bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Designing Redox-Active Organic Molecules (ROMs) for Fast-Charging Battery Electrodes with High Stability
Authors: Kwon Ji Eon 
Published: December 2024

Redox-active organic molecules (ROMs) are drawing significant attention as promising alternatives to conventional transition metal oxide electrodes. Their appeal stems from numerous benefits including abundance, sustainability, biocompatibility, cost-effectiveness, and ease of chemical tunability. Notably, their flexible nature with large free volume, owing to loosely packed intermolecular structures, is expected to facilitate fast diffusion of charge-carrying ions – a key attribute for enhancing the high-rate performance of electrode materials. Yet, the practical application of ROMs is hindered by their slow rate capability with limited capacity utilization, a consequence of their intrinsically electron insulating properties. Furthermore, the high solubility of ROMs in organic electrolytes has caused rapid capacity fading within the first few cycles, compelling one to prepare polymers via complicated synthesis and/or to fabricate composites with expensive nanocarbons. These factors increase production costs and significantly deteriorate processability in the electrode fabrication process.
In this talk, we introduce novel molecular design strategies to improve both cycle stability and rate performance in simple small molecule ROMs, paving the way for the development of fast charging batteries.
(Invited) Rapid Photochemical Control of Surface Chemical Properties and Molecular Assembly Formation Using Novel Amphiphilic Lophine Dimers
Authors: Sakai Hideki , Sakai Kenichi , Akamatsu Masaaki 
Published: December 2024

Photo-induced rapid control of molecular assemblies formed by amphiphilic molecules, such as micelles and vesicles, enables effective and on-demand release of drugs or active components, with applications such as drug delivery systems (DDS) and cosmetics1). Thus far, no attempts to optimize the responsiveness of photoresponsive molecular assemblies have been reported. We previously reported photoresponsive surfactants bearing a lophine dimer moiety that exhibit fast photochromism in confined spaces, such as inside a molecular assembly. However, rapid control of the micelle structures and solubilization capacity have not yet been demonstrated.
In the present study, photo-induced morphological changes in micelles were monitored using in-situ small-angle neutron scattering (SANS) and UV/Vis absorption spectroscopy2,3). An amphiphilic lophine dimer (3TEG-LPD) formed elliptical micelles. These were rapidly elongated by ultraviolet light irradiation, which could be reversed by dark treatment, both within 60 s (Fig. 1). For a solution of 3TEG-LPD micelles solubilizing calcein as a model drug molecule, fluorescence and SANS measurements indicated rapid release of the incorporated calcein into the bulk solvent under UV irradiation. Building on these results, we investigated rapid controlled release via hierarchical chemical processes: photoisomerization, morphological changes in the micelles, and drug release. This rapid controlled release system allows for effective and on-demand DDS.
References
1) M. Akamatsu, K Sakai, H Sakai, Chemistry Letters, 52 (7), 573 (2023). (Highlight Review)
2) M. Akamatsu, K. Kobayashi, H. Iwase, Y. Sakaguchi, R. Tanaka, K. Sakai, H. Sakai, Scientific Reports, 11:10754 (2021).
3) H. Iwase, M. Akamatsu, Y. Inamura, Y. Sakaguchi, K. Kobayashi, H.Sakai, Langmuir 39 (35), 12357 (2023).

Figure 1
(Invited) Influence of Hydrogen Bond Networks on Hydrogen Evolution Reaction in Aqueous Systems
Authors: Ikeda Katsuyoshi 
Published: December 2024

