bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Digital Presentation) Excitonic Photoluminescence Properties of Locally Functionalized Single-Walled Carbon Nanotubes Using Molecular Modifiers
Authors: Shiraki Tomohiro , Hayashi Keita , Niidome Yoshiaki , Aoki Haruka , Fujigaya Tsuyohiko 
Published: July 2022

Excitons in single-walled carbon nanotubes (SWCNTs) show unique properties due to strong quantum confinement and weak dielectric screening effects which give rise to high binding energies based on strong Coulombic interactions. By this feature, stable and mobile excitons are generated in SWCNTs and its radiative recombination produces photoluminescence (PL) in the near infrared (NIR) region. Recently, local chemical functionalization of SWCNTs has attracted great attention because of enhancement of their NIR PL properties.[1-5] This functionalization dopes local defects such as sp3 carbon to the semiconducting sp2 carbon networks of SWCNTs based on the covalent bond formation between the tube walls and modifier molecules. As a result, emissive doped sites that have narrower band gaps and exciton trapping features are created in the locally functionalized SWCNTs (lf-SWCNTs). For lf-SWCNTs, E
11* PL newly appears with red-shifted wavelengths and increased PL quantum yields compared with original E
11 PL of pristine SWCNTs. Currently, chemical functionalization methods and E
11* PL wavelength modulation techniques are being developed for further functionalization of lf-SWCNTs. [1-5] In this presentation, E
11* PL properties of lf-SWCNTs synthesized using newly designed chemical modifiers are discussed. For example, an azide compound is found to produce the emissive doped sites in lf-SWCNTs via a [2+1] cycloaddition reaction. The E
11* PL peak was observed at 1118 nm and N1s peak in X-ray photoelectron spectroscopy was detected around 400 eV regions based on the chemical bond formation. Moreover, solvatochromic PL energy shifts of the E
11* PL showed a different trend from those observed for typical lf-SWCNTs synthesized using diazonium chemistry. This result indicates that the chemical structures of the doped sites could be a key factor to modulate excitonic properties of localized excitons in lf-SWCNTs. Therefore, the molecular chemistry approach would provide unique exciton engineering tools for lf-SWCNTs and develop advanced excitonic NIR materials applicable to quantum cryptography technologies and high-performance bio/medical imaging and sensing.
[1] T. Shiraki, Chem. Lett., 50, 397 (2021); [2] T. Shiraki et al., Acc. Chem. Res., 53, 1846 (2020); [3] S. Tretiak et al., Acc. Chem. Res., 53, 1791 (2020); [4] Y. Wang et al., Nat. Rev. Chem., 3, 375 (2019); [5] J. Zaumseil, Adv. Optical Mater. 2101576 (2021).
(Invited, Digital Presentation) Carbon Nanotube-Based Nanomechanical Signal Receiver
Authors: Funayama Kieta , Tanaka Hiroya , Hirotani Jum , Shimaoka Keiichi , Ohno Yutaka , Tadokoro Yukihiro 
Published: July 2022

Carbon nanotube(CNT) has attracted much attention as one of the nanomaterials for future sensing devices because of their excellent properties. The mechanical vibration of an individual CNT has shown outstanding potential for detecting the force1, mass2, electromagnetic waves3 sensitively via CNT’s elastic and electric properties, chemical stability, and lightweight structure. In terms of communication field, some research groups have suggested the concept of the mechanical signal receiver consisted of CNT3,4,. Although the previous studies have achieved to show the basic demonstration via the detection of electromagnetic signal, there have not been a research that quantitatively evaluates the communication performance and considers the effect of noise has been absent. In addition, it is significant to investigate the comprehensive systems include such CNT-based mechanical sensor.
Herein, we experimentally demonstrate for the first time that a CNT-based signal receiver can transfer a large amount of digital data, 393,216 bits, encoded from a color image5. Although there are some errors in bit decision from the received signal, we successfully decode the original digital image data by combining error collection. In addition, we experimentally evaluate the communication performance of the CNT-based mechanical receiver. The channel capacity obtained by the demonstration indicates that the data-transfer capability approaches the theoretical limitation. The results show that the nanoscale mechanical receiver has great potential for contributing to the incoming new technology relates our life, e.g., internet of things (IoT) and artificial intelligence (AI) by combining with information and communication technology.
1) Jensen, K. Kim, A. Zettl, Nature Nanotecnol.,
3, 533, (2008).
2) Moser, J. Guttinger, A. Eichker, M. J. Esplandiu, D. E. Liu, M. I. Dykman, A. Bachtold, Nature Nanotecnol., 8, 493 (2013).
3) Jensen, J. Weldon, H. Garcia, A. Zwttl, Nano Lett., 7, 3508 (2007).
4) Gouttenoire, T. Barois, S. Perisanu, J.-L. Leclercq, S. T. Purcell, P. Vincent, A. Ayari, Small, 6, 1060 (2010).
5)Funayama, H. Tanaka, J. Hirotani, K. Shimaoka, Y. Ohno, Y. Tadokoro, ACS Appl. Nano Mater., 10.1021/acsanm.1c02563 (2021).
Polyazaacenes Generation By Using Precursor Methods
Authors: Chan Yee Seng , Hayashi Hironobu , Aratani Naoki , Yamada Hiroko 
Published: July 2022

