bluuebunny/crossref_metadata_2025_split huggingface dataset:
Covalent Functionalization of Kevlar Fabric with Graphene Nanosheets
Authors: Sideri Ioanna K. , Canton-Vitoria Ruben , Vasilakos Sozon , Siamidis Dionysios , Tagmatarchis Nikos 
Published: September 2023

Whilst technical textile requirements for personal protecting clothing have dramatically increased during the past years due to the climate and health crisis, as well as the human factor, garment industry is in search of new fabrics that will meet these emerging needs. Aiming in the realization of superior fabrics performing under extreme environmental and operational conditions, carbon nanostructures and graphene-related 2D nanomaterials offer their mechanical strength and functionalization capability in this new challenge.1 However, most techniques developed for the hybridization of fabric fibers with carbon nanostructures and related 2D nanomaterials are based on physisorption and surface coating. Herein, we present a protocol for the covalent modification of Kevlar fibers in order to generate free amine groups on their aromatic rings that can be chemically manipulated to covalently attach graphene nanosheets. In particular, Friedel-Crafts type nitration of Kevlar fibers, followed by hydrogenation to furnish amine moieties, allows condensation with a small amino acid that serves as the connector with oxidized graphene flakes (Figure 1).2 Optimized conditions and in depth spectroscopic study are provided that collectively offer an easy-monitoring protocol of each step and allow the transfer of this knowledge to other related 2D nanomaterials. Considering the ability of 2D nanomaterials to carry designed properties via functionalization, this methodology allows the realization of multipurpose custom fabrics with enhanced qualities of choice.
Partial financial support by the European Regional Development Fund of the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call RESEARCH-CREATE-INNOVATE (project code: Τ2EDK-01316) is acknowledged.
References
[1] I. K. Sideri, N. Tagmatarchis, Mater. Horiz., 2021, 8, 3187.
[2] Manuscript in preparation.

Figure 1
Symmetric Electrochemical Supercapacitors Based on Electrodes of Graphene Nanoribbons/Iron-Doped Lanthanum-Strontium-Manganese Based Perovskite Oxides
Authors: Heiba Asmaa R. , Abou Shahba Rabab M. , Dhmees Abdelghaffar S , Taher Fatma A , El Sawy Ehab 
Published: September 2023

The dramatic increase in the world population and industrialization have resulted in unprecedented levels of humanity's hunger for energy. The total global energy production has increased from 23 in 1900 to 548 Exajoules (1018 J = EJ) in 2016.1 A significant contribution of the internment renewable energy resources to the energy production before the mid of this century becomes a necessity to significantly reduce fossil fuel usage and hence limit global warming.1 This creates a great incentive to identify the best ways to store energy when it is not needed.
Supercapacitors have gained significant attention due to their fast charging/discharging speed, high power density, and long-term cycling stability in contrast to traditional batteries.2 In recent years, perovskites and graphene nanoribbons have been significantly considered promising materials for electrochemical energy storage. The graphene-based materials have a highly tunable surface area, outstanding electrical conductivity, good chemical stability, and excellent mechanical behavior.3 While the perovskite materials provide the possibility of both anionic and cationic storage mechanisms.4

This presentation reports the in situ preparation of iron-dopped lanthanum-strontium-manganese-based perovskite oxides (La0.7Sr0.3MnxFe1-xO3-δ, LSMFO) in the presence of graphene nanoribbons (GNRs), and the evaluation of the supercapacitive behavior of the synthesized composites. The physical/chemical structure of LSMFO was evaluated using XRD, TEM, FT-IR, Raman spectroscopy, EDS, BET, and XPS. Integrating the perovskite materials that possess redox reaction ability with graphene nanoribbons that exhibit good electronic properties is found to improve the supercapacitor performance in comparison to the single components. The symmetric supercapacitor devices based on LSMFO/GNRs showed good stability (capacitive retention of 95% over 10,000 cycles at a higher current density of 10 A g-1), a wide potential window (up to 1.7 V), and a relatively high capacitance. The best composite with optimum LSMFO:GNRs ratio that shows the highest supercapacitance is identified and explained in correlation with its surface chemical structure.

