bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solid State Synthesis of Aluminum Doped Li7La3Zr2O12 Garnet with Enhanced Thermal Processing Stability
Authors: Heywood Stephen , Sofie Stephen , Driscoll David 
Published: July 2022

Lithium lanthanum zirconium oxide garnet (LLZO) is a solid-state lithium ion conducting electrolyte being studied extensively for all-solid-state batteries (ASSB) owing to its high lithium conductivity and chemical stability against lithium metal anodes. This material, though useful, is highly sensitive to lithium stoichiometry in terms of crystalline stability and functional properties including conductivity. Stabilizing agents such as aluminum oxide and excess lithium are needed to preserve the cubic phase and compensate for lithium volatility during high temperature processing. Material engineering that allows LLZO to be fabricated with lower sensitivity to processing conditions is an important enabler in ultimate implementation of this material.
Given the range of ceramic materials processing constraints such as ball milling, calcination, and sintering at temperatures above 1000oC, lithium volatility can drive deleterious phase formation. This study was designed to consider mechanisms that reduce the processing sensitivities of aluminum doped LLZO along its path to being utilized in a ceramic-manufacturing optimal ASSB. Processing sensitivities ameliorated via direct incorporation of excess lithium within LLZO lattice provides a key advantage towards the densification over topical additions of excess lithium precursors. By utilizing thermogravimetric analysis in conjunction with in-situ XRD analysis of solid state LLZO precursor synthesis the sensitivity of the LLZO cubic phase to lithium volatility can be reduced via early incorporation of excess lithium carbonate during initial formation. Details of in-situ phase evolution of LLZO from precursors were further clarified via temperature resolved mapping of diffraction patterns. The improved suppression of lithium volatilization has helpful implications for the scalable production of LLZO powders and assembly of ASSBs.
(Digital Presentation) Fabrication of Single-Crystal Layered Oxide Cathode through Variation on Heating Process
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Kenneth Fung , Chang Chia-Chin 
Published: July 2022

Since the announcement of a million-mile battery by Tesla, single-crystal processing of layered oxide cathode has received great attention recently. From single-crystal process, high Ni layered oxides with grain size in mm range tends to give better cycling performance due to better structural integrity against repeated charge/discharge cycles.
However, during heating/calcination process of oxide/carbonates/nitrates powder compacts, it may involve decomposition, chemical reactions, diffusion, oxidation, sintering, grain-growth. For single-crystal process, the powder compacts need to be heated to higher temperatures (~950°C) for certain period of time. On the other hand, enough air/oxygen is need for Ni oxidation and better crystallization in Ni-rich layered structure. Therefore, it is important to investigate the processing of single-crystal Ni-rich layered oxide based on the sintering behavior, thermal gravimetric analysis, and phase transformation.
Nevertheless, the lithiation/oxidation of Ni-containing oxides involves charge compensation resulted from defect reactions. As a result, the affected electrical, optical, structural, and electrochemical properties of layered oxides will be discussed based on defect chemistry consideration. The structural, microstructural and electrical properties of decomposed precursors and doped layered oxides will be examined using XRD, SEM and DC/AC impedance measurements. CV and charge/discharge tests from assembled coin cells will be used to evaluate electrochemical properties of single-crystal Ni-rich layered oxides.
(Invited) Nano Ontario - A Model for Regional Cooperation in Nanotechnology
Authors: Mascher Peter 
Published: July 2022

Nano Ontario is a not-for-profit corporation representing the interests of academic, industrial, government and financial community members in the development of nanotechnologies in Ontario, Canada. Members work together to raise the profile, increase the research, build the investment and drive economic returns from nanotechnology in the province and across Canada.
In this presentation I will discuss how this multi-sector cooperation serves to achieve the following main objectives:

Be a trusted source of information for all nanoscience and nanotechnology activity in Ontario;

Advise government organizations on economic opportunity, policy, standards & regulations that nanotechnology can offer, to enable Ontario to benefit and capitalize from its nano research, development, and commercial capacity;

Map Ontario’s capacity in nanotechnology research, development, and commercialization;

Serve as the main point of contact for Ontario’s community of practice in nanoscience & nanotechnology;

Build and facilitate new connections between nanotechnology groups in universities, government organizations and industries within Ontario, across Canada, and internationally; and