Hydrogen evolution reaction (HER) is one of the key issues to achieve “carbon neutrality”. Driving the electrocatalytic HER in aqueous solutions with solar-energy cells is considered as a green and sustainable way to produce hydrogen molecules (H2). To achieve effective H2 production, it is required to reduce HER overpotential using appropriate heterogeneous electrocatalysts such as Pt. The HER activities of catalytic metals have a strong correlation with the hydrogen adsorption free energies on their surfaces, which is known as a so-called volcano-like relation. Because the optimum adsorption energy and hence maximum HER activity are found at the top of the volcano, most of the studies to develop electrocatalysts focus on tuning of the adsorption energy. However, the hydrogen adsorption step, i.e., discharge reaction of proton, at the surface is strongly influenced by hydrogen bonding with the bulk phase of liquid water. Recently, we have developed a surface-selective THz-vibrational spectroscopy based on surface-enhanced Raman scattering, which can obtain dynamical and structural information on hydrogen bond networks of water at interfaces with the frequency range of 10 - 100 cm-1 (0.3 – 3 THz) [1-6]. Using this technique, we have examined the potential-induced behavior of interfacial hydrogen bonds under the HER process on various metal surfaces with different HER activities and found that there is a correlation between the HER activities and hydrogen bond structures at interface. The details will be discussed in the presentation. We will also present a new strategy to produce hydrogen gas more efficiently using a non-traditional electrochemical cell structure.
[1] M. Inagaki, K. Motobayashi, K. Ikeda, J. Phys. Chem. Lett., 8, 4236-4240 (2017).
[2] M. Inagaki, T. Isogai, K. Motobayashi, K. -Q. Lin, B. Ren, K. Ikeda, Chem. Sci., 11, 9807-9717 (2020).
[3] M. Inagaki, K. Motobayashi, K. Ikeda, Nanoscale, 12, 22988-22994 (2020).
[4] R. Kamimura, T. Kondo, K. Motobayashi, K. Ikeda, Phys. Status Solidi B, 259, 2100589 (2022).
[5] T. Kondo, M. Inagaki, K. Motobayashi, K. Ikeda, Catal. Sci. Technol., 12, 2670-2676 (2022).
[6] T. Isogai, M. Inagaki, M. Uranagase, K. Motobayashi, S. Ogata, K. Ikeda, Chem. Sci. 14, 6531-6537 (2023).
Unique Photothermal Materials for Cutting-Edge Interfacial Solar Desalination and Wastewater Purification
Authors: Tatachari Santhanagopalan Shridharan , Ho Lee , Tan Runfa , Sivanantham Arumugam , Cho In Sun 
Published: December 2024

Harnessing renewable solar energy for solar desalination shows great promise for addressing freshwater scarcity. However, conventional solar desalination suffers from low photothermal conversion and excessive heat dissipation, limiting its practicality for meeting water demand. Interfacial solar steam generation (ISSG) has emerged to address these limitations, leveraging advances in photothermal absorber materials, structural design, and thermal management. The photothermal material (PTM) plays a crucial role as it facilitates the conversion of solar energy into localized heat energy, leading to water evaporation within a localized high-temperature zone.1 In this talk, we present unique photothermal absorber materials that are not common for ISSG, such as bismuth copper oxysulfide (BiCuSO; BCSO), silicon (Si), and red phosphorus (RP), exhibiting broad light absorption, low thermal conductivity, and high heat localization. 2–5 We employed a mechanochemical activation method to regulate particle size and surface defects simultaneously, thus enhancing the optical, thermal, and photothermal properties. Utilizing the 1D water path architecture, we achieved an outstanding water evaporation rate of 2.2 (photothermal efficiency: 107.9%), 1.77 (96%), and 1.75 kg/m2·h (94.0%) using Si, BCSO, and RP absorber materials, respectively, under 1 sun illumination (100 mW/cm2). Furthermore, our photothermal absorbers demonstrated excellent ion rejection capabilities when subjected to continuous measurement for 50 h with both seawater and industrial wastewater. The emerging interface solar-driven steam generation technology promises to meet future human needs for freshwater, energy, and environmental sustainability.

Keywords: Photothermal materials; Mechanochemical activation; Defect control; Interfacial solar desalination; Wastewater purification.

