bluuebunny/crossref_metadata_2025_split huggingface dataset:
Probing the Growth and Ion Transport Properties of SEI Layers with NMR Using Novel 6Li/7Li Exchange Experiments
Authors: Ilott Andrew , Jerschow Alexej 
Published: February 2020

Detecting and observing changes in the surface electrolyte interphase (SEI) is difficult due to the small size and amorphous nature of this layer, while its reactivity calls for characterization to be performed in situ, further limiting the applicability of many techniques. Nuclear Magnetic Resonance (NMR) can be performed in situ, but not in conjunction with magic angle spinning (MAS), which is often needed to enhance sensitivity and resolve the broad signal associated with the crystalline environments making up the SEI. It has therefore been necessary to devise alternative NMR approaches to probe the SEI.
Even in an isolated lithium metal electrode in contact with a standard electrolyte, an SEI forms and acts as an intermediary in the exchange between lithium ions in the electrolyte and the metal. Self-diffusion in the metal further complicates this picture, although its impact is only apparent when changes in the local 6Li/7Li isotopic concentration can be considered. This is possible with NMR and, coupled with the skin effect that limits the detected NMR signal to the micron-thickness surface region of the lithium metal, provides a unique, time resolved “window” into the lithium ion dynamics at the metal-SEI-electrolyte interfaces. We will describe how this “window” can be used to extract information about the growth of the SEI layer and measure the diffusion of lithium ions through it using NMR experiments on well-designed, isotopically-enriched systems (see Figure).
Figure caption: Model of the ion dynamics at the lithium metal electrode – SEI – electrolyte interface. Information about the diffusion, exchange and transport properties of the ions through the SEI can be accessed via carefully designed 6Li and 7Li NMR experiments.

Figure 1
Nanocomposites of Metal Oxide@Graphene@Ni Foam for Energy Storage Applications
Authors: Shim Jae-Jin , Sahoo Sumanta , Nguyen Van Hoa , Hwang Jinho 
Published: February 2020

Nanocomposites of metal oxide@graphene@Ni foam have been developed for energy storage applications such as supercapacitors. Electrochemical performance of the graphene-based metal compounds nanocomposites has been improved due to the synergistic effect of excellent conductivities and mechanical properties of graphene sheets and the high pseudocapacitance of metal oxides and metal sulfides. Most metal oxides and sulfides are low costs and doping of graphene with metal oxide or sulfide nanoparticles enhances the energy density remarkably, resulting in an excellent performance as an electrode material for supercapacitors. Recently, metal foam has been getting tremendous attention as it provide a large surface area and large pores that enables electrolytes and charges penetrates freely. However, to meet the demands of industry for higher capacitance, energy density and power density, a new approach is required.
Various metal oxides and sulfides will be compared. The benefits of using graphene will also be discussed. In the synthesis of these materials, a cleaner technology has been employed. Nanocomposites that show high surface areas, high conductivities, and remarkable electrochemical properties will be introduced and, especially, materials for high performance supercapacitors will be presented for future energy storage application.
Scalable Study on Nanostructured Carbon –Sulfur Composite Electrodes for High Energy Lithium Sulfur (Li-S) Battery
Authors: Tripathi Balram , Martinez Monika Lopez Victoria , Katiyar Rajesh Kumar , Sharma K.B. , Katiyar Ram S 
Published: February 2020

Sulfur is a promising cathode material for lithium sulfur batteries due to its high theoretical capacity (1675 mAh/g). Sulfur cathodes generally suﬀers from fast capacity degradation and poor Coulombic eﬃciency originated from the dissolution of intermediate discharge products (polysulﬁdes, Li2S) in the electrolyte. The polysulﬁde dissolution causes loss of active sulfur and suppresses its deep lithiation, which becomes especially severe during slow charge−discharge processes and deteriorates the electrochemical performances at low cycling rates. Here we report a scalable study on nanostructured carbon-sulfur (S1-x Cx where x=.50,& .40 etc.) composites as a cathode fabricated by ballmiling technique for lithium sulfur battery. To enhance the electrochemical performance of lithium- sulfur battery, carbon black as a conductive material has been dispersed in sulfur. The initial characterization of these nanostructured composites have been performed by XRD, SEM and RAMAN spectroscopy. For electrochemical performance coin cells have been fabricated and are under testing for charge/discharge charcteristics by SOLATRON.

