bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modeling the Effect of the Design of Air Cooling Channels on the Thermal Behavior of a Lithium-Ion Battery Module
Authors: Lee Myoung Kyou , Koo Boram , Shin Chee Burm 
Published: February 2020

The lithium-ion battery (LIB) is one of the preferred candidates for electric vehicle (EV) and hybrid electric vehicle (HEV) applications due to its outstanding characteristics such as high energy density, modular scalability, long cycle life, and low self-discharge rate among others. In a battery module for EV applications, an uneven temperature distribution in the module can be created depending on the operating conditions and the types of thermal management. Uneven temperature distribution in a module could cause an electrical imbalance and thus lead to the lower performance and shorter life of battery. Therefore, it is important to calculate accurately the uneven temperature distribution in a battery module in order to achieve the optimum performance and long life of the battery module.
In this work, a three-dimensional modeling is performed to investigate the effects of the design of air cooling channels on the thermal behavior of an LIB module. Thermal conductivities of various compartments of the battery are estimated based on the equivalent network of parallel/series thermal resistances of battery components. Heat generation rate in an LIB cell is calculated by using the modeling results of the potential and current density distributions of a battery cell.
Fig. 1 shows the schematic diagram of the battery module composed of 24 cells with two types of air cooling channels. The average temperatures from the experimental measurement for the LIB module for US06 cycle profile are compared with those predicted by the modeling in Fig.2.

Figure 1
Redox-Active Organic Electrodes for Pseudocapacitor Applications
Authors: Liu Tianyuan , Lee Byeongyong , Lee Seung Woo 
Published: February 2020

Current lithium-ion battery technology depends on inorganic cathode materials, such as LiCoO2 and LiFePO4. However, large-scale energy storage applications, including renewable energy storage and load-leveling, require more sustainable and cost-effective electrode materials. Organic electrode materials have been studied owing to their potential advantages, including the use of earth-abundant sources, environmental friendliness, and high energy density.1 We also have been investigating various redox-active organic electrodes by utilizing dopamine,1 pyrene derivatives,2 and glucose.3 Here, we further investigate the charge storage properties of the biomass-derived carbonaceous materials with Li- and Na-ions. We reveal that the synthesized carbonaceous materials can exhibit high capacities over 180 mAh/g in both Li- and Na-ions by based on double layer capacitance and redox reactions. These carbonaceous materials can be fabricated as the composite electrodes by mixing with conductive nanocarbons, including carbon nanotubes or reduced graphene oxides. These carbon-based composite electrodes show a high rate-capability and remarkable cycling stability. These high-performance organic electrodes could be promising candidates for developing large-scale energy storage devices.
References
1. T. Liu, K. C. Kim, B. Lee, Z. Chen, S. Noda, S. S. Jang and S. W. Lee, Energy & Environmental Science, DOI: 10.1039/C6EE02641A (2017).
2. J. C. Bachman, R. Kavian, D. J. Graham, D. Y. Kim, S. Noda, D. G. Nocera, Y. Shao-Horn and S. W. Lee, Nature Communications, 6:7040 (2015).
3. T. Y. Liu, R. Kavian, Z. M. Chen, S. S. Cruz, S. Noda and S. W. Lee, Nanoscale, 8, 3671 (2016).
(Invited) Modification of Lithium-Ion-Containing [60]Fullerene: Synthesis and Successful Preparation of Each [5,6]- and [6,6]-Isomer
Authors: Matsuo Yutaka , Okada Hiroshi , Ueno Hiroshi , Aoyagi Shinobu 
Published: February 2020

Lithium-ion-containing [60]fullerene, Li+@C60, is a highly electron accepting material, which have been utilized in electron transfer chemistry, supramolecular chemistry, photovoltaics, singlet oxygen generation, and so on. Considering what chemical modification of fullerene has played in, that for Li+@C60 would be a significant step for further functionalization of this compound.[1-7] In addition, chemical modification of Li+@C60 can solve this compound's drawback of low solubility in organic solvents due to rock salt packing of [Li+@C60][PF6
–].
Li+@C60 was modified with diphenyl(diazo)methane as an easily available diazoalkane to obtain lithium-ion-encapsulated [5,6]- and [6,6]-diphenylmethano[60]fullerenes, Li+@C61Ph2. Successful separation of each [5,6]- and [6,6]-isomer was performed with a positive-ion exchange columns. Both [5,6]-open and [6,6]-closed structures of Li+@C61Ph2 were determined with X-ray crystallographic analysis.