References:

1 X. Cui, Q. Ruan, X. Zhuo, X. Xia, J. Hu, R. Fu, Y. Li, J. Wang and H. Xu, Chem. Rev., 2023, 123, 6891–6952.
2 T. S. Shridharan, M. J. Kang, A. Sivanantham, S. Kim and I. S. Cho, Desalination, 2022, 540, 115984.
3 T. S. Shridharan, A. Sivanantham, R. Tan, S. Y. Hong, D. H. Kim and I. S. Cho, Desalination, 2023, 561, 116700.
4 T. S. Shridharan, A. Sivanantham, J. H. Lee, S. Y. Hong, Y. J. Jeong, S. S. Shin and I. S. Cho, Chem. Eng. J., 2024, 486, 150247.
5 T. S. Shridharan, J. H. Lee, R. Tan, A. Sivanantham, H. S. Han, H. S. Jung and I. S. Cho, Desalination, 2024, 579, 117464.

Figure 1
(Invited) Cleaning Coastal Environments through Electrocatalysis and Electromicrobiology
Authors: Nakamura Ryuhei 
Published: December 2024

Coastal environments play an increasingly important role in the world's food supply. However, excessive inputs of carbon and nitrogen compounds to the seafloor are severely damaging the benthic ecosystem, causing eutrophication, algal blooms and red tides. Therefore, the development of new technologies to maintain the health of the benthic ecosystem is essential for sustainable use of marine resources. In this study, we investigated the redox homeostasis of benthic ecosystems using a marine oligochaete as a model benthic organism to assess the ecological resilience of aquafarms to nutrient influx. Real-time monitoring of the redox potential of a model benthic ecosystem allowed assessment of the homeostatic response of the system to nutrient addition. We also found that the movement and metabolic activity of benthic animals can be controlled by artificially manipulating the redox potential of the sediments. Further, we have developed electrocatalysts for nitrification, denitrification, and anaerobic ammonium oxidation to alleviate the nitrogen nutrient imbalance in marine environments. Given the importance of benthic animals in maintaining coastal ecosystems, electrochemical monitoring, and physiological regulation of marine oligochaetes, together with the electrocatalytic control of nitrogen cycling, could provide an intriguing approach towards sustainable use of marine resources.
Reference

Shono, M. Ito, A. Umezawa, K. Sakata, A. Li, J. Kikuchi, K. Ito, R. Nakamura, Tracing and regulating redox homeostasis of model benthic ecosystems for sustainable aquaculture in coastal environments, Front. Microbiol., 13:907703. DOI: 10.3389/fmicb.2022.907703

He, H. Ooka, Y. Li, Y. Kim, A. Yamaguchi, K. Adachi, D. Hashizume, N. Yoshida, S. Toyoda, S. H. Kim, R. Nakamura, Regulation of the electrocatalytic nitrogen cycle based on sequential proton–electron transfer, Nat. Catal., 2022, 5, 798-806.

He, K. Adachi, D. Hashizume, R. Nakamura, Copper sulfide mineral performs nonenzymatic anaerobic ammonium oxidation through a hydrazine intermediate. Nat.Chem (in press)
(Invited) Human-AI-Robotics Collaboration for Catalysts Discovery in Electrochemical Reactions
Authors: Zhang Zhen , Ren Zhichu , Li Ju 
Published: December 2024