Coordinate public outreach activities to advocate the societal benefits enabled by nanoscience and nanotechnology.
(Invited) Impact of Pore Morphology and Surface Hydrophobicity of the Carbon Matrix on the Macrokinetics of the Oxygen Reduction Reaction Performance for Atomically Dispersed Fe-N-C Catalysts
Authors: Liu Yuanchao , Murphy Eamonn , Mamania Divija Nitin , Khedekar Kaustubh , Asset Tristan , Jaouen Frederic , Zenyuk Iryna V. , Atanassov Plamen 
Published: July 2022

Atomically dispersed transition metal catalysts are an important family of non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The iron-nitrogen-carbon (Fe-N-C) catalyst, wherein the iron metal centers are coordinated by nitrogen atoms (FeNx) on carbonaceous supports, exhibits outstanding ORR activity in both rotating disk electrode (RDE) and membrane electrode assembly (MEA) configurations.[1] The pore structure[2] and surface hydrophobicity[3] of the carbon matrix are of particular significance to the MEA performance, where the high current throughput requires good mass transport capability and controlled water flooding on the electrodes. In this work, we employed two widely used Fe-N-C catalysts – one pyrolyzed from metal organic framework (MOF-derived)[4] and the other produced by using the sacrificial support method (sacrificial templated)[1]. Specifically, nitrogen physisorption and water vapor physisorption were used to study the pore morphology and the specific surface hydrophobicity, respectively. As shown in Figure 1, the sacrificial templated Fe-N-C catalyst showed a significant mesoporosity as compared to the MOF-derived counterpart, while its surface was much more hydrophobic, as indicated by the less water uptake through whole pressure range (Figure 1f). Such difference of carbon morphology was further correlated to their macrokinetic performance in a MEA configuration, to reveal the impact of the morphological and hydrophilic/hydrophobic balance on these two types of Fe-N-C catalysts.

Reference

[1] T. Asset and P. Atanassov, Joule, 2020, 4, 33.
[2] Y. Huang, Y. Chen, M. Xu, T. Asset, P. Tieu, A. Gili, D. Kulkarni, V. de Andrade, F. de Carlo, H. S. Barnard, A. Doran, D. Y. Parkinson, X. Pan, P. Atanassov, and I. Zenyuk, Materials Today, 2021, 47, 53.
[3] L. Liu, S. J. Tan, T. Horikawa, D. D. Do, D. Nicholson and J. Liu, Adv Colloid Interface Sci, 2017, 250, 64.
[4] K. Kumar, T. Asset, X. Li, Y. Liu, X. Yan, Y. Chen, M. Mermoux, X. Pan, P. Atanassov, F. Maillard and L. Dubau, ACS Catalysis, 11, 484.

Figure 1. XRD (a) and AC-STEM (b-d) images of the Fe-N-C catalyst produced by the sacrificial support method. Nitrogen (e) and water vapor (f) physisorption isotherms of MOF-derived and sacrificial templated Fe-N-C catalysts. (g) Pore size distribution of the two catalysts by the BJH method based on the N2 adsorption branch.

Figure 1
Effect of Heteroatoms Doped Nanoporous Carbon for Aqueous Zinc–Bromine Battery
Authors: HAN Sunghoon , Kang Jisue , Kim Jong Gyeong , Pak Chanho 
Published: July 2022

As interest in renewable energy increases, the importance of batteries that store surplus power is also increasing. However, frequent ignition issues with the lithium-ion secondary battery arose. One of the next-generation batteries, Zinc-Bromine based aqueous flow batteries, are being actively studied based on advantages of high safety and environmental benignity. However, there is an exorbitant price for flow battery due to the use of a membrane, an electrolyte tank, and a pump. In order to eliminate the shortcomings, this research introduced a form of membraneless and flowless systems.
In this study, a nanoporous carbon material doped with nitrogen and boron heteroatoms was synthesized and coated on graphite felt. Differences in electrochemical performance were observed when carbon was coated with different slurry compositions (activated carbon: conductive carbon: binder), dopant amount of heteroatoms, and carbon loading mass. Cyclic voltammetry was performed with a three-electrode system to observe the faradaic reaction of active materials according to the potential change. Besides the difference in contact angle for ZnBr2 electrolyte, there are differences in single cell test at 20 mA/cm2 & 2 mAh/cm2 and performance test at 20 mA/cm2 & 24.3 mAh/cm2. These causes can be explained not only by the effect of the different slurry compositions, but also by the interaction of the active material with the coated carbon. Also, the redox reactions of bromine anion during charging process could be a clue for the battery capacity. Cathodic reactions for polybromide [Br2 + Brn
– → Brn+2
– , (n=1,3,5...)] can be analyzed by Raman spectroscopy. The peak shift and deconvolution of the Raman data can measure the progress of cathodic reactions. The boron dopants can stabilize the reversibility of faradaic reactions and induce high resistance to strong acid electrolytes (For ZnBr2 electrolyte of 2.0 M or higher, it has a value under the pH 4).

