bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Site-Selective Introduction of MnO2 Co-Catalyst to Gold Nanocubes for Enhanced Plasmonic Photocatalysis
Authors: Tatsuma Tetsu , Nishi Hiroyasu 
Published: September 2023

Plasmon-induced charge separation (PICS) is known to take place at the interface between a nanoparticle exhibiting localized surface plasmon resonance (LSPR) and a semiconductor such as titanium oxide.1 PICS has been applied to photovoltaics, photocatalysis, and so on.2 For energy harvesting based on plasmonic photocatalysis, it is important to optimize geometrical arrangements of the plasmonic nanoparticles, semiconductor, and co-catalyst if any, to enhance the charge separation efficiency and minimize charge recombination probability.
Since LSPR confines light to a nanoscale region smaller than visible light wavelength, PICS allows one to fabricate plasmonic materials in nanoscale beyond the diffraction limit.3-7 We have reported fabrication of wide variety of plasmonic nanostructures via site-selective reactions such as oxidative dissolution of silver and oxidative deposition of lead oxide.
In the present work, gold nanocubes were adsorbed onto a thin film of titanium oxide to obtain a plasmonic photocatalyst. Then, lead oxide was deposited on the top or bottom part of the gold nanocube via the site-selective oxidation of lead ions based on PICS. Lead ions in the deposited lead oxide were replaced with manganese ions by galvanic replacement and the lead oxide was transformed to manganese oxide. The manganese oxide moieties on the gold nanocubes serve as co-catalyst of the plasmonic photocatalyst.
We examined photocatalytic currents for ethanol oxidation by PICS. As a result, the photocurrents were enhanced by introducing manganese oxide to the top part of the gold nanocubes. In marked contrast, the photocurrents were suppressed when the manganese oxide was introduced to the bottom part of the nanocubes. In the latter case, charge recombination occurs between the holes injected to manganese oxide and the electrons injected to titanium oxide. On the other hand, the charge recombination is suppressed in the former case, because manganese oxide is not directly contact with titanium oxide. Thus we found that the position of a co-catalyst greatly affect the activity of plasmonic photocatalysts.8

1. Y. Tian and T. Tatsuma, J. Am. Chem. Soc., 127, 7632 (2005).
2. T. Tatsuma, H. Nishi, and T. Ishida, Chem. Sci., 8, 3325 (2017) [review].
3. I. Tanabe and T. Tatsuma, Nano Lett., 12, 5418 (2012).
4. K. Saito, I. Tanabe, and T. Tatsuma, J. Phys. Chem. Lett., 7, 4363 (2016).
5. H. Nishi, M. Sakamoto, and T. Tatsuma, Chem. Commun., 54, 11741 (2018).
6. K. Saito and T. Tatsuma, Nano Lett., 18, 3209 (2018).
7. T. Tatsuma and H. Nishi, Nanoscale Horiz., 5, 597 (2020) [review].
8. K. Kim, H. Nishi, and T. Tatsuma, J. Chem. Phys., 157, 111101 (2022).
(Invited) Ultrafast Charge Transfer Dynamics in WS2–Au Nanohybrid System Fabricated by Pulsed Laser Ablation in Liquid
Authors: Furube Akihiro , Sasaki Kohei , Kokufu Tatsuki , Katayama Tetsuro , Pankaj Koinkar 
Published: September 2023

Nanosheet semiconductor materials have attracted much attention in recent years due to their unique optical, electronic, and chemical properties for various applications such as photodetectors, light emitters, photocatalysts, and biosensors. We have fabricated tungsten disulfide (WS2) nanostructures by pulsed laser ablation in liquid. We applied nanosecond and femtosecond lasers and found the latter to be suitable for nanosheet fabrication [1]. Visible light response was enhanced by attaching gold nanoparticles (AuNPs) onto WS2 nanosheets [2]. The charge transfer dynamics in the WS2-Au nanohybrid system was characterized using femtosecond diffuse reflectance spectroscopy. The nanosheet structure was found to reduce the bulk carrier property. Furthermore, modification with AuNPs was found to enhance the formation of carriers trapped deeply in the WS2 nanosheets. These findings will be useful for the design of future metal-nanosheet semiconductor hybrid systems.
Reference