Figure 1
(Invited) Effect of Covalent Chemistry on the Electronic Structure and Properties of the Carbon Allotropes
Authors: Bekyarova Elena , Chen Mingguang , Tian Xiaojuan , Moser Matthew , Li Wangxiang , Li Guanghui , Itkis Mikhail E 
Published: February 2020

Covalent chemistry exerts characteristic changes to the geometric and electronic structures of the carbon allotropes associated with modification of the conjugation. There are two limiting cases: (a) conventional addition chemistry leading to the formation of σ-bonds to the graphitic surface in which there is full rehybridization of the derivatized carbon atoms from sp2 to sp3; in this case the carbon atoms are removed from conjugation (destructive rehybridization) and (b) covalent chemisorption with formation of an organometallic hexahapto-metal bond that largely preserves the graphitic band structure (constructive rehybridization). 1, 2

We focus our discussion on the organometallic chemistry of the carbon allotropes and the possibility to electronically interconnect graphitic surfaces by means of covalent bonding. This mode of functionalization allows the formation of atomic scale interconnects that consist of bis-hexahapto-metal-bonds between benzenoid ring systems and it may be used to increase the dimensionality of the electronic structure of the materials leading to enhanced conductivity. We will discuss the effect of bis-hexahapto bond formation on the electronic properties of percolating networks of single walled carbon nanotubes, small scale graphite nanoplatelets and graphene.
1. Bekyarova, E.; Sarkar, S.; Wang, F.; Itkis, M. E.; Kalinina, I.; Tian, X.; Haddon, R. C., Effect of Covalent Chemistry on the Electronic Structure and Properties of Carbon Nanotubes and Graphene. Acc. Chem. Res.
2013, 46, 65-76.
2. Bekyarova, E.; Niyogi, S.; Sarkar, S.; Tian, X.; Chen, M.; Moser, M. L.; Ayub, K.; Mitchell, R. H.; Haddon, R. C., Stereochemical Effect of Covalent Chemistry on the Electronic Structure and Properties of the Carbon Allotropes and Graphene Surfaces. Synth. Met.
2015, 210, 80-84.
(Invited) Synthesis and Characterization of Unprecedented D2h
-Symmetrical Trans-1-(S,R,R,S-bis-pyrrolidine)-Tetra-malonate Hexakis Adducts of C60
Authors: Castro Edison , Hernandez Andrea , Azmani Khalid , Liu Shuming , Rodríguez-Fortea Antonio , Poblet Josep M. , Echegoyen Luis 
Published: February 2020

The unique chemical and physical properties of fullerenes and their derivatives is mainly the result of their unique electron accepting abilities and their high charge transport capabilities in three dimensions. The octahedral arrangement of the addends in hexaadducts of C60 is unique in organic chemistry. However, stereo-chemically controlled functionalization of fullerenes has been scarcely addressed so far. Here we report the synthesis and characterization of unprecedented D2h
-symmetrical trans-1-(S,R,R,S-bis-pyrrolidine)-tetra-malonate hexakis adducts of C60, employing the topologically controlled method introduced by Krӓutler et al., followed by a 1,3-dipolar cycloaddition reaction.

Figure 1. Synthesis of D2h
-symmetrical trans-1-(S,R,R,S-bis-pyrrolidine)-tetra-malonate hexakis adducts of C60.

Figure 1
(Invited) Stereodivergent-at-Metal Synthesis of [60]Fullerene Hybrids
Authors: Vidal Sara , Filippone Salvatore , Martín Nazario 
Published: February 2020

The preparation of chiral metal complexes and, specifically, chiral at metal complexes, is a highly sought after goal in current organometallic chemistry due to its relevance in enantioselective metal-mediated processes.1.
Despite the wealth of metal-fullererene hybrids reported to date, only a few are optically actives.2 To the best of our knowledge, only a single case presents a stereogenic metal center,3 while in all of them the chiral information stems from the stoichiometric use of other chiral ligands.4 In this regard, the use of asymmetric organo- and metal-catalysis in fullerene chemistry has provided an easy access to optically active derivatives through a precise stereocontrol in the newly formed asymmetric carbon atoms.5 Conversely, the control of the metal-centered chirality is not a trivial issue due to the configurational lability of the metals that often undergo rapid ligands exchange.1

In this communication, we report the first enantioselective synthesis of fullerene hybrids endowed with a stable stereogenic metal center whose configuration can be defined at will by the proper chiral catalyst choice. In these reactions, iridium, rhodium and ruthenium pyrrolidino[3,4:1,2][60]fullerene half-sandwich complexes with four new stereocenters are formed, namely the two C-2 and C-5 chiral car bons at the pyrrolidine ring, the asymmetric nitrogen atom and the transition metal center (Scheme). The suitable functionalization and stereochemistry of the chiral fullerene ligand determine the final configuration of the metal center. Interestingly, the chiral metal center does not undergo any epimerization process as evidenced by temperature dependent NMR analysis as well as by DFT theoretical calculations.6

References

B. Bauer, Chem. Soc. Rev.
2012, 41, 3153-3167.

L. Balch, M. M. Olmstead, Chem. Rev. 1998, 98, 2123-2166.

Y.-W. Zhong, Y. Matsuo, E. Nakamura, Chem.
Asian J.
2007, 2, 358-366.

