck Hans-Georg
Published: August 2024

Lithium-ion batteries (LIBs) are widely recognised as essential parts of portable electronics, electric vehicles, and grid storage. As such, LIBs have considerable potential to contribute to our modern society, especially as a fundamental component in the development of a sustainable energy system [1]. Despite their success, many fundamental questions in the context of LIBs still puzzle researchers today. These involve interfaces and interphases [2]. For example, the structure and speciation of the potential- and surface-dependent electric double layer (EDL) (especially in advanced concentrated electrolytes) is currently not well understood. Relatedly, basic knowledge of multiple properties of the solid electrolyte interphase (SEI), a passivation layer formed on anode surfaces by electrolyte reduction products, needs to be unravelled to predict electrolyte behaviour as well as cell kinetics and lifetime [3].

To understand the structural properties of these solid-liquid interfaces and interphases, X-ray reflectivity (XRR) is a powerful method that employs model electrodes such as single crystals or thin films [4,5]. XRR provides surface sensitivity with sub-Ångström resolution, is non-destructive, allows probing buried nanoscale layers, and, importantly, can be carried out in operando modality [3]. One of the main challenges of XRR is that it is typically employed for a single electrochemical cell at a given time, and a single experiment takes on the order of several hours up to one day. In this scenario, the experiments are not photon-limited and continuous data collection is not necessary to obtain meaningful results because changes are slow towards later stages of the experiment (even though initial processes occur relatively fast). To overcome this limitation, we designed a high-throughput setup and corresponding experimental workflow, in which up to ten electrochemical cells can be measured via XRR and other surface-sensitive X-ray scattering methods (e.g., GISAXS and GIWAXS) quasi-simultaneously in an interleave fashion. We will present our novel experimental setup and first results.

Literature:

[1] G. Zubi, R. Dufo-López, M. Carvalho, & G. Pasaoglu,Renewable and Sustainable Energy Reviews, 89, 292-308, 2018.

[2] K. Xu, Journal of Power Sources, 559, 232652, 2023.

[3] C. Cao, H.-G. Steinrück, Encyclopedia of Solid-Liquid Interfaces, 391–416, Elsevier, 2024.

[4] T. T. Fister, X. Hu, J. Esbenshade, ... & P. Fenter, Chemistry of Materials, 28(1), 47-54, 2016.

[5] C. Cao, H.-G. Steinrück, B. Shyam, K. H. Stone, & M. F. Toney, Nano Letters, 16(12), 7394-7401, 2016.
Advancements in Dry Coating for Battery Electrodes: Scalable Extrusion Mixing for Control of Electrode Microstructure and Electrochemical Performance
Authors: Quérel Edouard , Dolder Valentin , Stössel Philipp , Hänsel Christian , Spillmann Adrian , Battaglia Corsin
Published: August 2024

Dry coating of battery electrodes is emerging as a promising alternative technology to the prevailing slurry coating and drying process widely adopted in the lithium-ion battery industry.1,2,3 To date, the most energy-intensive step in cell manufacturing is the drying of slurry-coated electrodes,1 and the adoption of dry coating aims to mitigate both the environmental impact and production costs associated with electrode production. Beyond environmental and economic concerns, producing higher mass-loading electrodes, a crucial aspect for increasing cell energy density, faces inherent challenges with the slurry-coating process: the drying of thick coatings often leads to issues such as electrode cracking and the formation of inhomogeneous electrode microstructures.

Bühler and Empa have collaboratively developed and are in the process of scaling up a dry-coating manufacturing method.4 Our process centers around the extrusion mixing of electrode components, followed by calendering of the dry mixture to produce the final electrode and direct lamination onto a current collector. In this presentation, we showcase the adaptability of extrusion mixing in inducing shear fibrillation of polytetrafluoroethylene (PTFE) binder, crucial for achieving the desired electrode microstructures (see Figure 1a and 1b). Furthermore, we demonstrate the capability of our dry-coating technology to produce high-mass loading electrodes with areal capacities of 5 mAh cm-2 or more (see Figure 1c).

The presentation encompasses a thorough characterization of dry-coated electrodes, including their microstructure and electrochemical performance in lab-scale batteries. Key aspects, such as rate capability and capacity retention, are evaluated. A comprehensive comparison with slurry-coated electrodes, fabricated using identical active electrode materials, mass fractions, and mass loading, reveals that our dry-coated electrodes exhibit comparable performance to their slurry-coated counterparts.5 The scalability of our dry-coating technology is underscored, highlighting the achievable throughputs necessary for gigafactory-scale production with a single extruder.