Figure 1
Characterizing Li-Ion Batteries Using in Situ MRI
Authors: Ilott Andrew , Mohammadi Mohaddese , Chang Hee Jung , Grey Clare P. , Jerschow Alexej 
Published: February 2020

We will describe our work on the development of techniques for assessing Li-ion batteries and battery materials via magnetic resonance imaging (MRI). The goal of these studies is to analyze battery degradation and energy storage mechanisms in situby imaging changes in both the electrolyte and the electrodes in a noninvasive fashion while a cell is charged or discharged.
We will discuss recent breakthroughs we have made in performing MRI experiments on commercial pouch and coin cell batteries that allow diagnostic tests to be obtained without disassembling the cells. These tests can be run in situ or ex situ and can be used to indicate cycling properties of new battery components, to give a ‘fingerprint’ of manufactured cells for comparison and quality control purposes, or to offer engineering insights into the physical properties of the battery.
We will also report on specific applications of MRI in functioning lithium metal batteries [1], where the technique can be used to correlate the behavior of the electrolyte concentration gradient to the type and rate of dendrite growth on the surface of the Li metal electrode. These studies have confirmed the existence of separate growth mechanisms in different charging regimes. The methodology is extremely sensitive to Li dendrite formation, opening the possibility of testing a broad range of materials and operating conditions to understand when dendrites grow and how they can be prevented.
By developing a detailed understanding of the impact lithium dendrites have on their surroundings, we have been able to design fast 1H MRI experiments that are extremely sensitive to local dendrite growth [2]. The experiments allow for the 3D structure of the dendrites to be reconstructed, and are fast enough to capture the dendrite growth in real time, shedding light on the growth behavior, rate and morphology of the structures formed. Moreover, through simulations and a detailed analysis of the results obtained, we show how the MRI can be used to quantify the volume of dendrites grown.
1. Chang, H. J.; Ilott, A. J.; Trease, N. M.; Mohammadi, M.; Jerschow, A.; Grey, C. P. J. Am. Chem. Soc.
2015, 137(48), 15209–15216.
2. Ilott, A. J.; Mohammadi, M.; Chang, H. J.; Grey, C. P.; Jerschow; Proc. Natl. Acad. Sci.
2016
113 (39), 10779–10784.
Figure caption: Regions of microscopic lithium dendrites that have grown between two lithium metal electrodes. The image is reconstructed from a 15 minute 1H MRI scan.

Figure 1
(Invited) Endohedral Single Molecule Magnets
Authors: Greber Thomas 
Published: February 2020

It took a while to discover the first endohedral single molecule magnet. In 2012 it was shown that DySc2N@C80 has, at a temperature of 2 K, magnetic relaxation times longer than 104 s [1]. The Figure depicts an image of this molecule, where the Jz =15/2 groundsate of the Dy 4f9 shell is colored in red. This anisotropic electronic ground state is oriented and stabilized by the strong ligand field, mainly of the central nitrogen ion, which causes the single ion magnetism. After DySc2N@C80 a series of new endofullerene single molecule magnets with a variety of different magnetic ground states were reported. For example, one, two or three encaged Dy ions display tunneling of the magnetisation, long remanence, or a frustrated ground state, which indicates a strong magnetic interaction within the cage [2].
I will discuss x-ray magnetic circular dichroism (XMCD) as a particularly sensitive tool for the detection of the magnetism inside the carbon cages and how these experiments may be complemented with superconducting quantum interference device (SQUID) measurements down to 400 mK temperature.
It will furthermore be shown that endohedral units may get preferentially oriented on surfaces [3], and that this proves the carbon cages to be "leaky Faraday cages", with tunable interaction across the carbon shell.
References:
[1] An Endohedral Single-Molecule Magnet with Long Relaxation Times: DySc2N@C80, Westerström et al. J. Am. Chem. Soc. 134 (2012) 9840.
[2] Tunneling, remanence, and frustration in dysprosium-based endohedral single-molecule magnets, Westerström et al. Phys. Rev. B 9 (2014) 060406.
[3] Surface Aligned Magnetic Moments and Hysteresis of an Endohedral Single-Molecule Magnet on a Metal, Westerström et al. Phys. Rev. Lett. 114 (2015) 087201.
Figure: Model of the first endohedral single molecule magnet: DySc2N@C80 (see: www. spinshuttle.ch, courthesy Ari Seitsonen).