The exploration and discovery of materials for electrochemical reactions have traditionally been a tedious and time-intensive process. The complexity inherent in the design of materials with high-dimensional parameters and the exhaustive nature of data acquisition are the primary causes of this bottleneck [1]. To overcome this challenge, we introduce the Copilot for Real-world Experimental Scientist (CRESt). CRESt employs a large multimodal model (LMM) to guide a robotic system that is adept at active learning (driven by the Gaussian process-Bayesian optimization process), thereby streamlining the entire workflow—ranging from the selection of composition through to the high-throughput synthesis of materials, electrochemical screening, materials characterization, and device testing—for the optimization of electrocatalysts (see video demonstrations in [2-4]). Through this method, we have been able to rapidly screen thousands of catalysts with minimal human intervention. Our development of high entropy alloy catalysts, which comprise more than five elements, have demonstrated exceptional performance in applications such as direct formate fuel cells and alkaline water electrolyzers. This strategy holds the promise of broad implementation across a spectrum of electrochemical systems.
Reference:
[1] Ren, Z., Ren, Z., Zhang, Z. et al. Autonomous experiments using active learning and AI. Nat. Rev. Mater.
8, 563–564 (2023).
[2] https://www.youtube.com/watch?v=iRauT95ECmo&t=82s
[3] https://www.youtube.com/watch?v=POPPVtGueb0&t=340s
[4] https://www.youtube.com/watch?v=sibCICesrEY
(Invited) Insights from Cyclic Voltammetry into Active Sites on Carbon Electrodes and Their Importance in Vanadium Flow Batteries and Other Electrochemical Applications
Authors: Al Hajji Safi Maria , Bourke Andrea , Buckley D. Noel , Lynch Robert P. 
Published: December 2024

Flow battery technology is uniquely positioned to fill the niche of long duration energy storage that will be needed to enhance grid reliability and power quality. Vanadium Flow Batteries (VFBs) and other flow battery technologies use carbon as their electrodes. The behaviour of carbon as an electrode is complex and there is considerable variation in the literature regarding the kinetics of flow battery reactions at carbon electrodes.
The electrochemical response of a carbon electrode towards redox reactions is known to be improved after electrochemical treatments. For the past decade we have investigated the effect of electrochemical treatment on the electrode activity of carbon towards vanadium redox reactions. We have reported that cathodic treatment in acidic solution enhances the kinetics of the positive (VIV-VV) electrode in VFBs but inhibits the kinetics of the negative (VII-VIII) electrode, while anodic treatment inhibits the kinetics of the positive electrode but enhances the kinetics of the negative electrode1-3. We also showed that the activity of carbon-based material is strongly dependent on the surface history, and in particular on the most positive and the most negative potential used to treat an electrode4.
In this presentation, we report some interesting results from our investigations of carbon electrode pretreatment in H2SO4. The cyclic voltammetry behavior which we observe shows a remarkable correlation with kinetics measurements in vanadium-containing electrolytes. We believe that our results provide a novel method of investigating the behavior of active sites on carbon electrodes. This is particularly important in the context of flow battery electrodes but may also, in a much broader context, provide a route to understanding the electrocatalytic behavior of carbon electrodes in many other applications.
References.

A. Bourke, M. A. Miller, R. P. Lynch, X. Gao, J. Landon, J. S. Wainright, R. F. Savinell and D. N. Buckley, J. Electrochem. Soc.
163, A5097 (2016).

A. Bourke, M. A. Miller, R. P. Lynch, J. S. Wainright, R. F. Savinell and D. N. Buckley, J. Electrochem. Soc., 162, A1547 (2015).

M. A. Miller, A. Bourke, N. Quill, J. S. Wainright, R. P. Lynch, D. N. Buckley and R. F. Savinell, J. Electrochem.
Soc., 163, A2095 (2016).

M. Al Hajji Safi, A. Bourke, D. N. Buckley, R. P. Lynch, ECS Trans., 109, 67-84 (2022).
Direct Surface Sulfidation of Layered Metal Hydroxides Using Bis(trimethylsilyl) Sulfide
Authors: Muramatsu Keisuke , Sugimoto Wataru 
Published: December 2024