References:

1 F. Degen, M. Schütte, Journal of Cleaner Production, 2022, 330, 129798

2 B. Schumm, S. Kaskel, Next Energy, 2023, 100009

3 Y. Lu, C.Z. Zhao, H. Yuan, J.K. Hu, J.Q. Huang, Q. Zhang, Matter, 2022, 5, 876–898

4 InnoSuisse Flagship project CircuBat

5 E. Quérel, V. Dolder, C. Hänsel, P. Stössel, C. Battaglia, in preparation

Figure 1
Scalable Synthesis of Single Crystal Ni-Rich Cathodes for Advanced Lithium-Ion Batteries
Authors: Bi Yujing , Xu Yaobin , Wang Chongmin , Xiao Jie
Published: August 2024

Long-range electrical vehicles require high energy density lithium-ion batteries that utilize stable, high-energy cathode materials. Among various cathodes, Ni-rich NMC cathodes with a layered structure, knows for their high capacity, high voltage, and cost-effectiveness, stand out as one of the most promising cathodes. Traditional polycrystalline Ni-rich NMC encounter issues such as pulverization, gas generation and moisture sensitivity, limiting their widespread use in EV batteries on large scale. The single crystal format of Ni-rich cathode can effectively eliminate and mitigate these issues. However, synthesizing of high-performance single crystal Ni rich NMC, especially when Ni ≥0.8, presents a significant challenge.

We’ve explored an innovative phase separation approach for direct synthesis of high-performance single crystal NMC811. The comprehensive investigation into the reaction mechanism of single crystal growth was conducted to understand the relationship between synthesis, morphology, and performance in growing single crystal NMC811. The enhanced performance of these materials was realized through the precise morphological and structural control of precursors and has been confirmed in practical 2Ah pouch cells. The developed approach is readily adaptable to current industry manufacturing processes and provides valuable new insights that can be broadly applied to cost-efficient large-scale synthesis of single crystals and various advanced battery materials technologies.
Freeze Tape Casting Electrode with Bi-Layered Architecture for High-Performance Lithium-Ion Batteries
Authors: Tao Runming , Polyzos Georgios , Dixit Marm , Sharma Jaswinder , Li Jianlin
Published: August 2024

A facile freeze tape casting (FTC) strategy is utilized to prepare bi-layered cathodes with a high LiNi0.6Co0.2Mn0.2O2 active material loading of 4 mAh cm-2. The bottom layer is a conventional non-aqueous electrode, which has dense structure for high-energy purpose. The top layer is prepared by the proposed FTC, exhibiting porous feature for high-power requirement. With the assistance of FTC, the bi-layered electrodes successfully deliver enhanced rate and cyclic performance due to the improved lithium-ion diffusion kinetics and pathways. Therefore, the proposed FTC strategy and its delivered electrodes are promising for energy- and power-density lithium-ion batteries, potentially enlightening the research and development of lithium-ion battery manufacturing.
Characterization and Analysis of Coal-Derived Graphite for Lithium-Ion Batteries
Authors: Paul Abigail , Magee Regan , Wilczewski Warren , Wichert Nathan , Gula Caleb , Olson Rudolph , Shereda Eric , Lowe Jeffrey , Al-Majali Yahya , Trembly Jason , Wolfe Kody D , Staser John A. , Garrick Taylor R.
Published: August 2024

Graphite is a critical material used as the negative electrode in lithium-ion batteries. Both natural and synthetic graphites are utilized, with the latter obtained from a range of carbon raw materials. In this work, efforts to synthesize graphite from coal as a domestic feedstock for synthetic graphite are reported. The performance in lithium-ion coin cells of this coal derived graphite is compared to commercial battery-grade graphite. This includes characterization of the thermodynamics of the coal derived graphite using the multi-species, multi-reaction (MSMR) model, characterization of the entropy and enthalpy of the material, and estimation of the rate capability. This enables modeling of synthetic coal-derived graphites and virtual evaluation[1] of these materials towards electric vehicle and grid storage applications.

References

1. T. R. Garrick, Y. Zeng, J. B. Siegel, and V. R. Subramanian, "From Atoms to Wheels: The Role of Multi-Scale Modeling in the Future of Transportation Electrification." Journal of The Electrochemical Society 170.11 (2023): 113502.
Sustainable Modification of Naturally Available Resources for Metal-Ion Storage Applications
Authors: Kamali Ali Reza
Published: August 2024