Figure 1
(Invited) High Pressure Measurements of Two Polymorphs of C60
.2S8
Authors: Olmstead Marilyn M. , Ghiassi Kamran B. , Beavers Christine M. 
Published: February 2020

We recently reported the occurrence and crystal structures of two, concomitant, rotationally disordered polymorphs of C60•2S8 at room temperature, the α- and γ- forms, and their crystal-to crystal transformations to fully ordered polymorphs named β- and δ- C60•2S8, respectively, at low temperatures.1 At 90 K, certain ball---ball centroids of both forms are relatively close, the shortest being 9.881 Å and 9.855 Å, respectively. Polymerization of C60 has received attention over the years in quest of interesting properties. These studies have primarily utilized powdered C60. We were curious to see happens to C60 under high pressure in a crystalline, binary phase such as with S8, and if crystal-to-crystal transformations would occur. Possibly S8would catalyze polymerization and help to prevent fullerene collapse, and orientational ordering would occur. High pressure measurements have been carried out at the Advanced Light Source, Lawrence Berkeley National Lab, and our results will be summarized.

1Ghiassi, et al., Cryst. Growth Des. 2015, 15, 404.
(Invited) Isolation and Structural Characterization of Lu2C2n
Authors: Shen Wangqiang , Lu Xing 
Published: February 2020

Endohedral metallofullerenes (EMFs) with a composition of M2C2n may exist as di-EMFs, M2@C2n, or as carbide cluster metallofullerenes (CCMFs), M2C2@C2n-2. Although metals with a small ionic radius such as scandium were found to form cluster EMFs and some have been incorrectly assigned as conventional EMFs.[1-3] , Lu-containing EMFs remain largely unexplored in spite that lutecium has a similar ionic radius to that of scandium. In this work, we report the isolation and single-crystal X-ray crystallographic characterization of several unprecedented Lu- containing EMFs: Lu2@C2n (2n=82, 84, 86) EMFs. Theoretical results demonstrate that four electrons are transferred from the two divalent Lu ions onto the fullerene cages.

References：
(1) Lu, X.; Akasaka, T.; Nagase, S. Acc. Chem. Res.
2013, 46 (7), 1627.
(2) Lu, X.; Feng, L.; Akasaka, T.; Nagase, S. Chem. Soc. Rev.
2012, 41 (23), 7723.
(3) Popov, A.; Yang, S.; Dunsch, L. Chem. Rev.
2013, 113, 5989-6113.
(Invited) Molecular Recognition and Assembly of Fullerene and Carbon-Based Materials with Biomolecules
Authors: Osuna Sílvia , Garcia-Borràs Marc , Feixas Ferran , Atienza Carmen , Martín Nazario , Echegoyen Luis 
Published: February 2020

Fullerenes and related carbon-based compounds have shown several promising biological applications, mainly due to their ability to be extensively functionalized.[1]
The development of nanohybrid materials combining biological entities and carbon-based materials such as SWCNTs is a cutting-edge area with high impact in fields such as medicine, and energy production.[2] This can be achieved thanks to the favorable recognition and assembly of fullerene and related compounds with proteins. An example of this recognition process is given by the recent finding of some (metallo)fullerene derivatives that were found to exhibit strong anti-viral activity on the replication of HIV-1 in human cells.[3] Although the mechanism of action is not known, it was suggested to be HIV-1 protease independent. The dynamic nature of processes such as assembly, or biomolecular recognition cannot be captured in detail using experimental techniques, and thus computations can provide dramatic new insights. In this talk, a dynamic view of such important biological processes will be presented with an special emphasis on the nanohybrid formation and HIV-1 maturation inhibition.
[1] Garcia-Borràs, M.; Osuna, S.; Swart, M.; Luis, J. M.; Solà, M., Chem. Soc. Rev.
2014, 43, 5089
[2] Mejias, S. H.; Lopez-Andarias, J.; Sakurai, T.; Yoneda, S.; Erazo, K. P.; Seki, S.; Atienza, C.; Martín, N.; Cortajarena, A. L. Chem. Sci.
2016, 7, 4842
[3] Martinez, Z. S.; Castro, E.; Seong, C.-S.; Ceirón, M. R.; Echegoyen, L.; Llano, M. Antimicrob. Agents Chemother.
2016, DOI: 10.1128/AAC.00341-16
Experimental and Theoretical Investigation on the Molecular Structures of Pr@C72, Pr2@C72 and and Their Functionalized Adducts
Authors: Zhao Yanli , Yu Haitao , Lian Yongfu 
Published: February 2020