V. I. Sokolov, V. V. Bashilov, F. M. Dolgushin, N. V. Abramova, K. K. Babievsky, A. G. Ginzburg, P. V. Petrovskii, Tetrahedron Lett.
2009, 50, 5347-5350.

a) S. Filippone, E. E. Maroto, A. Martín-Domenech, M. Suárez, N. Martín, Nat. Chem.
2009, 1, 578-582; b) E. E. Maroto, M. Izquierdo, S. Reboredo, J. Marco-Martínez, S. Filippone, N. Martín, Acc. Chem. Res. 2014, 47, 2660-2670.

J. Marco-Martínez, S. Vidal, I. Fernández, S. Filippone, N. Martín, Angew. Chem. Int. Ed.,
2017, accepted for publication.
(Invited) Polypeptides As Complexing Units
Authors: Solladie Nathalie 
Published: February 2020

One of our research field concerns porphyrin-functionalized a-polypeptides to control the spatial organization of the chromophores and enable exciton migration through the pool of porphyrins to mimic the light harvesting antennae of the photosynthetic system.1

In the photosynthetic system, the solar energy is collected by pigment molecules attached to the light harvesting complexes, in which the chlorophylls are held in a parallel orientation by fairly short α-helical polypeptides. When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached.1 Succeeding in organizing the porphyrins in a similar way as nature does should provide information about the relation existing between the orientation of the chlorophylls and the efficiency of nature in transferring an excited state over a very long distance and with minimal loss of energy.
The right-handed 310 helical conformation adopted by our poly-L-lysine functionalized with eight porphyrins induces an overlap of the chromophores (studies realized in collaboration with Prof. T. Keiderling, University of Chicago, US), which thus present sufficient electronic coupling to promote a good exciton migration within the molecular wire.
The properties of our peptides with pendant porphyrins were studied extensively in collaboration with with Professor S. Fukuzumi (Univeristy of Osaka, Japan) and applications were found as organic photovoltaic cells,2 multiple photosynthetic reaction centers3 and for the successful purification of Single-Walled Carbon Nanotubes.4

Acknowledgements

This work was supported by the CNRS and the French Ministry of Research.

References

W. Kühlbrandt, Nature
1995, 374, 497-498.

T. Hasobe, K. Saito, P. V. Kamat, V. Troiani, H. Qiu, N. Solladié, K. S. Kim, J. K. Park, D. Kim, F. D'Souza, S. Fukuzumi, J. Mater.
Chem.
2007, 39, 4160-4170.

S. Fukuzumi, K. Saito, K. Ohkubo, V. Troiani, H. Qiu, S. Gadde, F. D’Souza and N. Solladié, Phys.
Chem. Chem. Phys.
2011, 13, 17019-17022.

Kenji Saito, Vincent Troiani, Hongjin Qiu, Nathalie Solladié, Takao Sakata, Hirotaro Mori, Mitsuo Ohama, Shunichi Fukuzumi, J. Phys. Chem. C
2007, 111, 1194-1199.

Figure 1
(Invited) Subphthalocyanine-Fullerene Conjugates
Authors: Torres Tomas , Zango German , Mariñas Victor , Carrascosa Hector , Lavarda Giulia , Medina Diana Paola , Muñoz Nicolas , Trukhina Olga , Rodriguez-Morgade M. Salome , Martínez-Díaz M. Victoria 
Published: February 2020