The adoption of naturally abundant resources for energy storage applications represents a pivotal strategy in advancing large-scale sustainable green energy solutions across diverse sectors. This presentation provides an overview of E2MC's approaches to the green modification of naturally occurring materials at a low cost, focusing on their metal-ion energy storage capabilities. Key natural materials discussed include molybdenum disulfides (MoS2), ilmenite and natural graphite minerals, as well as corn waste. (a) The thermal oxidation of MoS2 is explored as a straightforward and effective method to produce layer-structured molybdenum trioxide (α-MoO3) with crystalline defects, showing enhanced Li-ion storage kinetics. The molten salt treatment of MoS2 produces sodium dimolybdate with improved Li-ion and Na-ion storage performances. Additionally, a hybrid nanostructure comprising metastable monoclinic molybdenum trioxide (β-MoO3), hexagonal MoS2 secondary crystals and graphene nanosheets is produced through mechanochemical-molten salt treatment. This hybrid structure exhibits an interesting Li-ion storage performance. (b) Carbonization of largely available corn lignocellulosic waste in the presence of molten salt is discussed as a facile approach for the preparation of biocarbons with appropriate specific surface area, pore volume, and elemental carbon purity. The partial dissolution of biomass impurities into the molten salt enhances the Li-ion and Na-ion storage performance of the biocarbon. Additionally, the treatment of corn-derived silica with Fe2O3 and graphite-derived graphene nanosheets, leads to the preparation of a nanostructure in which ferric oxide particles are coated with iron silicate, and these hybrid nanostructures are integrated with graphene nanosheets, showcasing an interesting Li-ion storage performance. (c) Efficient exfoliation of naturally available graphite minerals in molten salt is introduced leading to the formation of carbon nanostructures with promising applications in both Li-ion and Na-ion storage. The economic and strategic advantages associated with utilizing such naturally available resources for energy storage applications are also discussed.

References

W. Zhu, A.R. Kamali*, J. Alloy Compd. 932 (2023) 167724

W. Zhu, A.R. Kamali*, J Alloy Compd. 968 (2023) 171823

A.R. Kamali*, H. Zhao, J. Alloy Compd. 949 (2023) 169819

W. Zhu, A.R. Kamali*, J. Alloy Compd. 831(2020) 154781

H. Zhao, A. Rezaei, A.R. Kamali*, J. Electrochem. Soc. 169 (2022) 054512

A.R. Kamali*, J. Ye, Miner. Eng. 172 (2021) 107175

S. Li, A.R. Kamali*, Chem. Eng. Sci. 265 (2023) 118222

S. Li, A.R. Kamali*, Gels 9 (2023) 701

S. Li, A.R. Kamali*, Colloids Surf. A 656 (2023) 130275

H. Fu, A.R. Kamali* et al, Chem. Eng. J. (2023) 146936

W. Zhu, A.R. Kamali*, J. Electrochem. Soc. 168 (2021) 046517
Fabrication of 60μm-Thick Free-Standing Bilayer Solid Electrolytes for Solid-State Batteries Using Solution Processing and Lamination
Authors: Kim Younggyu , Juarez Yescaz Carlos , Liao Daniel W. , Jangid Manoj K. , Joshi Prerna , Yang Heng , Zahiri Beniamin , Braun Paul V. , Dasgupta Neil P.
Published: August 2024

Development of solid-state batteries with a high voltage cathode and lithium metal anode could enable high energy density while avoiding safety issues of flammable liquid electrolytes. However, the solid electrolyte (SE) should meet multiple requirements, including 1) electrochemical stability at both the cathode and anode side interfaces, 2) small thickness (tens of μm) to maximize energy density of the cell, and 3) fabrication with a scalable manufacturing method. Using bilayer SEs with different electrochemical stability windows could enable stability at both cathode|SE and anode|SE interfaces. In this work, we developed a manufacturing process to fabricate thin (60 μm) free-standing bilayer SE films from slurry casting and lamination, which can be used for large scale manufacturing of SSBs.

Halide SE (Li3InCl6) and sulfide SE (Li6PS5Cl) were slurry casted on different substrates, and then were dried in vacuum before being laminated onto each other to make a free-standing bilayer film. The parallel slurry casting approach eliminates cross-compatibility requirements of the solvents used for slurry preparation. The resulting bilayer films after densification were pin-hole free without intermixing between the two phases. The ionic conductivity of the bilayer SE film was ~70% of the bilayer SE pellet (1 mm thickness in total) made with a conventional powder pressing method. However, because the thickness of bilayer SE film (60 μm) was much smaller than the bilayer SE pellet (1 mm), the bilayer SE film had ~10x lower area-specific resistance (ASR) compared to the bilayer SE pellet. Because of the lower total cell resistance, the cell made with the bilayer SE film had a better rate capability compared to the reference cell in pellet geometry.