Azaacenes are the analogue of acenes, comprising nitrogen atoms in the carbon-based molecular skeleton, have been gaining attention because of their potential application in organic electronics and material science. However, it is normally difficult to synthesize such large aromatic molecules because of the poor solubility and low stability. On the other hand, we have developed precursor methods to overcome these problems. Briefly, bicyclo[2.2.2]octadiene(BCOD)-fused acenes can be converted its corresponding acenes by thermally induced retro-Diels–Alder reaction, while α-diketone-type precursors can be converted simply by photoirradiation.[1] Significantly, these precursor molecules are often more soluble and stable than its converted forms. More crucially, their corresponding acenes can be prepared quantitatively in solutions or in films, if the precursors are sufficiently pure. So far, by using the precursor methods, we have successfully synthesized polyacenes under anaerobic conditions either at ultrahigh vacuum conditions or at the interior of single crystals to avoid undesirable oxidation of the resulting polyacenes.[2–4]
Here we report a series of tetraazapolyacene precursors synthesis. Briefly, the BCOD moieties were introduced in the tetraazaacenes as the thermally removable leaving group. The possibility of conversion of the precursors into its corresponding tetraazaacenes was examined by thermogravimetric analysis respectively. In addition, α-diketone-type precursor of tetraazaheptacene was also synthesized. Furthermore, we also report the one-pot synthesis of macrocyclic azacyclacene precursor by reacting bis-α-diketo-tetrahydro-diethanopentacene with benzene-1,2,4,5-tetraamine tetrahydrochloride. Here, the targeted compound was clearly confirmed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The obtaining precursor compounds will be subjected to transformation to investigate its optical and physical properties.
References

H. Yamada, D. Kuzuhara, M. Suzuki, H. Hayashi, N. Aratani, Bull. Chem. Soc. Jpn.
2020, 93, 1234–1267.

J. I. Urgel, S. Mishra, H. Hayashi, J. Wilhelm, C. A. Pignedoli, M. D. Giovannantonio, R. Widmer, M. Yamashita, N. Hieda, P. Ruffieux, H. Yamada, F. Roman, Nat. Commun.
2019, 10, 861.

H. Hayashi, N. Hieda, M. Yamauchi, Y. S. Chan, N. Aratani, S. Masuo, H. Yamada, Chem. Eur. J.
2020, 26, 15079–15083.

K. Eimre, J. I. Urgel, H. Hayashi, M. D. Giovannantonio, P. Ruffieux, S. Sato, S. Otomo, Y. S. Chan, N. Aratani, D. Passerone, O. Gröning, H. Yamada, R. Fasel, C. A. Pignedoli, Nat. Commun. in press.
Medium-Temperature Sodium-Iodine Battery System
Authors: Schäfer Frank , Holzapfel Michael , Tübke Jens 
Published: July 2022