Figure 1
Charge and Hydrogen Storage Capacities of Electrodeposited Graphene Derivatives
Authors: Avraham Hanan , Kadosh Yanir , Korin Eli , Bettelheim Armand 
Published: July 2022

Graphene’s theoretical capacitance and physical hydrogen storage abilitiesmark it as one of the best candidates for energy storage application. Graphene oxide (GO) is easy to manufacture in bulk synthesis and can be considered as a precursor for graphene synthesis. The application of graphene on the surface of electrodes can be achieved by different techniques as drop-coating and electrodeposition. It has been reported that the electrochemical hydrogen storage is favored in samples with a well-developed porosity and a low content in surface oxygen complexes. Both features indicate that the unsaturated carbon atoms in the carbon materials have an important role for the hydrogen uptake. It has also been suggested that the total capacity of hydrogen storage is proportional to the interlayer distance and not to the carbon specific surface area.
The present work presents an investigation of electrodeposited GO coatings (ED), which have subsequently been electroreduced to various degrees of rGO, and relate their charge capacitance and hydrogen storage capacity to the preparation mode, morphological structure, and surface chemistry. These properties were compared to those of drop-cast (DC) coatings of GO.
The ED coatings were characterized by more accumulated graphene sheets imperfections as observed by cross section TEM analysis. These coatings, when reduced at -1.6 V vs Hg/HgO showed more efficient removal of phenolic groups than DC ones treated at the same potential (remaining contents of 2.1 and 18.1 %, respectively). They also showed lower charge transfer resistance (5.2 and 28 Ω cm2, respectively), higher capacitance (73.2 and 42.6 F/g, respectively), and higher hydrogen storage capacity (119 and 57 mAh/g, respectively). Moreover, they showed higher stability towards H2 charge/discharge cycles (retained hydrogen capacities of 95 and 40 % after 15 and 6 cycles for ED and DC coatings reduced at -1.5 V, respectively).
The removal during the electroreduction process of phenolic groups located at the graphene sheets edges of the ED coatings and their higher pseudo-capacitance can explain their lower charge transfer resistance and their higher pseudo-capacitance, respectively. Their superior stability towards hydrogen charge/discharge cycles is suggested to stem from evolving hydrogen escape routes created during the ED process. The superior performance properties of coatings obtained by ED and subsequently electro-reduced make them promising electrode materials for energy storage.
(Invited, Digital Presentation) Carbon Nanotube Near-Infrared Fluorescent Labels, and Biodistribution of Carbon Nanotubes after Intravenous Injection
Authors: Okazaki Toshiya 
Published: July 2022

Single-walled carbon nanotubes (CNTs) are promising candidates for near-infrared (NIR) fluorescent labels in diagnostic fields. We here report a complex of oxygen-doped CNT (o-CNT) and streptavidin (SA) to prepare CNT-based NIR labels with a high reaction efficiency in immunoassays [1]. This complex specifically binds to biotin molecules by conjugating a linker molecule of phospholipid polyethylene glycol (PL-PEG) to SA (o-CNT-SA). The immunoprecipitation (IP) reaction efficiency between o-CNT-SA and biotin reaches 79.3% by uniformly covering the surface of o-CNTs with SA conjugated PL-PEG (SA-PEG). Further, we also report the biodistribution and toxicity of oxidized super-growth single-wall carbon nanotubes (oxSG) injected intravenously into mice over 3months [2].
[1] K. Kojima, Y. Iizumi, M. Zhang, T. Okazaki, submitted.
[2] M. Zhang, Y. Xu, M. Yang, M. Yudasaka, T. Okazaki, 15, 798-811 (2021).
(Invited) Using Cell Lensing and Nanosensor Chemical Cytometry to Characterize Immune Cell Populations
Authors: Gong Xun , Cho Soo-Yeon , Koman Volodymyr , Jin Xiaojia , Strano Michael 
Published: July 2022