The strategy developed in this work could be integrated into current manufacturing infrastructure of battery fabrication as it is based on slurry casting, which is already a well-established fabrication method for lithium-ion batteries. Moreover, it could be used to fabricate multi-layered solid-state architectures in general, which are challenging to manufacture due to solvent compatibility issues during slurry casting. The study will assist the progress of solid-state battery manufacturing by providing a scalable manufacture method to prepare thin free-standing bilayer SEs.
High Throughput Quality Control Tools for Carbon-Related Materials: A Raman Approach
Authors: Miao Peng
Published: August 2024

Carbon-based materials play a pivotal role in battery technology, serving as negative electrode materials, conductive additives, and coating layers for both positive and negative electrode materials. Traditional characterization methods, such as transmission electron microscopy (TEM) and X-ray diffraction (XRD), fall short in providing comprehensive quality control, especially when distinguishing the structure of amorphous carbon materials. Raman spectroscopy as a convenient, simple tool is widely used to study the structure of carbon materials. It provides insights into the degree of crystallization, doping degree, and subtle structural differences arising from various preparation processes. By quantifying Raman spectrum testing results through statistical methods and providing relevant statistical outcomes, we demonstrate the potential of Raman spectroscopy as a quality control method for carbon material characterization. With extensive sample testing and automation, along with standardized spectral data processing and analysis software, we propose Raman spectroscopy as a suitable tool for high-throughput quality control in industrial production.
Bridging the Gap: Unraveling the Mechanisms of Nanobubble Detachment from Electrode Surfaces
Authors: Aydin Fikret , Gemeda Hawi Bacha , Yu Henry , Lin Tiras Y , Davis Jonathan T. , Kang Shinyoung
Published: August 2024

Gas evolution reactions play a fundamental role in the functionality of various electrochemical devices. Recent experimental studies have provided valuable insights into the behavior of gas bubble formation on nanoelectrodes; however, the experiments have limited spatial resolution to fully understand the underlying mechanisms governing the formation of nanobubbles and their stability on the surface as well as the effects of nanoscopic surface defects on their behavior. A comprehensive understanding of how bubbles behave on electrode surfaces and in the electrolyte is essential for optimizing and designing electrochemical processes. In this work, we employ all-atom molecular simulations to explore the effects of surface chemistry and defect geometry on detachment behavior of hydrogen gas bubbles on nickel electrodes at molecular level. Analyzing the dynamics of bubble detachment on the surfaces with different chemistries reveals that the rate of bubble detachment is higher on the strongly hydrophilic surface compared to the surface exhibiting weak hydrophilicity. In addition, our findings indicate that the defect geometry has significant effects on the detachment of bubbles from the surface. Specifically, the width and depth of canonical-shaped defects are demonstrated to be critical parameters affecting the behavior of the hydrogen bubbles on the nickel surface. Overall, our results show there is a complex balance between the degree of surface wettability and surface defects, determining the stability of nanobubble formation on the electrode surfaces. The results of this study could enhance our understanding of bubble detachment dynamics on the electrode surfaces, providing valuable insights for the future design of practical applications.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC5207NA27344. Release: LLNL-ABS-858292
(Invited) Multimodal Operando Studies of Dynamic Cu Nanocatalysts for CO2 Electroreduction
Authors: Yang Yao , Yang Peidong
Published: August 2024

In an era of shifting the energy paradigm from fossil fuels to renewable energy, CO2 reduction reaction (CO2RR) emerges as a promising approach to covert greenhouse gas into valuable chemical fuels and close the carbon cycle for a sustainable energy supply. Since Cu remains the sole element for CO2RR to multicarbon products (C2+), significant efforts have been devoted to developing Cu electrocatalysts with higher selectivity and activity. However, the complex nature of active sites and the intrinsic structures under reaction conditions have remained largely elusive due to the lack of operando/in situ methods.1-3

In our previous studies, we reported that small Cu nanoparticles (sub-10 nm NPs) showed superior C2+ superior C2+ selectivity, relative to the larger sized Cu NPs, especially at low overpotentials.4,5 In this work, we present a comprehensive operando correlative study of dynamic evolution during the life cycle of a family of monodisperse Cu NP ensemble electrocatalysts under CO2RR.1
Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and 4D-STEM resolves microscopic dynamic morphological and structural evolution at the nm scale. Correlated operando high-energy-resolution fluorescence-detector (HERFD) X-ray absorption spectroscopy (XAS)6 reveals dynamic macroscopic changes in valence states and coordination environment. Statistical analysis of interparticle dynamics was probed by operando resonant soft X-ray-based small-angle X-ray scattering (SAXS).2 The operando correlative strategies, described herein, elucidates the longstanding enigmatic nature of Cu active sites as metallic Cu nanograins for selective CO2 electroreduction (Fig. 1). The strategy described herein can serve as a general platform to resolve the electrocatalytic interface of nanoparticle catalysts under real-time operating conditions across multiple time and length scales, thus serving the fundamental understanding necessary to development of many other electrochemical reactions for renewable energy technologies.