A medium-temperature sodium-iodine battery system is presented. The rechargeable molten-sodium system works at approx. 100 °C with high efficiency, and potentially lower cost than existing high-temperature sodium-batteries (which are usually operating at a temperature of around 300 °C). Our battery system uses an aqueous iodine/iodide solution as catholyte and sodium-ion conductive Zr-based NaSICON ceramic material as solid electrolyte. The free halogen, which is formed upon charge, is complexed as highly soluble triiodide. Long-term stability of sodium-ion conductive material in contact with aqueous electrolytes, generally, is a concern. NaSICON-based ceramic material has shown not only an enhanced stability [1] against these electrolytes but also an increased sodium-ion conductivity [2], compared to sodium β″-alumina used in sodium-sulfur batteries. The sodium-iodine system has shown to operate in a stable manner with a catholyte allowing for a high total iodine concentration (>3.0 mol/L) [1]. Substitution in the NaSICON composition allows for increased ionic conductivity and enhanced stability against the aqueous cathode. In the case of fissuring of the NaSICON ceramic separator, only solid products are formed. This stops the direct reaction of active materials.
[1] M. Holzapfel, D. Wilde, C. Hupbauer, K. Ahlbrecht, T. Berger, Electrochim. Acta 237 (2017), 12-21.
[2] S. Naqash, Q. Ma, F. Tietz, O. Guillon, Solid State Ionics 302 (2017), 83-91.
This work is funded by the German Federal Ministry of Education and Research in the project „MiTemp – Mitteltemperatur-Natriumbatterien mit flüssiger Natriumanode und wässriger Iodkathode“ (03XP0183A).

Figure 1
In-Operando FTIR Study on the Redox Behavior of Sulfurized Polyacrylonitrile As Cathode Material for Li-S Batteries
Authors: Pereira Rhyz , Sarode Krishna Kumar , Rafie Ayda , Kalra Vibha 
Published: July 2022

Sulfurized polyacrylonitrile (SPAN) has been shown to be an attractive cathode material for Lithium-Sulfur (Li-S) batteries demonstrating high gravimetric capacity of up to 650mAh/g, and stable cycle performance due to the lack of a polysulfide shuttle in commercially viable carbonate electrolyte. While carbonate electrolyte works well with the cathode of Li-SPAN batteries, it is known to destabilize lithium metal, leading to inactive lithium on the anode and poor coulombic efficiencies (CE). Ether electrolytes in contrast have shown much more stable lithium metal behavior, with consistently high CE. While ether-based electrolytes offer advantages in their ability to stabilize the lithium metal anode, SPAN’s performance in ether-based electrolytes suffers from rapid capacity fade possibly due the dissolution of polysulfide species into the electrolyte during the charge discharge cycle. In this work, we investigated the redox behavior of SPAN in ether electrolytes using in-operando FTIR, and the role of lithium nitrate in cycling stability in SPAN batteries.
Our cyclic voltammetry measurements have revealed that the presence of lithium nitrate in sufficient concentration (0.5M) prevents the appearance of redox peaks at 2.1V and 2.3V associated with soluble polysulfides seen in cells using ether electrolyte lacking lithium nitrate. High concentrations of lithium nitrate also prevented rapid capacity loss in cells made using ether electrolyte during long term cycling. XPS measurements showed higher concentrations of lithium fluoride in cells cycled with high concentrations of lithium nitrate, suggesting the formation of a robust cathode electrolyte interface. We developed an in-situ FTIR cell utilizing an attenuated total reflectance (ATR) accessory that can detect the major features of SPAN, such as the cyclized ring structure, the C-S bond, and the S-S bonds. For the in-operando cell, we fabricated a freestanding SPAN cathode and constructed a Li-SPAN cell on top of the ATR accessory. We examined the behavior of polysulfides to understand the role that lithium nitrate plays in preventing the shuttle effect by examining the S-S vibrational modes at 500 cm-1. Additionally, we studied the interactions between the lithium ion and the carbon backbone of SPAN by examining the cyclic behavior of vibrational modes associated with SPAN’s ring structure in the fingerprint region (1000-1500 cm-1), and ring breathing modes (800 cm-1). These peaks disappear during discharge from our in-situ spectra when the cell is at 1.7 V, which corresponds with the major redox peak of SPAN and reappears and returns to its initial position at 2.35V during charge. This indicates that the change in the ring structure is associated with a redox process, which we attribute to the intercalation of lithium into the SPAN structure.
Zero-Emission Solutions for MW-Scale Energy Systems
Authors: Fortin Patrick 
Published: July 2022