Pankaj Koinkar, Kohei Sasaki, Tetsuro Katayama and Akihiro Furube, International Journal of Modern Physics B, 35, 2140007 (2021)

Tatsuki Kokufu, Daichi Nakayama, Tetsuro Katayama, Koinkar Pankaj, and Akihiro Furube, The 13th Asia-Pacific Conference on Near-Field Optics, OL30-A13 (2022)
(Invited) Semiconductor Heterostructures for Photocatalysis Applications
Authors: Hsu Yung-Jung 
Published: September 2023

With the inherently high degree of complexity, heterostructures composed of two or more materials joined in unique architectures may exhibit superior synergetic properties that are difficult or impossible to acquire from their individual constituents [1-3]. For semiconductor heterostructures, the relative band alignment of the constituents promotes effective charge separation to bring them desirable properties for photocatalysis applications. Several representative works from our lab will be introduced to demonstrate the promising potentials of semiconductor nanoheterostructures.
References: (Times New Roman, 11pt)
[1] Chun-Wen Tsao, Mei-Jing Fang, Yung-Jung Hsu*, “Modulation of interfacial charge dynamics of semiconductor heterostructures for advanced photocatalytic applications”, Coordination Chemistry Reviews 2021, 438, 213876 (Invited Review).
[2] Mei-Jing Fang, Chun-Wen Tsao, Yung-Jung Hsu*, "Semiconductor Nanoheterostructures for Photoconversion Applications", Journal of Physics D: Applied Physics 2020, 53, 143001 (Invited Review).
[3] Yi-An Chen, Yu-Ting Wang, Hyun Sik Moon, Kijung Yong, Yung-Jung Hsu*, "Yolk-shell nanostructures: synthesis, photocatalysis and interfacial charge dynamics", RSC Advances 2021, 11, 12288-12305 (Invited Review; selected as themed collections of Photocatalysis).
Investigations of Charge Transfer Processes on Plasmonic Cathode Electrodes
Authors: Minamimoto Hiro , Tajiri Yuto , Sato Daiki , Murakoshi Kei , Mizuhata Minoru 
Published: September 2023

The establishment of efficient light energy conversion system is an important issue in the field of photoelectrochemical region. For the realization of it, the wide-band semiconductor electrode could be the good candidate. However, semiconductor electrodes often have the limitation to the ultraviolet region because of their band gap energy. Because the sunlight energy mainly consists of visible light, the visible-light induced photoenergy conversion is a challenging issue. As the breakthrough for it, recently, the combination of the plasmonic metal nanostructures with wide semiconductor electrodes has been received much attention because of the addition of visible light response characters. Up to now, the various systems of the anodic reaction controls have been established. Recently, the cathode system which can control the reduction reactions at metal semiconductor interfaces have been reported via the introduction of plasmonic metal nanostructures into the p-type semiconductor electrodes. In our previous study, we have established the plasmonic photocathode by using the Ag nanostructures with the p-type GaP electrode [1]. In this system, it can be considered as the holes excited in the metal structures injected into the valence band of the p-type semiconductor and the remained electron are consumed in the hydrogen evolution reaction. In addition, we have observed the unique pH dependence on the hydrogen evolution which could not be observed on conventional metal electrodes. For understanding the unique reaction selectivity on the plasmonic cathode electrode, the detail understanding about both the charge transfer process and absolute electrochemical potential of generated electrons. In this study, we have attempted to obtain such information through the various chemical reactions using the various types of plasmonic structures. Through the various photoelectrochemical measurements, we have confirmed the changes in the electrochemical potential of excited electrons depending on the optical characters of plasmonic structures. The unique molecular selectivity was also observed. Our current research would provide the novel insight for the accurate design of the high efficient visible light conversion device.
[1] H. Minamimoto et al., Chem. Lett., 2020, 49, 806.
Microstructure and the Plating/Stripping Behavior of Magnesium Metal Negative Electrode for Rechargeable Magnesium Batteries
Authors: Chang Yung-Jen , Huang Yu-Shan , Chu Peng-Wei 
Published: September 2023