References:

Yang, Y., Yang, P. et al. Operando Studies Reveal Active Cu Nanograins for CO2

Nature
2023, 614, 262.

Yang, Y., Yang, P., et al. Operando Resonant Soft X-ray Scattering Studies of Chemical Environment and Interparticle Dynamics of Cu Nanocatalysts for CO2
J. Am. Chem. Soc

. 2022, 144, 8927−8931.

Yang, Y., Abruña, H. D. et al. Operando Methods in Electrocatalysis.
ACS Catal
. 2021, 11, 1136-1178.

Kim, D., Yang, P. et al. Copper Nanoparticle Ensembles for Selective Electroreduction of CO2 to C2−C3
Proc. Natl. Acad. Sci. U.S.A

. 2017, 114, 10560−10565.

Li, Y., Yang, P. et al. Electrochemically Scrambled Nanocrystals are Catalytically Active for CO2-to-Multicarbons.
Natl. Acad. Sci. U.S.A
. 2020, 117, 9194−9201.

Feijoo, Yang, Y. et al. Operando High-Energy-Resolution X-ray Spectroscopy of Evolving Cu Nanoparticle Electrocatalysts for CO2 Reduction.
J. Am. Chem. Soc.
2023, 145, 20208

Figure 1
Efficient Exploration of Electrochemical Pre-Treatment on the Performance of Nanocrystal Electrocatalysts By Design of Experiments
Authors: Mule Aniket Sandip S. , Tran Kevin , Aleman Ashton M. , Cornejo-Carrillo Yamile , Kamat Gaurav A. , Burke Stevens Michaela , Jaramillo Thomas F.
Published: August 2024

Activation, break-in, or pre-treatment protocols are electrochemical techniques applied in energy-storage or -conversion devices, like fuel cells, before regular operation. Although these protocols have been demonstrated to optimize the utilization of thin-film electrocatalysts, their impact on the intrinsic physical properties and the performance of the practically relevant nanocrystal-based catalysts remains poorly understood. This study employs a design-of-experiments (DoE) approach to investigate how electrochemical pre-treatment affects the performance of electrocatalytic oxygen reduction reaction (ORR) in carbon-supported Pt-nanocrystal catalysts. First, we designed various pre-treatment protocols using a central composite design for five different levels of five electrochemical factors: 1) upper potential (UPL), 2) potential sweep depth, 3) sweep rate, 4) number of cycles, and 5) hold time at potential extrema. These protocols were then tested in a flow cell combined with an inductively-coupled plasma mass spectrometer (online ICP-MS). Utilizing the DoE approach, we achieved comprehensive insights through a limited set of experiments. Moreover, our online ICP-MS setup yielded mass-transfer limited current densities and simultaneously provided real-time data on catalyst dissolution (down to 0.1 ppb). Such an experimental strategy enabled us to efficiently and rapidly explore the effect of a vast parametric space on the electrocatalytic performance. Surprisingly, unlike Pt-based thin films, our results indicate that none of the pre-treatment protocols tested resulted in significant improvements to Pt nanocrystal ORR performance. Instead, high UPLs (~ 2 VRHE) during pre-treatment were found to lower the onset potential for ORR. Additionally, combining such high UPLs with a low potential sweep depth (~ 0.7 V) in pre-treatment led to increased dissolution during ORR. To understand these findings, we explored five potential degradation mechanisms: 1) carbon corrosion 2) Ostwald ripening of nanocrystals 3) Pt dissolution 4) coalescence of nanocrystals, and 5) surface changes in Pt by employing various in-situ and ex-situ characterization techniques. Our investigations identified surface changes in Pt at high UPLs in pre-treatment as the primary cause of performance deterioration during ORR. Therefore, by combining DoE with in-situ and ex-situ characterization techniques, we demonstrate a powerful approach to gain a mechanistic understanding of pre-treatment protocols on electrocatalytic performance that can be broadly applied to various reaction chemistries and material libraries.
Development of Thin-Film Nanoporous Ruthenium Electrocatalysts Using Atom Probe Tomography
Authors: Hatipoglu Ezgi , Saksena Aparna , Schneider Jochen , Gault Baptiste , El-Zoka Ayman A.
Published: August 2024