Recently, we developed a method called Nanosensor Chemical Cytometry (NCC), where an optical nanosensor array embedded within microfluidics can be used to interrogate chemical species efflux from individual cells. The cell itself was found to perform as an informative Gaussian lens, projecting both the nIR emission of the single-walled carbon nanotube sensors as well as various cellular physical properties. We found NCC to be able to profile immune heterogeneities at attomolar sensitivity in a completely non-destructive and real-time manner with rate of ~600 cells/hr.
Macrophages are a critical part of the human immune response, and their collective heterogeneity is implicated in disease progression and prevention. Here, we use the NCC technique to profile the heterogeneity of inducible nitric oxide synthase (iNOS) responses from macrophage populations. Parameters measured nitric oxide (NO) efflux and refractive index (RI) changes at a single-cell level. Using NCC, NO was measured with (10−18 mol) sensitivity in a nondestructive and real-time manner with a throughput of exceeding the 200 cells/frame. With lipopolysaccharide (LPS) activation, NO efflux elevated from 342 (σ = 199) to 464 (σ = 206) attomol/cell·hr, in agreement with previously reported Griess assay results. This work provides an efficient strategy for chemical analysis of cell populations for manufacturing and biopharmaceutical engineering.
(Invited) Multivalent [60]Fullerene Hexakis-Adducts for Biomedical Applications
Authors: Illescas Martínez Beatriz M. , Patino-Alonso Jennifer , Nieto-Ortiz Gema , Cabrera-González Justo , Martín Nazario 
Published: July 2022

Now more than ever we are aware of the need of development of new antiviral materials to fight off unknown virus and overcome the multidrug resistance shown by different pathogens. Such resistance is considered a public health threat and the WHO predicted millions of deaths during the next years caused by resistant microorganisms. Carbon based nanomaterials hold promise for alternative and innovative approaches as they are biodegradable and biocompatible materials with unique tunable optical, electronic and mechanical properties.
Many biological recognition processes take advantage of multivalency to enhance weak ligand-receptor affinities. Typical important multivalent interactions are the protein-carbohydrate recognition involved in viral entry, cell surface adhesion, and host-pathogen interactions. Among the carbon based nanomaterials, [60]fullerene constitutes a privileged scaffold with a highly symmetrical and rigid nanosized structure. We have modified it to form hexakis-adducts with octahedral geometry for the multivalent presentation of carbohydrates or amino acids.1,2 Tridecafullerenes constructed by a central [60]fullerene scaffold surrounded by other twelve fullerene units endowed with up to 360 disaccharides have been synthesized and studied in viral infection inhibition biological assays. These systems have shown a remarkable efficiency in the inhibition of the infectious process by Ebola, Zika and Dengue viruses, with IC50 values in the picomolar range.3

New multivalent nanostructures with different topology and/or fluorescent platforms are currently being synthesized and evaluated in our group. The latest results will be presented.

References:

[1] Muñoz, A.; Sigwalt, D.; Illescas, B. M.; Luczkowiak, J.; Rodríguez-Pérez, L.; Nierengarten, I.; Holler, M.; Remy, J.-S.; Buffet, K.; Vincent, S. P.; Rojo, J.; Delgado, R.; Nierengarten, J.-F.; Martín, N. Nat. Chem.,
2016, 8, 50-57.
[2] Ruiz-Santaquiteria, M.; Illescas, B. M.; Abdelnabi, R.; Boonen, A.; Mills, A.; Martí-Marí, O.; Noppen, S.; Neyts, J.; Schols, D.; Gago, F.; San-Félix, A.; Camarasa, M. J., Martín, N. Chem. Eur. J.
2021, 27, 10700–10710.
[3] Ramos-Soriano, J.; Reina, J. J.; Illescas, B. M.; De La Cruz, N.; Rodríguez-Pérez, L.; Lasala, F.; Rojo, J.; Delgado, R.; Martín, N. J. Am.
Chem. Soc.
2019, 141, 15403-15412.
(Invited) Influence of Vibrations on the Emission Properties of Single Graphene Quantum Dots
Authors: Liu Thomas , Tonnelé Claire , Elias Christine , Rondin Loïc , Carles Baptiste , Medina Lopez Daniel , Chassagneux Yannick , Narita Akimistu , Voisin Christophe , Campidelli Stephane , Beljonne David , Lauret Js 
Published: July 2022