Recently, rechargeable magnesium (Mg) battery systems attract lots of attention owing to their promising theoretical energy density, low cost from the natural abundance of Mg, and less dendritic growth of Mg during charging. Nevertheless, rechargeable Mg battery systems suffer from sluggish reaction kinetics on the electrodes and poor cycle life, which greatly limit their practical competitiveness. Most studies focus on the development of novel electrolytes and their feasibility for rechargeable Mg batteries, while the plating/stripping behavior of Mg metal negative electrode during the charge/discharge cycle is relatively less studied.
Therefore, in this research, the platting/stripping behavior of the Mg metal electrode and the resultant surface microstructure after cycling were investigated in an all phenyl complex (APC) (PhMgCl + AlCl3 in THF) electrolyte. A Swagelok-type Mg||Mg symmetric cell was used in this study with an air-free transfer system to prevent the charged/discharged electrode from oxidation when moving to a scanning electron microscope (SEM) to observe the surface microstructure.
When discharging the pristine pure Mg electrode, the stripping was found to be highly localized with numerous discharge holes on the electrode surface. Interestingly, in the subsequent charging stage, the platted Mg preferentially deposited along the circumferences of the discharge holes, which might be related to the distribution of Mg species right after discharge and the surface conditions of the discharged surface. Later discharge was found to preferentially strip the platted Mg and leave marks around the discharge holes. In addition to cycling on a pure Mg electrode, the platting/stripping behavior and the resultant microstructure of Mg metal deposited on a copper (Cu) current collector were also studied and will be discussed for potential anode-free Mg battery applications. Regardless of the platting/stripping conditions, no dendritic Mg was found during the charge/discharge cycles.

Figure 1
Al-Fe Based Molten Salts for Long Duration Energy Storage
Authors: Maraschky Adam M. , Small Leo J. , Spoerke Erik D. , Percival Stephen J. 
Published: September 2023

There is a need for high energy density long duration energy storage that utilizes earth abundant elements, such as Al and Fe. Energy storage devices that utilize molten salt electrolytes can take advantage of these earth abundant materials and promise to deliver high energy densities. Continued development and in-depth investigation of these fully inorganic, molten salt electrolytes is necessary for the continued progress of low-cost battery technologies. We have been exploring the properties of a new molten salt system which utilizes Al and Fe components and can feasibly be operated as an electrochemically active medium for long duration energy storage. Ternary molten salt compositions of AlCl3-FeCl3-NaCl and AlCl3-FeCl2-NaCl were evaluated for their phase behavior and electrochemical performance at intermediate temperatures (~160 - 210 °C). We found that certain compositions of AlCl3-FeCl3-NaCl were fully or nearly fully molten at 160 °C and that more AlCl3 was needed in the melt to facilitate the FeCl2 dissolution. The electrochemistry of these salts was probed and found that the Fe species will cycle between the Fe3+/Fe2+ oxidation states (as FeCl3/FeCl2) but that at lower temperatures, the FeCl2 will precipitate out of the melt and block the electrode. By increasing the test temperatures, the produced FeCl2 dissolves into the melt allowing the un-blocked electrode to sustain large reduction currents. Future work will investigate ways to increase FeCl2 concentration in the melt and to facilitate its oxidation in order to optimize the molten salt catholyte electrochemical behavior and demonstrate it in a working battery.
This work was supported by the U.S. Department of Energy’s Office of Electricity through the Energy Storage Research Program, managed by Dr. Imre Gyuk. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly-owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.
SAND2022-16623 A
Uncertainty Weighted Distribution of Relaxation Time Analysis of Battery Impedance Spectra Using Gaussian Process Regression for Noise Estimation
Authors: Bartsch Christian Hippolyt , Jin Limei , Bereck Franz Philipp , Mertens Andreas , Eichel Rudiger-A , Scheurer Christoph , Granwehr Josef 
Published: September 2023