Dealloying corrosion has been used to create high surface area nanoporous metals with promising catalytic properties towards alkaline water electrolysis [1], [2]. The selective dissolution of the less-noble metal from a solid-solution alloy results in a 3D open-pore, nanostructured substrate which is chemically rich in the more noble metal. Ruthenium, the cheapest Pt-group metal [3], has desirable catalytic properties for the hydrogen evolution reaction, however making nanoporous ruthenium (NPR) substrates by dealloying has been challenging due to its limited miscibility with Ag and Cu, compared to the more widely studied Au. Hence, the potential improvement of Ru catalytic properties through dealloying Ru-based systems remains unexplored

In this study, we use magnetron sputtering to make metastable, single-phase, Ag-Ru thin films, with the aim of electrochemically dealloying them to create uniformly NPR substrates. The impact of thin-film structures and chemistry on subsequent dealloying behaviors were investigated by integrating electrochemical measurements with high-resolution characterization techniques including atom probe tomography (APT), electron backscatter diffraction (EBSD), and scanning electron microscopy (SEM). Furthermore, we correlate the thin-film properties studied with the structure and chemistry of NPR formed during dealloying. Amongst the valuable insights attained, we reveal atomic-scale compositional fluctuations in as-deposited non-equilibrium Ag-Ru, that impact the nanoligament compositions in dealloyed nanoporous ruthenium. Finally, the electrocatalytic performance of different NPR substrates are reported for hydrogen evolution reaction. Thereby, advancing the development of novel Ru-based nanoporous electrocatalysts and outlining pathways for future guided optimization.

[1] Erlebacher, J., Newman, C. & Sieradzki, K. Fundamental physics and chemistry of nanoporosity evolution during dealloying. RSC Nanosci. Nanotechnol. 11–29 (2012). doi:10.1039/9781849735285-00011

[2] J. Tian et al., “Dealloying of an amorphous TiCuRu alloy results in a nanostructured electrocatalyst for hydrogen evolution reaction,” Carbon Energy, vol. 5, no. 8, Aug. 2023, doi: 10.1002/cey2.322.

[3] Johnson Matthey Inspiring science, enhancing life. Available at: https://matthey.com/products-and-markets/pgms-and-circularity/pgm-management (Accessed: 18 December 2023).
Leaded Bronze Foams As Innovative Electrodes for Organic Electrosynthesis
Authors: Gálvez-Vázquez María de Jesús , Moreno Garcia Pavel , Prenzel Tobias , Winter Johannes , Gálvez-Vázquez Liliana , Broekmann Peter , Waldvogel Siegfried R
Published: August 2024

The electrification of organic synthesis represents an outstanding green alternative to prepare valuable and fine chemicals. However, the design of electrode materials for organic electrosynthesis remains as an open field to investigate. Motivated by the superior performance of leaded bronzes as electrodes for reductive transformations,[1, 2, 3] we have developed highly porous binary and ternary leaded metal foams through the dynamic hydrogen bubble template method [4] and tested them as cathodes in the electro-organic synthesis of 2,6-dichlorobenzonitrile from 2,6-dichlorobenzaldoxime.[5]

The electrocatalytic performance of the novel leaded foams was compared to the one of the planar CuSn7Pb15 leaded bronze. The novel porous leaded foams outperformed the CuSn7Pb15 electrodes in terms of chemical yield and energy efficiency. Furthermore, due to their highly crystalline surface, these materials are mechanically more stable and less prone to cathodic corrosion than flat Pb and CuSn7Pb15 electrodes.

References:

1) C. Gütz, V. Grimaudo, M. Holtkamp, M. Hartmer, J. Werra, L. Frensemeier, A. Kehl, U. Karst, P. Broekmann, S. R. Waldvogel, ChemElectroChem 2018, 5, 247.

2) T.Wirtanen, E. Rodrigo, S. R.Waldvogel, Chem. - Eur. J. 2020, 26, 5592.

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Figure 1
Preliminary Electrochemical Analysis of Carbon Nanoparticles from Candle Soot
Authors: Lubanjar Binita , Avila-Gutierrez Mario , Trinh Minh Quang , Corona-Elizarraras Luis , Jaisi Shankar , Alpuche-Aviles Mario A.
Published: August 2024

Nanoparticles (NPs) generated by candle soot are of interest due to their potential applications. Because of their electronic properties, carbon-based zero-dimensional, one-dimensional, and two-dimensional nanomaterials such as graphene, fullerene, carbon nanotubes, and carbon nanofibers are extensively studied (1).However, synthesis of these nanomaterials is complex and expensive. Candle soot also contains fluorescent carbon NPswhich can be used for the preparation of fluorescent makers (2). The potential applications of candle soot NPs include energy storage [e.g., can be used for supercapacitor electrode material (3)], and conversion [fuel cells (4)]. Candle soot can be an excellent source of carbon NPs. In this presentation, we cover some challenges associated with carbon NPs, such as (a) instability of NPs due to agglomeration with time and increase in temperature and (b) separation and isolation of NPs. Thus, we focus on stabilization of NPs, isolation and characterization of NPs and to study electronic, optical, and electrochemical properties to determine whether they are promising candidate in the field of energy conversion.