An approach for employing SubPcs and SubPc fused dimers [1] as active units in molecular recognition of fullerenes and artificial photosynthetic systems has been developed. Thus, the preparation of multi-SubPc systems constituted by SubPc and SubPc fused dimer units connected by their mutual axial positions has been explored. For this purpose, a series of SubPcs and SubPc dimers bearing different conjugated spacers linked by alkyne bonds to the SubPc or SubPc dimer boron atoms have been synthesized. Two multi-SubPc hybrids comprised of a perfluorinated SubPc fused dimer (syn or anti topoisomer) axially functionalized with unsymmetrical octylthio-substituted SubPcs linked through their periphery by ethynyl linkers to the boron atoms of the dimer have been prepared. Electrochemical and steady state photophysical studies of the syn- hybrid suggest the existence of an electron transfer process from SubPc units to photoexcited SubPc dimer to generate a (SubPc•+-SubPc Dimer•-) radical pair.
Furthermore, the position that the two axial SubPc units acquire in this assembly gives rise to unique supramolecular recognition sites suitable for the complexation of fullerenes. Thus, the binding ability of this hybrid towards different fullerene derivatives, namely C60
, C70
, C60-PCBM and C70-PCBM, has been analyzed through UV-vis absorption, fluorescence and NMR titrations. It has been demonstrated that syn-compounds display a unique fullerene complexation mode. Initially, the formation of a 1:1 supramolecular complex, where the axial octylthio-substituted SubPcs embraces a guest molecule with remarkable association constants of around 106 - 104 M-1, is observed. The spatially-defined cavity generated by the rigid and short alkynyl linkers shows a higher affinity for the bigger fullerene derivatives. Then, a secondary supramolecular interaction between the perfluorinated SubPc syn dimer unit and another fullerene molecule has been detected and quantified, with significant binding constants of 104-103 M-1 that depend on the size and the host-guest electrostatic interactions, leading to the formation of the final 1:2 supramolecular ensemble [2].
Pristine and endohedral fullerene-subphthalocyanine conjugates [3,4] both covalent and supramolecular have been also prepared and studied as artificial photosynthetic systems.
[1] C. G. Claessens, D. González-Rodríguez, M. S. Rodríguez-Morgade, A. Medina, T. Torres, Chem. Rev.
2014,
114, 2192–2277.
[2] G. Zango, M. V. Martínez-Díaz, T. Torres, in preparation
[3] L. Feng, M. Rudolf, O. Trukhina, Z. Slanina, F. Uhlik, X. Lu, T. Torres, D. M. Guldi, T. Akasaka, Chem. Commun.
2015,
51, 330-333.
[4] M. Rudolf, O. Trukhina, J. Perles, L. Feng, T. Akasaka, T. Torres, D. M. Guldi, Chem. Sci.
2015,
6, 4141-4147.
(Invited) Multichromophoric Perylenediimide-Silicon Phthalocyanine-C60 System As an Artificial Photosynthetic Analogue
Authors: Sastre-Santos Ángela , D'Souza Francis 
Published: February 2020

Sequential photoinduced energy transfer followed by electron transfer and the formation of charge separated states, which are primary events of natural photosynthesis, have been demonstrated in a newly synthesized multichromophoric covalently linked triad, PDI-SiPc-C60. The triad was comprised of a perylenediimide (PDI) that primarily fulfils antenna functionality and electron acceptor; silicon phthalocyanine (SiPc) as an electron donor; and fulleropyrrolidine (C60) as a second electron acceptor. The multi-step convergent synthetic procedure developed here produced good yields of the triad and control dyads, PDI-SiPc and SiPc-C60. The structure and geometry of the newly synthesized donor-acceptor systems were established from spectral, computational and electrochemical studies with the help of appropriate control compounds. Ultrafast energy transfer from 1PDI* to SiPc in the case of PDI-SiPc and PDI-SiPc-C60 was witnessed. Energy level diagram established from spectral and electrochemical data suggested formation of two types of charge separated states, viz., of PDI-SiPc•+-C60
•- and PDI•--SiPc•+-C60 from the 1SiPc* in the triad; and that generation of the latter is energetically more favourable. However, photochemical studies involving femtosecond transient spectroscopy revealed formation of PDI-SiPc•+-C60
•- as a major charge separation product. This observation has been rationalized to the spatial closeness of C60 compared to PDI in the triad. The charge separated state lasted for a few nanoseconds prior to populating the 3SiPc* state during charge recombination.[1]
Acknowledgments
This work was supported by the Spanish Ministry of Economy and Competitiveness (Mineco) of Spain (CTQ2014-55798-R to ASS), Generalitat Valenciana (Prometeo 2012/010 to ASS) and National Science Foundation (Grant No. 1401188 to FD).
References
1. L. Martín-Gomis, F. Peralta-Ruiz, M. B. Thomas, F. Fernández-Lázaro, F. D’Souza, Á. Sastre-Santos. Chem. Eur. J.
2016, in press.