Recent years have shown an increasing number of studies dedicated to new light emitters for diverse applications such as optoelectronics, bio-imaging, and quantum technologies. In this context, graphene quantum dots (GQD) have important assets since bottom-up chemistry allows complete control of the structure, opening the way to wide customization of their electronic, optical, and spin properties [1-3]. The full benefit from these opportunities requires addressing GQD’s intrinsic photophysical properties.To do so, single molecule photoluminescence experiment is a powerfull tool [4]. Here, we highlight the influence of vibrations on GQDs’ optical properties, by comparing optical studies to extensive DFT/TDDFT calculations combined with molecular dynamics simulations. Specifically, we discussed their role in the transitions' oscillator strengths [5]. In order to get deeper in the photophysics of GQD, we investigate the spectroscopy of single GQDs at cryogenic temperatures. In particular, we show a narrowing of the emission lines at low temperature, that allows us to characterize and identify vibrational replicas that are characteristic to GQDs [6].
[1] M. G. Debije, J. Am.
Chem. Soc. 2004, 126, 4641
[2] X. Yan, X. Cui, and L.-s. Li, J. Am. Chem. Soc. 2010 132, 5944
[3] A. Konishi et al, J. Am. Chem. Soc. 2010, 132, 11021
[4] S. Zhao et al, Nature Communications, 2018, 9, 3470
[5] T. Liu et al, under review
[6] T. Liu et al, in preparation
(Digital Presentation) Chiroptical Effect in Aligned Carbon Nanotube Films
Authors: Doumani Jacques , Lou Minhan , Yanagi Kazuhiro , Kono Junichiro , Gao Weilu 
Published: July 2022

The dissymmetric interaction between circularly polarized light and solid-state materials is central to developing next-generation chiral photonic devices for applications such as spectroscopy and imaging. The strong quantum confinement in 1D single-wall carbon nanotubes (SWCNTs) features extraordinary electrical and optical properties and enables high-performance optoelectronic devices for the generation, modulation, and detection of light. The recent success of separating chirality-enriched [1], especially enantiomer-enriched, SWCNT suspensions and their macroscopic alignment assembly [2] further pushes the frontier of improving the performance and bringing new chiral functionalities of SWCNT-based optoelectronic devices. However, the chiroptical spectroscopy characterization mainly focuses on solution samples or individual SWCNTs. There has been no report of such studies in macroscopic solid-state films of SWCNTs. In this work, we investigate the circular dichroism (CD) spectroscopy of the solution and large-area films of non-racemic, chirality-mixture SWCNTs synthesized using the arc-discharge method. We prepared multiple films with various degrees of alignment using the controlled vacuum filtration method [2]. By carefully designing a cuvette that is manufactured through a stereolithography-type 3D printer (Fig. 1a) and performing a 4-configuration measurement by flipping and rotating samples (Fig. 1b), the effects from linear dichroism and birefringence can be minimized [3]. As expected, both solution and random film samples displayed zero CD; see Fig. 1c. In stark contrast, the aligned films displayed strong CD signals (~ 480 mdeg at the peak position). More surprisingly, the signs of obtained CD signals from different aligned films can be completely opposite even though their degrees of alignment, in terms of reduced linear dichroism (LDr) at the wavelength of 1035 nm, and thicknesses are nearly the same; see Fig. 1c. We will discuss possible origins of these surprising chiroptical responses in terms of slight and gradual twisted rotations of alignment directors, which can happen during spontaneous alignment in the vacuum filtration process.
[1] Ichinose, Y., Eda, J., Yomogida, Y. et al. Extraction of High-Purity Single-Chirality Single-Walled Carbon Nanotubes through Precise pH Control Using Carbon Dioxide Bubbling. The Journal of Physical Chemistry C
121, 13391-13395 (2017).
[2] He, X., Gao, W., Xie, L. et al. Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nature Nanotech
11, 633–638 (2016).
[3] Albano, G., Pescitelli, G. et al. Chiroptical Properties in Thin Films of π-Conjugated Systems. Chemical Reviews

120
, 10145-10243 (2020).

Figure 1