Candle soot formation depends on various parameters like substrate material, deposition time, flame temperature, wick dimension, and flame height (5). We developed a protocol for the collection of candle soot. With this proposed protocol, the carbon NPs generated from candle soot ranges from 50 nm to larger particle size which is confirmed by dynamic light scattering (DLS) technique shown in Fig. 1, and transmission electron microscope (TEM). We will include the electrochemical analysis such as investigation of oxidation/reduction processes to determine fundamental thermodynamic parameters of standard potential in organic solvents and aqueous solutions.

References

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J. Campbell, M.J. Andrews, K.J. Stevenson, New nanotech from an ancient material: Chemistry demonstrations involving carbon-based soot, J. Chem. Educ., 89 (2012) 1280-1287.

Zhang, D. Wang, B. Yu, F. Zhou, W. Liu, Candle soot as a supercapacitor electrode material, RSC. Adv., 4 (2014), 2586-2589.

Khalakhan, R. Fiala, J. Laukova, P. Kus, A. Ostroverkh, M. Vaclavu, M. Vorokhta, I. Matolinova, V. Matolin., Candle Soot as an efficient support for proton exchange membrane fuel cell catalyst, Fuel Cell., 16 (2016) 652-655.

N. Sahoo, B. kandasubramanian. An experimental design for the investigation of water repellent property of candle soot particles, Mater. Chem. Phys.,148 (2014), 134-142.

Figure 1
Three-Dimensional (3D) Porous Reduced Graphene Oxide Aerogel (RGA) Nanoelectrodes Consisted of Palladium Nanoparticles Embedded in Polyethlyenimine (PEI) for Detection of Bisphenol A and H2O2
Authors: Lee Kyu Hwan , Kim Min-Yeong
Published: August 2024

This research focuses on the development of three-dimensional (3D), hierarchically porous nanoelectrodes, which incorporate palladium nanoparticles within a polyethyleneimine-reduced graphene oxide aerogel (RGA-PEI-Pd). These nanoelectrodes are designed for sensitive detection of bisphenol A (BPA) and hydrogen peroxide (H2O2). The abundant positive charges in polyethyleneimine (PEI) facilitate the formation of a 3D porous structure by connecting to the reduced graphene oxide through carbon-nitrogen bonds, while also anchoring palladium nanoparticles uniformly across the aerogel. This structure maintains the aerogel's porosity.Palladium in its zero-valent (Pd0) and divalent (Pd2+) states plays a crucial role in the catalyst's performance, undergoing redox reactions to alternate between Pd2+ and Pd4+ states. This dynamic contributes to the electrode's ability to effectively oxidize BPA and reduce H2O2. The modified electrode showed low detection limits for BPA (25.5 nM) and H2O2 (16.2 nM) under optimal conditions. Extensive analytical methods, including electrochemical spectroscopy, were employed to delve into the unique electrocatalytic properties of these electrodes.The practical applicability of these electrodes was further demonstrated by their successful use in real-world environmental and biological samples, such as BPA-contaminated water from rivers and lakes, and clinical samples containing MCF-7 cells. The electrodes also exhibited impressive reusability, with recovery rates ranging from 96% to 104.3%.
Advanced MWCNTs/Al2O3 Modified SPE Immunosensor for Detection of Colistin in Chicken Liver
Authors: Umadevi Kovuri , Ali Mohd Imran , Indira K
Published: August 2024

The rising concerns regarding the presence of antibiotic residues in food commodities underscore the imperative need for the establishment of methods that are both rapid and precise for their identification. Specifically, given the widespread use and subsequent likelihood of residues of antibiotics such as colistin being found in various meat products, there is an urgency to address this. Even though colistin, a peptide antibiotic, has been prohibited for human consumption, its use in veterinary medicine and as a livestock feed additive remains prevalent. Our current study elaborates on the development of an immunosensor created through the immobilization of anti-colistin antibodies onto a surface composed of MWCNTs and Al₂O₃. This was achieved using a screen-printed electrode. The immunosensor exhibited the ability to generate electrochemical responses upon exposure to chicken liver samples treated with colistin. Responses were recorded using cyclic voltammetry (CV). To ensure accuracy, extensive characterization of the electrode’s surface was carried out at each fabrication stage using Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy (FTIR), and Electrochemical Impedance Spectroscopy (EIS). The immunosensor showcased a low limit of detection at 0.89 µg.kg⁻¹ and a coefficient of determination R² of 0.91 when evaluated using CV. For a broader perspective, the immunosensor’s performance was benchmarked against results from commercial chicken liver samples obtained via conventional methodologies. The findings indicate that the innovative MWCNTs/Al₂O₃-based electrode not only functions with remarkable speed but is also highly sensitive. This makes it an ideal choice for applications in biomedical sensing