Layered transition metal hydroxides have been extensively researched for applications such as electrodes and electrocatalysts owing to their tunable redox properties based on various cation compositions. To control critical physical properties such as chemical adsorption and conductivity in these applications, topochemical control of anion compositions will be effective. While many reports have demonstrated the synthesis of nitrides and sulfides by reacting layered metal hydroxides with different anion sources, the existing methods often result in the formation of microcrystalline aggregates.1 Even under mild conditions, core-shell structures are formed through dissolution and reprecipitation.2 Hence, it is necessary to develop a new approach that allows direct reaction of anionic species with metal species in the crystal framework. In this study, we propose a reaction using bis(trimethylsilyl) sulfide ((Me3Si)2S), commonly used for preparation of metal sulfide nanoparticles,3 as a sulfur source for the direct sulfidation of layered metal hydroxides.
Layered nickel hydroxide nanocrystals (Ni(OH)2nc) were reacted in a liquid phase with a desired amount of (Me3Si)2S. The product is denoted as S_Ni(OH)2nc. X-ray diffraction (XRD) patterns of S_Ni(OH)2nc shows that all peaks corresponded to β-Ni(OH)2, and no new peaks appeared. The original Ni(OH)2nc was an aggregate of hexagonal plate-shaped nanocrystals with sizes of 80 to 200 nm and thicknesses of 15 to 25 nm, and no significant changes in crystal morphology after the reaction were observed after the reaction. In contrast to the blue-green color of Ni(OH)2nc, S_Ni(OH)2nc was obtained as a blue-gray powder. X-ray photoelectron spectroscopy (XPS) spectra of S_Ni(OH)2nc revealed new photoelectron peaks attributed to S2p, which were within the range of sulfide compounds. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM-EDS) mapping detected sulfur species at locations corresponding to plate-like crystals. Furthermore, quantitative analysis by EDS estimated the atomic ratio of sulfur to nickel in S_Ni(OH)2nc to be 5.0%, which corresponded well to the proportion of anion sites on the outer surface of Ni(OH)2nc. These results suggest that (Me3Si)2S reacts with Ni on the outer crystal surface of Ni(OH)2nc to form nickel sulfide compounds. Thus, sulfidation of layered metal hydroxides by (Me3Si)2S is effective in controlling the anion composition on crystal surfaces.
(1) Y. Guo, T. Park, J.W. Yi, J. Henzie, J. Kim, Z. Wang, B. Jiang, Y. Bando, Y. Sugahara, J. Tang, and Y. Yamauchi, Adv. Mater., 2019, 31, 1807134. (2) B. Wang, C. Tang, H.-F. Wang, X. Chen, R. Cao, Q. Zhang, Adv. Mater., 2019, 31, 1805658. (3) R. García-Rodríguez, M. P. Hendricks, B. M. Cossairt, H. Liu, and J. S. Owen, Chem. Mater., 2013, 25,1233.
The g-C3N4 @Cdo/ZnO Ternary Composite: Photocatalysis, Kinetics and Acute Toxicity Studies
Authors: Berhanu Sintayehu Berhanu 
Published: December 2024

Binary and ternary nanocomposites (NCs) were synthesized by precipitation and through facile one-pot ultrasonic
assisted methods to serve as photocatalysts for treatment of wastewater as well as their toxicity toward aquatic
organism (Nile tilapia). The crystalline structure, band gap energy and functional groups of these materials were
characterized by XRD, UV-Vis, and FT-IR instrumental techniques. Based on the UV-Vis study, the band gap of
ZnO/CdO (ZC) to hybrid g-C3N4@ZnO/CdO (GZC) nanocomposite was reduced from 3.41 eV to 3.21 eV, sug-
gesting good charge carrier mobility. Photocatalytic degradation performances of ZC and GZC were further
assessed by conducting methyl red (MR) photodegradation reaction using UV light. The highest degradation
efficiency was achieved for GZC NCs (97.78%) than ZC (89.41%) in 2 h. The values of free energy, and enthalpy
were negative; showing spontaneous photodegradation of MR. The kinetics of photodegradation follows pseudo-
first-order reaction with rate order of 0.0713 min1 . The HO* and O2 * were main active species for the photo-
degradation of MR. The toxicity of NCs calculated and the lethal concentration (LC50 ) was 113 ppm after 12 h.
Understanding High Voltage Electrolyte Reactivity on Cation-Disordered Rock Salt Cathodes
Authors: Rastinejad Justin , McCloskey Bryan D. 
Published: December 2024