References

G. A. Jones and K. J. Warner, Energy Policy, 93, 206–212 (2016).

S. Ghosh, K. Anbalagan, U. N. Kumar, T. Thomas, and G. R. Rao, Applied Materials Today, 21, 100872 (2020).

O. D. Salahdin et al., Appl. Phys. A, 128, 703 (2022).

B.-M. Kim et al., Sci Rep, 12, 10043 (2022).
Cascaded Compression of the Size Distribution of Nanopores in Monolayer Graphene
Authors: Wang Jiangtao , Cheng Chi , Kong Jing 
Published: September 2023

Nanoporous graphene has shown great promise for membrane separations. Its atomic thickness, remarkable mechanical, chemical, and thermal robustness could enable ultrahigh-flux membrane processes addressing persistent challenges in a wide range of separation needs. On the other hand, molecular separations across nanoporous graphene rely dominantly on size-based mechanisms (e.g, size exclusion) that is highly sensitive to the nanopore size and size distribution of nanopore ensemble created on the graphene. However, among existing nanopore creation methods, the process of nanopore nucleation is often coupled with nanopore expansion, which results in a lognormal nanopore size distribution with a long tail. It remains a challenge to obtain both high density and narrow size distribution of nanopores in graphene. Here, we report a cascaded compression approach to engineering nanopores in monolayer graphene for molecular separations with the assistance of electrical control of chemical vapor deposition of graphene[1]. The formation of nanopores is split into many small steps, in each of which the size distribution of all the existing nanopores is compressed by a combination of shrinkage and expansion, and at the same time of expansion, a new batch of nanopores is created, leading to increased nanopore density by each cycle. As a result, high-density nanopores with a short-tail size distribution are obtained by the cascaded compression that show high rejection and ultrafast organic solvent nanofiltration exceeding the state-of-the-art.
Reference
[1] Wang J, Park J H, Lu A Y, et al. Electrical Control of Chemical Vapor Deposition of Graphene. Journal of the American Chemical Society, 20
(Invited) Graphene-Based Scaffolds for Electrochemical Energy Storage
Authors: Chandrasekaran Swetha , Lin Dun , Reale Batista Mariana Desiree , Li Hanyu , Carleton Adam , Xue Xinzhe , Luo Yunkai , Hu Bintao , Moran Bryan , Roy Thomas , Orme Christine , Dunn Bruce S. , Li Yat , Worsley Marcus Andre 
Published: September 2023

The efficient transport of charge species within energy storage devices is critical to realizing both large power and energy densities, especially when operating under extreme conditions (e.g. ultralow temperatures, high charge/discharge rates, etc.). A number of resistances can contribute to sluggish ion/electron transport in a cell such as charge transfer at interfaces, electrolyte resistance, electrode resistance, and diffusive transport within porous electrodes. Several strategies have been pursued to address these transport limitations. Electrolyte engineering is an effective approach as it can influence both electrolyte resistance and charge transfer resistances. Electrode materials discovery and development is another popular strategy as the charge storage mechanism and electrode resistance play a key role in kinetics of the device. Within electrode materials development, engineering of the electrode pore architecture is an extremely effective strategy to decrease the diffusive transport lengths and electrode resistances. This pore engineering can be achieved through synthetic chemistry for small pores (e.g. <10 um) and via additive manufacturing for larger pores (> 10 um). Here we show how electrolyte engineering and electrode materials development can be used to overcome sluggish transport in graphene-based electrodes. Particular focus will be given to the use of synthetic means to tune to the properties of a graphene aerogel scaffold (e.g. surface area, pore size, mechanical properties) and additive manufacturing to define the larger pore structure to facilitate uniform deposition of active materials (e.g. MnO2) and improve energy density and rate capability of the energy storage device. We explore a number of additive manufacturing techniques (e.g. direct ink write, projection microstereolithography, etc.) to print a variety of lattice structures and computer-guided designs to determine the optimal electrode architecture.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
(Invited) Progress in Materials and Process for Sustainable Perovskite Solar Cells
Authors: Jung Hyun Suk 
Published: September 2023

All solid-state solar cells based on organometal trihalide perovskite absorbers have already achieved distinguished power conversion efficiency (PCE) to over 25% and further improvements are expected up to 27%. Now, the research on perovskite solar cells (PSCs) has been moving toward commercialization. To facilitate commercialization of these great solar cells, some technical issues such as long-term stability, large scale fabrication process, and Pb-related hazardous materials need to be solved. Also, flexible perovskite solar cell using plastic substrate can be used in niche applications such as portable electrical chargers, electronic textiles, and large-scale industrial roofing.
This talk is dealing with our recent efforts to facilitate commercialization of perovskite solar cells. For examples, we introduce a recycling technology of perovskite solar cells, which covers the regeneration process of Pb contained perovskite layer as well as recycling process of Au electrodes and transparent conducting oxide glass. Also, simple fabrication technologies for realizing large scale perovskite module are introduced and recent effort for achieving high efficiency module is going to be presented. Finally, recent interesting results regarding ultra flexible perovskite cells will be discussed.
(Invited) Identification of a Self-Photosensitizing Hydrogen Atom Transfer Organocatalyst System
Authors: Mitsunuma Harunobu , Fuse Hiromu , Irie Yu , Fuki Masaaki , Kobori Yasuhiro , Kato Kosaku , Yamakata Akira , Higashi Masahiro , Kanai Motomu 
Published: September 2023