A novel Pr-based mono-metallofullerene derivative, Pr@C72(C6H3Cl2), was successfully prepared and isolated and its molecular structure was verified as Pr@C2(10612)-C72(C6H3Cl2) by combined UV-visible-near-infrared absorption spectroscopy and quantum mechanics characterization, as well as a comparison with the structurally characterized analogue La@C72(C6H3Cl2). Furthermore, an additional computation indicated that the pristine Pr@C72 has the lowest-lying structure as Pr@C2(10612)-C72, followed by Pr@C2v(11188)-C72, which lies only 0.62 kcal mol-1 above Pr@C2(10612)-C72. The charge transfer and orbital interaction between the endohedral Pr atom and the carbon cage as well as the electronic configuration and formal charge state of the encapsulated Pr atom temperature dependence of their thermodynamic distribution was also estimated based on the computed quantum mechanics data.
The pristine endohedral d-imetallofullerene Pr2@C72 was prepared and isolated [2]. Its structure was determined to be Pr2@D2(10611)-C72 by a combination of mass spectrometry, UV-visible-near-infrared absorption spectroscopy, and quantum mechanics characterization. Moreover, the reactivity of Pr2@D2(10611)-C72 was probed by 2-adamantane-2,3-[3H]-diazirine functionalization, and the resulting adducts were identified with mass spectrometry and high performance liquid chromatography. Additionally, the preferred addition positions and isomeric structures of the dominant mono-adduct Pr2@C72(Ad) were further investigated using density functional theory.
References
[1] Y. Zhao, Q. Zhou, Y. Lian and H. Yu. RSC Adv., 2015, 5, 97568.
[2] Y. Zhao, H. Yu, and Y. Lian. RSC Adv., 2016, 6, 115113.
Photoactive Anti-Cancer Nanovectors
Authors: Cunin Frederique 
Published: February 2020

The application of nanotechnologies into medicine promises to offer solutions when applied to health challenges such as cancer. In particular the development of new local and focal therapies such as photodynamic therapy will reduce side effects associated with systemic administration of chemotherapy drugs, and will allow preservation or limited resection of organs with small size tumors. Our research projects aim to develop biodegradable anti-cancer materials based on biodegradable porous silicon-based nanostructures to be used for local cancer treatment.
Porous silicon (pSi) nanostructures are fully biodegradable, and nontoxic in vivo. The primary biodegradation product of pSi is orthosilicic acid, which is the bioavailable form of silicon. PSi is easily prepared by electrochemical etching of crystalline silicon. Chemical modification provides a means to adjust the degradation rate of pSi, as well as to load drugs or photosensitizers. Due to their electronic semiconductor-derived properties, pSi nanostructures exhibit intrinsic photoluminescence amenable for imaging. Moreover, they can be excited by near infrared (NIR) two photon excitation light offering possibilities for phototherapies, and for light triggered and targeted treatment, based on tissue-penetrable NIR light response.
The development of photoactive pSi nanostructures functionalized with porphyrins for applications in imaging and photo-activated therapies will be presented.
Phthalocyanine in Bulk Heterojunction, Perovskites and Dye Sensitized Solar Cells
Authors: Sastre-Santos Ángela 
Published: February 2020

Phthalocyanines (Pcs) are outstanding dye candidates in for dye sensitized solar cells (DSSCs) due to their high extinction coefficient in the visible and near-infrared spectral region and to their high thermal and chemical stabilities[1]. Pcs incorporated in DSSCs have achieved PCEs as high as 6.4 %[2], still far away from the 12.75% PCE obtained by porphyrins, their closest relatives. An elegant strategy to improve the light-harvesting ability of the Pcs is the extension of the aromatic structure by generation aromatic-fused analogues of Pc having a red-shifted absorption. The same strategy will be also tested in perovskite solar cells (PSCs) as electron donor systems.
Herein, we will report our more recent results related with the synthesis of different unsymmetrically substituted phthalocyanines fully conjugated with electroactive systems[3] and the improvement in efficiency of DSSCs and PSCs[4].

Acknowledgements. This work has been supported by the Spanish Ministerio de Economía y Competitividad (Mineco) CTQ-2014-55798-R.
References

L. Martín-Gomis, F. Fernández-Lázaro, Á. Sastre-Santos, J. Mater.
Chem. A 2014, 2, 15672-15682.

(a) T. Ikeuchi, H. Nomoto, N. Masaki, M. J. Griffith, S. Mori, M. Kimura, Chem.
Commun.
2014, 50, 1941-1943. (b) M. E. Ragoussi, J.-H. Yum, A. K. Chandiran, M. Ince, G. de la Torre, M. Grätzel, M. K. Nazeeruddin, T. Torres, Chem.
Phys.Chem.
2014, 15, 1033-1036.