Figure 1
Sputtered Deposited Cu Functionalized MoS2 Nanoworm Thin Films for Nitrogen Dioxide (NO2) Gas Sensor
Authors: Singh Beer Pal , Tyagi Shrestha
Published: August 2024

Semiconducting nanostructures thin films are used in state-of-arts applications due to their heightened physical properties. Semiconducting metal sulfides nanostructures are a growing asset in current semiconductor technology due to their extraordinary physical, chemical, and electronic properties and their outstanding applications in different sensing and optoelectronic devices. The gas sensing capability of semiconducting nanostructures is a recent research interest of many researchers. The MoS2 thin films were grown using reactive sputteringand the sensing performance of pure MoS2 and Cu-MoS2 thin films was studied towards nitrogen dioxide (NO2) gas concentrations (2-200 ppm) at the optimum working temperature of 100℃. The Cu-MoS2 sensor provides a high sensing response as compared to the pure MoS2 thin-film sensor towards 20 ppm of NO2 gas with a fast response and recovery time of 54 s and 82 s, respectively. It was observed that the proposed sensor chip displays an almost stable signal up to the 5th cycle. It is observed that the proposed sensor device exhibits the highest response (30%) to NO2 concerning weak response (10%) towards additional potentially interfering gases (NH3, CO, and H2) at 100°C. It reveals that the Cu-MoS2 thin-film sensor chip is highly selective to NO2 gas at 100 °C.
Synergistic Effects of V2O5 Nanoparticles Decorated By 2-Amino-1,3,4-Thiazole Derivatives Based Schiff Bases for High-Performance D-Glucose Sensing
Authors: Bansal Smriti , Jain Purnima
Published: August 2024

V2O5 lamellar structure modifies its adsorption and conduction characteristics that makes it an extensively used biosensor for the detection of D-Glucose but its faster recombination rate limits its sensitivity. Here, V2O5 nanoparticles (NPs) decorated with 2-Amino-1,3,4-thiazole derivatives-based Schiff bases have been fabricated to enhance the sensing performance for D-Glucose detection. Decorated NPs exhibits unique physicochemical properties with enhanced surface area that attributes towards its better catalytic properties. Furthermore, modified V2O5 NPs surface with 2-Amino-1,3,4-thiazole derivatives facilitate efficient electron transfer and provides enhanced selectivity, sensitivity and repeatability towards glucose molecules that had been analyzed via. cyclic voltammetry and amperometry. Effect of different glucose concentration and scan rate at different time interval had been studied that illustrates the stability and sensitivity of NPs. Limit of detection (LOD), limit of quantification (LOQ), linear dynamic range (LDR), and durability has been acquired by a dependable current–voltage (I–V) process. Fabricated NPs shows potential for use in glucose sensing applications and advances biosensor technology to support the enzyme-free sensing technology.
(Invited) Skin-Interfaced Wearable Sweat Biosensors
Authors: Gao Wei
Published: August 2024

The rising research interest in personalized medicine promises to revolutionize traditional medical practices. This presents a tremendous opportunity for developing wearable devices toward predictive analytics and treatment. In this talk, I will introduce our efforts in developing wearable biosensors for non-invasive molecular analysis. Such wearables can autonomously access body fluids (e.g., human sweat) across the activities and continuously measure a broad spectrum of analytes including metabolites, nutrients, hormones, proteins, and drugs. I will highlight our recent works in the design of wearable and wireless devices for the real-time electrochemical detection of picomolar-level proteins (i.e., inflammatory biomarker C-reactive) and hormones (i.e., estradiol) in sweat. Laser engraving, inkjet printing, and direct-ink-writing 3D printing are used to manufacture high-performance nanomaterials-based biosensors at large scale and low cost. The clinical value of our wearable systems is evaluated through various human trials toward precision nutrition, stress/mental health assessment, chronic disease management, and drug personalization. I will also discuss our research progress on energy harvesting from the human body and the environment to realize battery-free wireless wearable sensing. These wearable technologies could open the door to a wide range of personalized monitoring, diagnostic, and therapeutic applications.