Li-ion battery demand is expected to increase dramatically to meet rapidly increasing energy storage demands. To address the expense and scarcity of cobalt and nickel used in current layered oxide cathodes, alternative cathode materials that rely on earth-abundant transition metals must be explored. Promising such materials are cation-disordered rocksalt (DRX) oxides, particularly those that are comprised of manganese and titanium, along with lithium excess to allow for high reversible capacities (>300 mAh/g). A substantial fraction of extractable lithium capacity in DRX materials occurs at high voltages, creating high energy density, but also leading to deleterious degradation processes. Recent studies have observed reactivity of the DRX surface when cycled to high voltages: >25% of transition metals migrating out of the cathode and continuous evolution of CO2 after 150 cycles [1]. 13C labeling has identified the carbonate electrolyte as the primary source of the CO2 after the first cycle [2]. This reactivity leads to a sharp increase in impedance and rapid capacity fade [1]. However, the exact cause of high voltage reactivity is still not fully understood for the electrolyte – DRX interface.
In this study, we quantify the surface reactivity of select electrolyte – DRX systems using operando gas measurements and inductively coupled plasma – optimal emission spectrometry (ICP-OES). Through this method, we can identify what electrolyte and DRX properties have the largest influence on surface reactivity. To monitor surface reactivity of the electrolyte, differential electrochemical mass spectrometry (DEMS) was used to quantify evolution of CO2 and other gaseous products during cycling. To track the surface reactivity of the DRX, ICP-OES was used to quantify transition metal dissolution. We show that ethylene carbonate oxidation is particularly problematic above 4.4 V, and that processes involving the conductive carbon, as well as Mn and O redox are culpable. The results of this study provide insight into the primary causes of capacity fade in DRX-based batteries, informing future designs of the electrolyte, DRX, and other cathode materials.
[1]: Matthew J. Crafton et al 2024 J. Electrochem. Soc.
171 020530
[2]: Manuscript in Preparation: Tzu-Yang Huang et al
2024. Chem. Of Mat. (Manuscript ID: cm-2024-007563)
Nucleation Behavior of Pitting and Evolution of Stripping on Lithium Metal Batteries
Authors: Zhang Hanrui , Ulusel Mert , Shi Feifei 
Published: December 2024

The stripping reaction of lithium will greatly impact the cyclability and safety of Li metal batteries. However, lithium pits' nucleation and growth, the origin of uneven stripping, are still poorly understood. In this study, we analyze the nucleation mechanism of Li pits and their morphology evolution with a large population and electrode area (>0.45 cm2). We elucidate the dependence of pit size and density on current density and overpotential, which is aligned with classical nucleation theory. With laser scanning confocal microscope, we reveal the preferential stripping on certain crystal grains and a new stripping mode between pure pitting and stripping without pitting. Descriptors like circularity and the aspect ratio (R) of pit radius to depth are used to quantify the evolution of lithium pits in three dimensions. As pits grow, growth predominates along the through-plane direction, surpassing the expanding rate at the in-plane direction. After analyzing more than 1000 pits at each condition, we validate that the overpotential is inversely related to the pit radius and exponentially related to the rate of nucleation. With this established nucleation-overpotential relationship, we can better understand and predict the evolution of surface area and roughness of lithium electrodes under different stripping conditions. The knowledge and methodology developed in this work will significantly benefit lithium metal batteries' charging/discharging profile design and the assessment of large-scale lithium metal foils. DOI of publication: 10.1021/acsami.4c01530
Acknowledgments: H.Z., M.U., and F.S. thank the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research Program. F.S. thanks the support from the National Science Foundation under Grant No. 2239690.