The carbon-hydrogen (C-H) bond is a fundamental chemical bond that constitutes organic molecules, and its direct conversion leads to highly efficient molecular synthesis. In recent years, the hydrogen atom transfer (HAT) catalysis using the energy of visible light, has been attracting attention. However, existing methods require the use of photoredox catalysts such as organic molecules with complex structures and expensive metal complexes. In this study, we developed an organocatalytic system that mimics the electron transfer process of enzymes in vivo and promotes functionalization of stable C-H bond without photoredox catalyst. We designed a thiophosphoric acid catalyst that contains both a redox-active binaphthyl moiety and a sulfur atom. We found that this catalyst forms charge-transfer complexes with electron-deficient heteroaromatics and catalytically produces thyil radical via multi-step electron transfer under visible light irradiation.
Based on the above design, we decided to investigate the formation of active HAT catalytic species in the absence of photoredox catalysis by the Minisci-type reaction using aldehydes and N-heteroaromatic rings. The results of the study confirmed that 29% of the product was obtained when using binaphtyl thiophosphoric acid (TPA) catalyst, as expected. Yield improved to 80% when an electron-donating group was introduced to the binaphthyl skeleton to enhance the donor-acceptor interaction. Changing the binaphthyl skeleton and thiophosphoric acid moieties markedly reduced reactivity, indicating that the presence of a sulfur atom in addition to a rigid binaphthyl skeleton is essential for the efficient reaction progress. With this optimized condition, alkylation of N-heteroaromatic rings by C-H bond activation of alcohols was found to proceed. Dehydrogenation of alcohols and benzylation of imines were also successfully achieved by using N-heteroaromatic catalyst. The mechanism of the electron transfer process has been confirmed by spectroscopic and computational methods, and will be presented in detail in the lecture.

Figure 1
(Invited) 5,15-Diazatetrabenzoporphyrins: Evaluation as Organic Semiconductors
Authors: Yamada Hiroko , Matsuo Kyohei 
Published: September 2023

Tetrabenzo-5,15-diazaporphyrin (TBDAP) is a structural hybrid molecule of tetrabenzoporphyrin (TBP) and phthalocyanine (Pc). As compared with TBP, TBDAP has energetically lower HOMO and LUMO because of the higher electronegativity of nitrogen atom at meso-position. Moreover, its optoelectronic properties, solubility and molecular arrangement in the solid state can be controlled by introducing various substituents at another meso-carbons. These electronic and structural tunabilities of TBDAP are advantageous to the organic electronic application such as organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), but selective and efficient synthetic methods for TBDAP are limited. Triisopropylsilyl (TIPS)-ethynyl group is one of the most popular substituents for organic semiconducting molecules. We synthesized 5,15- bis(triisopropylsilylethynyl)tetrabenzoporphine (TIPS-TBP) and its metal complexes. TIPS-TBP has reasonable solubility for solution-processed OFETs and exhibits excellent hole mobilities of 1.1 cm2 V−
1 s−
1 and 2.16 cm2 V−
1 s−
1 in dip-coating FET and single-crystal FET, respectively [1, 2]. These values are higher than that of pristine free-base TBP (0.07 cm2 V−1 s−1), indicating that TIPS-ethynyl group is also useful for porphyrin analogues. Herein, we report the synthesis of 10,20-bis(triisopropylsilylethynyl)tetrabenzo-5,15-diazaporphine (TIPS-TBDAP) by metal-template aza-annulation reaction [3,4]. TIPS-TBDAP exhibited efficient far-red fluorescence in solution and formed one-dimensional (1D) columnar structure in crystal packing. Its charge transporting property evaluated by preparing dip-coating FET and single-crystal FET will be also reported.
References
[1] K. Takahashi, B. Shan, X. Xu, S. Yang, T. Koganezawa, D. Kuzuhara, N. Aratani, M. Suzuki*, Q. Miao*, H. Yamada*, Engineering Thin Films of a Tetrabenzoporphyrin toward Efficient Charge-Carrier Transport: Selective Formation of a Brickwork Motif. ACS Appl. Mater. Interfaces 2017, 9, 8211-8218.
[2] J. Zhu, H. Hayashi*, M. Chen, C. Xiao, K. Matsuo, N. Aratani, L. Zhang, H. Yamada*, Single crystal field-effect transistor of tetrabenzoporphyrin with one-dimensionally extended columnar packing motif exhibiting efficient charge transport property J. Mater. Chem. C 2022, 10, 2527-2531.
[3] Y. Sugano, K. Matsuo*, H. Hayashi, N. Aratani, H. Yamada*, Synthesis of 10,20-substituted tetrabenzo-5,15-diazaporphyrin copper complexes from soluble precursors. J. Porphyrins Phthalocyanines 2021, 25, 1186-1192.
[4] Y. Sugano, K. Matsuo*, H. Hayashi, N. Aratani, H. Yamada*, Synthesis and properties of 10,20-bis(triisopropylsilylethynyl)-tetrabenzo-5,15-diazaporphine. J. Porphyrins Phthalocyanines 2022, 26, in press.
Colloidal Synthesis and Photoluminescence Property of Near-IR-Responsive Ag8GeS6 Quantum Dots
Authors: Rismaningsih Nurmanita , Kubo Junya , Fujihira Norikazu , Kameyama Tatsuya , Torimoto Tsukasa 
Published: September 2023