A common technique for characterizing electrochemical systems is the combination of electrochemical impedance spectroscopy (EIS) and equivalent circuit modeling (ECM). However, choosing a suitable electrical circuit usually requires a-priori knowledge of the investigated system. By combining ECM with a distribution of relaxation times (DRT) analysis, relevant features found in the impedance data can be distinguished more clearly and, ideally, their number can be determined.
Since the data acquired by EIS shows heteroscedastic noise behavior, using uniform weighting in the DRT can result in either under- or overregularization of certain parts of the data. This can lead to a significant misinterpretation of the system. To account for that, the frequency-dependent noise is estimated with statistical noise characterization by obtaining multiple EIS spectra of a commercial Lithium-ion coin cell at the same SOC. Since repeating a multitude of measurements in a real-life application is often impractical due to time constraints, Gaussian process regression (GPR) using only a single data set is introduced as an additional method for noise estimation.
It is shown that incorporating noise-weighted DRT analysis into ECM parameterization facilitates the choice of suitable equivalent circuits and can yield a more robust parameterization of the investigated system. Additionally, the use of GPR for noise estimation can supply sufficiently accurate results with the use of minimal input data.

Figure 1
Non-Nucleophilic Electrolytes with Non-Fluorinated Hybrid Solvents for Long-Life Magnesium Metal Batteries
Authors: Sun Yue , Lu Yi-Chun 
Published: September 2023

Growing energy demands and the widespread of renewable power sources call for high-energy storage systems beyond lithium-ion batteries (LIBs). Rechargeable magnesium batteries (RMBs) are high-energy, safer, and more cost-effective alternatives to LIBs and lithium metal batteries (LMBs) thanks to Mg’s high volumetric capacity (3832 mAh cm-3)1, low theoretical potential (-2.37 V vs SHE)2 and earth-abundance3. Non-nucleophilic and non-fluorinated compounds are the most important class of materials to enable sustainable rechargeable magnesium (Mg) batteries, however, they suffer from poor stability due to the formation of unstable solid-electrolyte-interphase (SEI).4 Here, we design a hybrid-solvent electrolyte by dispersing a non-nucleophilic solution in a non-fluorinated weakly-coordinating solvent to prevent parasitic reactions and form stable SEI. This strategy significantly improved the cycle life of the Mg anode from 24 to 4000 hours (in Mg-Mg symmetric cells) and realized a stable cycle life of Mg-Mo6S8 full cells for more than 2300 hours with an average CE of 99.96%. The non-fluorinated weakly-coordinating solvent suppressed uneven Mg growth and contributed to the formation of polymeric SEI, which filled the cracks of pristine SEI, preventing side reactions and passivation. This strategy revealed the critical role of weakly-coordinating solvents in stabilizing Mg anode for reversible Mg batteries.

References:

[1] H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky, A. G. Oliver, W. C. Boggess, J. Muldoon, Nat. Commun., 2 (2011) 427-433.
[2] R. Attias, M. Salama, B. Hirsch, Y. Goffer, D. Aurbach, Joule, 3 (2019) 27–52.
[3] W. Guo, S. Chen, N. Hussain, Y. Cong, Z. Liang, K. Chen, Plant Signal. Behav., 10 (2015) e992287.
[4] Z. Lu, A. Schechter, M. Moshkovich, D. Aurbach, J. Electroanal. Chem., 466 (1999) 203–217.

Acknowledgments:

This work is supported by a grant from the Innovation and Technology Commission of the Hong Kong Special Administrative Region, China (Project No. ITS/219/21FP).
Hydrogen Exchange and Diffusion Kinetics at Elevated Temperatures in Proton-Conducting Solid Oxide Materials
Authors: Yatoo Mudasir A , Skinner Stephen J 
Published: September 2023