The overall aim of this project is to establish a generic modelling platform for the design and operation of zero-emission MW-scale hybrid electric energy systems, with a particular focus on maritime transport applications. The project seeks to integrate battery and fuel cell degradation models with operating strategy models to minimize the total cost of ownership (TCO) of hybrid battery/fuel cell systems. The modelling approach used here, to simulate battery and fuel cell degradation, takes advantage of empirical modelling methods already established in the scientific literature. This approach offers three distinct advantages over alternative multi-physics models, in that empirical degradation models are (i) computationally efficient, (ii) can be integrated into other modelling frameworks, and (iii) can support the quick parameterization of different systems.
Real-life battery and fuel cell degradation data, collected using state-of-the-art materials, was used to quantify the model parameters and validate the proposed degradation models. A variety of advanced in-situ electrochemical characterization methods have been employed to quantify the relevant parameters at the beginning-of-life and again after various stages of ageing to determine degradation rates of the relevant parameters.
The second aspect of this project is the implementation of a technoeconomic optimization model that combines the data-driven degradation models with additional inputs such as operating conditions, operational profile (i.e., drive cycle), cost of hydrogen, cost of electricity, etc. to design optimal hybrid battery/fuel cell systems and determine optimal control strategies to minimize degradation and total cost of ownership over the system lifetime.
This talk will focus on the advanced in-situ electrochemical techniques that have been used to extract fuel cell degradation parameters and provide an overview of both the empirical degradation and technoeconomical models. Finally, we will present the optimization results obtained using our platform for the implementation of a hybrid energy system in a coastal Norwegian ferry.
(Digital Presentation) Kinetic Studies of Aorfb Posolyte on Graphite Micro-Fiber Electrodes
Authors: El Hage Ranine , Feynerol Vincent , Brites Helu Mariela , Liu Liang , Sehn-Canevesi Rafael-Luan , Fierro Vanessa , Etienne Mathieu 
Published: July 2022

Aqueous organic electrolytes used as posolyte for redox flow battery applications are growing in interest due to their fast kinetics on carbon materials. The determination of their kinetic constants remains a necessity for a better understanding of their overall electrochemical behavior but also for a fine evaluation of the effect of surface activation and possible electrode aging during cycling.
However, the studies performed on carbon felts have shown a lack of accuracy due to the macro-porosity and high surface area of these materials, even at very low electrolyte concentrations (10-4 M). Thus, in this study, we propose another system, allowing to shift from the macro to the micro scale: microelectrodes prepared with single fibers extracted from the corresponding graphite porous felt [1-2]. These microelectrodes allow the qualitative study of solutions at higher concentrations (up to 0.5 M in K4[Fe(CN)6]) and a quantitative analysis through EIS and CV modelling for solutions at 10-2 M with the determination of kinetic constants on activated and non-activated single fibers.
In addition, the effect of activation treatments of graphite felts, on the oxidation kinetics of ferrocyanide is investigated through cyclic voltammetry. In fact, this method allows to determine optimal treatment conditions of carbon felts for a better performance of the battery. Moreover, the degradation of the activation over time can be also studied, which means that the same method could be applied for the study of the aging of the felt after cycling in the battery.
References:
[1] L. Landon-Lane, A. T. Marshall, D. A. Harrington, EIS at carbon fiber cylindrical microelectrodes, Electrochemistry Communications, 109 (2019) 106566
[2] L. Landon-Lane, A. J. Downard, A. T. Marshall, Single fibre electrode measurements – A versatile strategy for assessing the non-uniform kinetics at carbon felt electrodes, Electrochimica Acta, 354 (2020) 136709
Acknowledgement:
This work has been supported by the European Union under HIGREEW, Affordable High-performance Green Redox Flow batteries (Grant Agreement no. 875613).
(Invited) Metal-Cage Interactions in Actinide Mono-Metallofullerenes: Some Insights from Computations
Authors: Rodriguez-Fortea Antonio , Roselló Yannick , Abella Laura , Poblet Josep M. 
Published: July 2022

Intensive research has been devoted to the family of closed-cage carbon nanostructures since the discovery of buckminsterfullerene in 1985.1 Endohedral metallofullerene La@C60, with La inside the cage void space, was already detected the same year and La@C82 was isolated few years later.2 During the last two decades, many different M atoms have been encapsulated inside carbon cages of different sizes, in particular those metals of the lanthanide series.3 More recently, the first metallofullerene containing an actinide, Th@C82, was isolated and characterized.4 Later, other mono-actinidofullerenes as non-IPR U@C80, Th@C80 and U@C76; or IPR U@C82, U@C84 and U@C86 have been also characterized.5 In these actinide endofullerenes, the actinide tends to act with oxidation state +4, which involves an important metal-cage interaction with significant covalent contributions. Consequently, the predictions made by the ionic model are less reliable than for lanthanofullerenes. We here analyze in detail this actinide-cage interaction focusing on symmetry aspects of the cage patterns that mostly stabilize the internal actinide.
References

Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature
1985, 318, 162-163.

a) Heath, J. R.; O’Brien, S. C.; Zhang, Q.; Liu, Y.; Curl, R. F.; Kroto, H. W.;Tittel, F. K.; Smalley, R. E. J. Am. Chem. Soc.
1985, 107, 7779-7780; (b) Chai, Y.; Cuo, T.; Jin, C.; Haufler, R. E.; Felipe Chibante, L. P.; Fure, J.; Wang, L.; Alford, J. M.; Smalley, R. E. J. Phys. Chem.
1991, 95, 7564-7568.

Popov, A. A.; Yang, S.; Dunsch, L. Chem. Rev.
2013,
113, 5989-6113.

Wang, Y.; Morales-Martínez, R.; Zhang, X.; Yang, W.; Wang, Y.; Rodriguez-Fortea, A.; Poblet, J. M.; Feng, L.; Wang, S.; Chen, N. J
. Am.
C
hem. Soc.
2017, 139, 5110-5116.

a) Cai, W.; Abella, L.; Zhuang, J.; Zhang, X.; Feng, L.; Wang, Y.; Morales-Martínez, R.; Esper, R.; Boero, M.; Metta-Magaña, A.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L.; Chen, N. J. Am. Chem. Soc.
2018, 140, 18039-18050; b) Yao, Y.-R.; Roselló, Y.; Ma, L.; Puente Santiago, A. R.; Metta-Magaña, A.; Chen, N.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L. J. Am. Chem. Soc.
2021, 143, 15309-15318.
(Invited) Untethering the Tether Towards Spontaneously Self-Assembled Donuts
Authors: Caballero Ruben , Barrejon Myriam , Cerda Jesus , Arago Juan , Seetharaman Sairaman , de la Cruz Pilar , Orti Enrique , D'Souza Francis , Langa Fernando 
Published: July 2022

Functional materials comprised of spontaneously self-assembled electron donor and acceptor entities capable of generating long-lived charge-separated states upon photo-illumination are in great demand as they are key in building the next generation of light energy harvesting devices. However, creating such well-defined architectures is challenging due to the intricate molecular design, multi-step synthesis, and issues associated in demonstrating long-lived electron transfer.
Here, we have newly synthesized, by tether-directed functionalization, a [60]fullerene e-bisadduct carrying two Zn-porphyrins (Figure), and demonstrate supramolecular organization and photophysical events. Remarkably, the supramolecular assembly of the present bisporphyrin-C60 forms donut-shape aggregates, primarily via π-π type charge transfer interactions. Upon photoexcitation, the supramolecular assembly generates long-lived charge-separated states of »1−40 μs lifetime due to electron/hole delocalization within the supramolecular structure
Reference

Caballero, M. Barrejón, J. Cerdá, J. Aragó, S. Seetharaman, P. de la Cruz, E. Ortí, F. D’Souza, F. Langa. J. Am. Chem. Soc. 2021, 143, 11199.

Figure 1
Chemical Isolation of Isomerically Purified Sc3n@C68
Authors: Ashcroft Chloe A. , Stevenson Steven 
Published: July 2022

Metallofullerenes with fused pentalenes are rare in arc soot. By far, the majority of endohedral fullerene cages obey the isolated pentagon rule (IPR). In a recent landmark paper (Santiago et al., JACS, 2021, 143, 6037-6042) by the Echegoyen group, they experimentally demonstrated the use of Sc3N@C68 as a new molecular catalyst for Hydrogen Evolution Reactions. Indeed, this fused pentalene metallofullerene (Sc3N@C68) successfully outperformed six other “conventional” (i.e., IPR) endohedrals. Thus, application development for fused pentalene metallofullerenes may open new doors.
In this presentation, we discuss our chemical-based purification approach specifically designed for fused pentalene systems such as Sc3N@C68. We find that after two types of selective chemical reaction, we obtain a highly enriched sample of primarily two species, Sc3N@D3(6140)-C68 and Sc3N@Ih(7)-C80. Due to the large retention time difference between C68 and C80 endohedral cages, only a single injection is necessary for a final purification step.