Semiconductor nanocrystals of a few nanometers in size, called quantum dots (QDs), exhibit unique photochemical properties due to quantum size effect. In recent years, high-quality near-infrared responsive QDs such as CdTe and PbS have been used for wide-ranged applications from light-energy conversions to biomedical applications. However, the contents of highly toxic elements, Cd and Pb, restrict their practical use. On the other hand, group IV-based multinary compound semiconductors, such as Ag2ZnSnS4, Ag8SnS6, and Ag8GeS6, have attracted much attention because of their less toxicity and light absorption property in visible and near-IR region. However, there are only a few reports to prepare size-quantized nanocrystals for tuning their photoelectrochemical properties. In this study, we report the preparation of Ag8GeS6 core and Ag8GeS6@ZnS core/shell QDs using a feasible liquid-phase chemical synthesis method.
As a moisture and air stable Ge precursor, Ge(gly)2(H2O)2 was prepared by the literature method with slight modification[1]. Precursor powders of Ge(gly)2(H2O)2, silver(I) diethyldithiocarbamate, and thiourea were dispersed in a mixture solvent of 1-dodecanethiol and oleylamine, followed by the heat treatment at 423 K for 20 min. Thus-obtained QDs were isolated from the reaction solution by the addition of methanol and ethanol as a non-solvent. Then, the obtained QDs were finally dispersed in chloroform. The obtained Ag8GeS6 QDs were further surface-coated with thin ZnS layer to form Ag8GeS6@ZnS core/shell QDs.
The onset wavelengths in the absorption spectra of Ag8GeS6 and Ag8GeS6@ZnS were observed at 850 nm and 830 nm, respectively. The XRD analysis showed that the obtained nanocrystals had an orthorhombic Ag8GeS6 crystal structure. TEM measurements revealed that the prepared Ag8GeS6 QDs had an average particle size of 4.53 nm while that of Ag8GeS6@ZnS was 5.80 nm. From the difference between the sizes before and after ZnS coating, we estimated the ZnS shell thickness of Ag8GeS6@ZnS to 0.63 nm. The energy gap of Ag8GeS6 QDs was slightly decreased from 1.45 eV to 1.37 eV with an increase in Ge/(Ge+Ag) ratio. Ag8GeS6 QDs with Ge/(Ge+Ag) = 0.8 exhibited a broad photoluminescence (PL) peak at 850 nm with PLQY of about 25%. The surface coating with ZnS remarkably increased the PLQY to 65%, which was considerably high in comparison to those of near-IR-emissive multinary QDs in our previous papers such as Ag–In–Ga–Se and Ag–In–Ga–S–Se QDs [2,3]. Thus, the present Ag8GeS6@ZnS QDs seem to be a promising probe for bio-imaging with near-IR photoluminescence.
[1] A.S.R. Chesman, et al., Chem. Mater, 26, 5726 (2014).
[2] T. Kameyama, et al., ACS Appl. Nano Mater, 3, 3275-3287 (2020).
[3] N. Rismaningsih, et al., J. Mater. Chem. C, 9, 12791-12801 (2021).
Machine-Learning Assisted Identification of Battery Life Models
Authors: Gasper Paul , Collath Nils , Hesse Holger , Jossen Andreas , Smith Kandler 
Published: September 2023