Figure 1
(Invited) Electron Donor-Nanocarbon Electron Acceptor Composites Linked with Oligophenylene Bridge
Authors: Imahori Hiroshi 
Published: February 2020

During the last few decades, considerable efforts have been made toward the construction of donor–acceptor (D–A) linked systems that efficiently cause photoinduced charge separation, a fundamental step in natural photosynthesis and solar energy conversion. Among the building units for such D–A systems, nanocarbons deserve a special mention because it shows notable electronic conductivity, tenacious mechanical strength, and huge specific surface area. These singular properties place nanocarbon-based D–A systems in an attractive position as the next-generation material for energy-conversion devices such as solar fuels and organic photovoltaics. With this in mind, a variety of studies have been done to synthesize covalently linked systems of electron-accepting nanocarbons with electron-donating units such as pyrenes, porphyrins and phthalocyanines. However, the D–A interface frequently undergoes a rapid relaxation of the partially charge-separated (CS) exciplex or the completely CS state to the ground state, failing to generate a long-lived CS state that is crucial for solar energy conversion. In-depth understanding of the correlation between the structure and photodynamics of the electron donor-nanocarbon electron acceptor linked systems is important for extracting the full potential of such D–A materials for the potential applications.
In this talk I will show an overviw of our recent achievements related with photodynamics of pyrene- and porphyrin-attached chemically converted graphenes linked with oligophenylene bridge.
[1] T. Umeyama, J. Baek, Y. Sato, K. Suenaga, F. Abou-Chahine, N. V. Tkachenko, H. Lemmetyinen, and H. Imahori, Nat. Commun., 6, 7732 (2015).
[2] T. Umeyama, J. Baek, J. Mihara, N. V. Tkachenko, and H. Imahori, Chem. Commun., in press.
[3] T. Umeyama, T. Hanaoka, J. Baek, T. Higashino, F. Abou-Chahine, N. V. Tkachenko, and H. Imahori, J. Phys. Chem. C, in press.
(Invited) Excited State of Y-Nitride Clusterfullerene: Luminescence and EPR Spectroscopy Study
Authors: Krylov Denis , Zalibera Michal , Schiemenz Sandra , Ziegs Frank , Rosenkranz Marco , Savitsky Anton , Popov Alexey A. 
Published: February 2020

Empty fullerenes are known to have very fast intersystem crossing with near 100% yield of the T1 state, which results in very low quantum yield of fluorescence and relatively short fluorescence lifetimes (less than 1 ns). In endohedral metallofullerenes, the intersystem crossing is even faster due to the internal heavy-atom effect, and hence fluorescence can hardly be expected. However, Y3N@C80 is known to exhibit reasonably high yield of fluorescence (1%) and unusually long lifetimes of 800 ns.1, 2 Such unusual photophysical parameters indicate that simple fluorescence mechanism cannot explain experimental facts. In this contribution we describe steady-state and lifetime luminescence as well as light-induced electron paramagnetic resonance studies of Y3N@C80 at different temperatures aimed at clarification of photophysical properties of Y3N@C80.
1. Bharadwaj, L.; Novotny, L., Plasmon-Enhanced Photoemission from a Single Y3N@C80 Fullerene. J. Phys. Chem. C 2010, 114, 7444-7447.
2. Toth, K.; Molloy, J. K.; Matta, M.; Heinrich, B.; Guillon, D.; Bergamini, G.; Zerbetto, F.; Donnio, B.; Ceroni, P.; Felder-Flesch, D., A Strongly Emitting Liquid-Crystalline Derivative of Y3N@C80: Bright and Long-Lived Near-IR Luminescence from a Charge Transfer State. Angew. Chem.-Int. Edit. Engl. 2013, 52, 12303-12307.
Enhancing the Ion Detection of Graphene Field Effect Transistors at the Quantum Capacitance Limit
Authors: Fakih Ibrahim , Mahvash Farzaneh , Siaj Mohamed , Szkopek Thomas 
Published: February 2020

Graphene field effect transistors (FETs) are attractive candidates for sensing applications because of their high charge carrier mobility and the ideal coupling between graphene charge carriers and surface potential. However, depositing a selective layer on the graphene for these sensing applications can degrade graphene’s electrical properties, increase hysteresis, and present a challenge for maintaining its sensitivity and stability. Here, we protect the graphene by encapsulating it with an ultrathin layer (4-8 nm) of parylene, a hydrophobic polymer, and then deposit 3-5 nm sensing layers, either aluminum oxide or tantalum pentoxide for sensing pH. We demonstrate gate capacitances approaching the quantum limit with 0.6 uF/cm2 and near Nernstian pH sensitivities of 55.2 mV/pH. We also observe significant improvements in field effect mobilities of 7000 cm2V-1s-1 and in transconductance with limited hysteresis compared to previous work. The improvements due to encapsulation have resulted in a detection limit of 0.1 mpH at a 60 Hz electrical bandwidth. We demonstrated our pH response by monitoring the change in acidity of carbonated water in real time.

Figure 1