V. M. Blas-Ferrando, J. Ortiz, V. González-Pedro, R. S. Sánchez, I. Mora-Seró F. Fernández-Lázaro, Á. Sastre-Santos, Adv. Funct. Mater.
2015, 25, 3220-3226. (b) V. M. Blas-Ferrando, J. Ortiz, V. González-Pedro, R. S. Sánchez, I. Mora-Seró F. Fernández-Lázaro, Á. Sastre-Santos, Chem. Commun.
2015, 5, 4785-4793. (c) D. Molina, M. E. El-Khouly, M. El-Kemary, S. Fukuzumi, F. Fernández-Lázaro, Á. Sastre-Santos Chem. Eur. J.
2016, 22,17800 –17807.(a)

(a) D. Molina, C. Parejo, J.C. Álvarez, L. Martín-Gomis, F. Fernández-Lázaro, Á. Sastre-Santos, in preparation. (b) J. Follana, M. M. León, L. Martín-Gomis, F. Fernández-Lázaro, Á. Sastre-Santos, in preparation.
Protection of Aluminium in Acidic Environment and Inhibition Efficiency of Aminophenol-N-Benzylidene -Theoretical and Practical Investigation
Authors: Naik Unnati Jayesh , Shah Nisha K. 
Published: February 2020

Aluminium has a remarkable industrial importance. Aluminium and its alloys are exposed to the action of acid in industrial processes where acid play an important role such as oil well acidizing, acid pickling, acid cleaning and descaling. This can lead to substantial metal loss due to corrosion. The use of inhibitors is one of the most practical options to protect metal from corrosion. Organic and inorganic compounds are usually added to HCl as corrosion inhibitors.
The present work is carried out to find the effective inhibitor with minimum concentration but maximum inhibition. The corrosion inhibition effect of o,m,p-Aminophenol-N-Benzylidene (o,m,p-AmphNB) for pure Aluminium in 1M HCl were investigated by means of weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Electrochemical studies were carried out using standard three electrode cell where Calomel electrode act as a reference electrode, Platinum electrode as counter electrode and Aluminium electrode as working electrode. The values of ΔGads indicates the competitive Chemisorption and physisorption, Potentiodynamic polarization parameters revealed the mixed mode of inhibition with predominance of cathodic inhibition. The EIS showed linear correlation with concentration of inhibitor & Rctl while Cdl inversely correlated. Quantum chemical calculations based on density functional theory (DFT) method were performed on studied inhibitors to ascertain relationship between molecular structure and their inhibition efficiency. Correlation analyses between experimental and theoretical values were performed to conclude that the inhibition effect of inhibitors could be explained in terms of electronic properties.

Figure 1
Corrosion of Austenitic Steels and Their Components in Molten Nacl–Kcl–UCl3
Authors: Abramov Aleksandr V. , Polovov Ilya B. , Dedov Kirill V. , Karpov Vyacheslav V. , Zhilyakov Arkadiy Yu. , Belikov Sergey V. , Volkovich Vladimir A. , Rebrin Oleg I. 
Published: February 2020

The fused halides can be used for nuclear fuel reprocessing and as working media for molten salt nuclear reactors. However practical implementation of such technologies is limited by the problem of finding suitable corrosion resistant materials capable of long-term working in contact with molten salts. From the economical point of view the application of stainless steels as construction materials for the molten salt media is one of the most prospective ways.
In the present study the corrosion behaviour of metallic iron, nickel, chromium, molybdenum, AISI 316L and 12Kh18N10T (analogue of AISI 321) austenitic steels was studied in NaCl–KCl–UCl3(1 wt.% U) melts at 750 ºC.
Gravimetric measurements served as a basis for estimating corrosion resistance of studied materials. Quenched melts were analyzed using ICP-AES method. The surface of the alloy samples after corrosion tests was characterised using XRD, SEM and Х-ray microanalysis. The foils of corroded materials were examined by TEM.
The corrosion rates of studied metals in NaCl–KCl–UCl3melt decrease in the following order: Cr>Fe>Ni>Mo, which correlates well with the formal standard potentials of metals in chloride melts indicating electrochemical nature of the corrosion processes. Molybdenum is the only corrosion resistant metal in the uranium-containing chloride melts and it can be used as a construction material for molten salt reactors.
The major products of stainless steel corrosion in chloride melts are iron, chromium and manganese species. The surface of the corroded samples of austenitic stainless steels was depleted in manganese and chromium and enriched in nickel and molybdenum. Intergranular corrosion was observed for all types of austenitic steels. In terms of intensity and depth of the corrosion layer in NaCl–KCl–UCl3 the studied steels can be ranged in the order AISI 321>AISI 316L that correlates with the amount of excessive phases formed (figure).

Figure 1