Predictive battery life models are commonly utilized to extrapolate degradation trends observed during accelerated aging tests for simulation of degradation in real-world applications. Thus, fitting accelerated aging data as accurately as possible and with low uncertainty is crucial for making believable projections of battery lifetime, but it is challenging to identify algebraic expressions that accurately fit multivariate degradation trends. A review of models published in literature reveal some common expressions for fitting calendar aging data, which is only dependent on temperature and state-of-charge, but no consistency across many models for fitting cycle aging data, indicating the need for a statistically rigorous data driven approach for developing empirical models.
This talk will describe a machine-learning assisted method for identification of predictive battery life models utilizing bilevel optimization and symbolic regression. Bilevel optimization with cross-validation is used to statistically determine cell- and stress-dependent model parameters, while symbolic regression identifies both linear and multiplicative candidate expressions to predict stress-dependent degradation rates by selecting low-order subsets of features from a generated feature library. Because model expressions are identified empirically, it is crucial to ensure resulting models behave according to physical expectations, so the stability of models for interpolation or extrapolation is interrogated qualitatively through simulation and quantitatively through cross-validation and uncertainty quantification via bootstrap resampling. This model identification approach substantially improves upon models identified purely using expert judgement in terms of both accuracy and uncertainty.
Model simulation and validation is then conducted by deriving a state-equation form of the predictive model, enabling simulation of battery aging under dynamic stresses. This enables validation of the predictive battery model on lab-based tests with varying conditions or on drive-cycle or application-cycle testing protocols. Parameter uncertainty can be carried forward into model simulation, giving lifetime estimates and confidence windows for cell- or system-level lifetime. The financial impact of battery model uncertainty can be estimated by incorporating uncertainty into a technoeconomic model.
Conductive Metal Organic Framework as Trapping Cathode Additive for High Performance Lithium-Sulfur Batteries
Authors: Nazir Aqsa , Motevalian Saeme , El-Zahab Bilal 
Published: September 2023

Lithium-Sulfur (Li-S) batteries with high capacity and energy density have arisen as one of the most promising secondary batteries. However, higher order lithium polysulfide (LiPSs) shuttling and insulating nature of sulfur cathode results in capacity degradation and premature failure of the cell [1]. Here for the first time, we have implemented conductive Cu metal-based Metal organic framework (Cu-MOF) as a Li-S battery cathode material. Cu-MOF cathode catalyst not only reduce the LiPSs shuttle effect but also increase the conductivity of Li-S battery cathode [2].
Here, Cu-MOF pore morphology will trap the polysulfides and further prevent LiPSs shuttling. In addition, the well-defined architecture of organic ligands of Cu-MOF also participate to explicate the involved surface-binding mechanisms of S and polysulfide products. Furthermore, Cu-MOF improve the diffusion rate of Li ions, shackling LiPSs, upsurging conduction of electrons/ions, and regulating the deposition of Li2S2/Li2S towards cathode side [3]. Furthermore, sulfur active material is well percolated inside the pores of conductive Cu-MOF which shows the long-cycling performance as shown in Figure 1.
Benefiting from the unique fibrous, porous, interwoven structure, the conductive MOF@S-composite cathode demonstrates a high initial capacity of 1671 mAh g–1 at 0.05 C rate with a good coulombic efficiency of >95% and the outstanding capacity of 849 mAh g-1 cycles even after 200 cycles at the 0.5 C-rate with coulombic efficiency of 98.3%. It is believed that, the experimental findings and mechanistic understanding of Cu-MOF cathode in this work will open a new avenue for the further development of other conductive MOFs in the Li-S batteries.

Figure 1: Cycling performance of S@Cu-MOF composite at 0.5 C-rate.

References

Mingyue Wang, Zhongchao Bai, Ting Yang, Chuanhao Nie, Xun Xu, Yunxiao Wang, Jian Yang, Shixue Dou, and Nana Wan."Advances in High Sulfur Loading Cathodes for Practical Lithium-Sulfur Batteries." Energy Mater, no.12 (2022): 2201585.

Dan Luo, Chaojie Li, Yongguang Zhang, Qianyi Ma, Chuyin Ma, Yihang Nie, Matthew Li, Xuefei Weng, Rong Huang, Yan Zhao, Lingling Shui, Xin Wang, Zhongwei Chen. "Design of Quasi-MOF Nanospheres as a Dynamic Electrocatalyst toward Accelerated Sulfur Reduction Reaction for High-Performance Lithium–Sulfur Batteries." Mater, no.34 (2022): 210554.

Jun Zhang, Ye Shi, Yu Ding, Lele Peng, Wenkui Zhang, Guihua Yu. "A Conductive Molecular Framework Derived Li2S/N,P-Codoped Carbon Cathode for Advanced Lithium–Sulfur Batteries." Energy Mater, no.7 (2017): 1602876.

Figure 1