Storage of purified hydrogen is one of the central challenges in addressing climate change and reducing our reliance on fossil fuels for energy conversion and storage, and therefore there is a global surge in research and development concerning hydrogen purification and storage. In this regard, we are studying proton conduction in solid oxide materials at elevated temperatures for applications in hydrogen separation and compression membranes. Hydrogen compression is the most recommended method to store hydrogen for automotive applications as it allows an increase in the hydrogen volumetric energy density.
Traditionally the protonic conductivity in these materials is measured by indirect methods. For example, conductivity measurements in mixed gas atmospheres, comparing for example dry N2 with humidified N2, thereby allowing the contribution of protons to be evaluated. In this study, we for the first time report the evaluation of protonic conductivity in BaZr1-xCexY0.2O3−δ, BaZr0.1Ce0.7Y0.2–xYbxO3–δ and Ba7Nb4MoO20 by direct measurements afforded by the Isotope Exchange Depth Profiling technique with deuterium labelling. We also report the kinetics of H/D transport through the bulk materials and across metal-ceramic interfaces with a particular interest in the behaviour of the interface between the key Pd/Pd alloy catalyst component and the hydrogen-transporting oxide ceramic material. The transport and interface behaviour information will be of significance in designing hydrogen separation and compression membranes.

Figure 1
(Digital Presentation) Renewable Itaconic Acid As a Cathode Additive Stabilizing Ni-Rich Layered Cathode Materials for Lithium-Ion Batteries
Authors: Han Yongkang Kang , Xiao Qiang Feng 
Published: September 2023

Renewable materials applied in lithium-ion batteries industry has obvious advantages because of its wide range of sources and low cost. The residual lithium compounds on the surface of nickel-rich LiNi1-x-yCoxMnyO2 (Ni-rich NCM) cathodes hinder its large-scale industrial application in lithium-ion batteries. In the past, researchers proposed several approaches including coating (Al2O3, Li3PO4), water washing coupling heat treatment. These conventional approaches have been found beneficial for mitigating the residual lithium and improving electrochemical performance of high rich nickel cathode. However, most of these used conventional additions are non-renewable precious metal or salt accompanied by extra processing/handling costs. More seriously, layer Ni-rich NCM cathodes cost more than lithium iron phosphate, because transition nickel salt is expensive. Obviously, it is crucial for Ni-rich NCM cathodes to develop green and low-cost modification process.
In this work, renewable itaconic acid (IA) as a cathode addition is used to convert the residual lithium on the Ni-rich NCM cathodes into sacrificial organic lithium salts containing polar carboxylic acid and unsaturated carbon-carbon double bond to build the Li conductive cathode-electrolyte interphase (CEI) rich in organic component containing polycarbonates/polymeric specie during the electrochemical process. As a result, the capacity of the 0.5wt% IA modified NCM cathode retains 94.1 % after 90 cycles. Itaconic anhydride, an important renewable resource, is widely used in food processing and other fields because of its wide range of sources and low price. As such, our work proposes a practical approach to mitigates residual lithium issue and control CEI formation, developing high energy and long spans lithium-ion batteries by utilizing cheap and renewable organic acid.

Figure 1
Solid-State Electrochemistry on Supramolecular Assemblies with Strong Isotropic Property
Authors: Awaga Kunio 
Published: September 2023

It has been mathematically proven that only honeycomb, diamond, and K4 lattices have a special symmetry called "strong isotropy". Note that crystallographic symmetry is determined only by the position of atoms, while strong isotropy is governed by both the position of atoms and bonds. The K4 lattice, called by various names such as gyroid lattice and srs network, is characterized by the fact that it exhibits chirality. It is recognized that their mathematically-defined “line graphs” correspond to kagome, hyper-kagome, and pyrochlore lattices, respectively, which are well known as spin frustration lattices. This relation suggests that the materials with the strong isotropic lattices possess “hidden” frustration. It is also noteworthy that the band structure of the three lattices contains exotic band dispersions such as Dirac cones due to their lattice symmetry, and that they possess porous structures. From this perspective, we proposed to form the supramolecular assemblies with the with strong isotropic property, and to carry out electrochemical valence control for realizing exotic physical properties such as Dirac electron, spin frustration, etc.
In this presentation, we will explain our previous works on the solid-state electrochemistry of LiPc as an introduction. Then, we will report the rational synthesis of the molecule-based honeycomb and K4 structures, using MOF/COF- and supramolecular-chemistry, the nanohybridization using their porous structures, the physical properties such as spin frustration and circularly polarized luminescence, and the solid-state electrochemical redox control on them without destroying the original frameworks.