bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Exohedral Functionalization in Actinide Mono-Metallofullerenes: Computations Are Able to Explain Experiments
Authors: Rodriguez-Fortea Antonio , Abella Laura , Torrens Daniel , Poblet Josep M. 
Published: September 2023

Since the isolation of the first endohedral metallofullerene La@C82,1 intensive research has been devoted to this family of compounds that encapsulate metal atoms or clusters in their inner void space.2 Recently, the first metallofullerene containing an actinide, Th@C82, was isolated and characterized.3 Other mono-actinidofullerenes as non-IPR U@C80, Th@C80 and U@C76; or IPR U@C82, U@C84, U@C86, Th@C80 and Th@C82 have been also characterized.4 In mono-actinidofullerenes, the actinide tends to have oxidation state +4, which involves an important metal-cage interaction with significant covalent contributions. This feature makes them different from lanthanofullerenes, where the metal is usually with oxidation state +3. Consequently, the electronic structure, properties as well as reactivity of actinidofullerenes are expected to be different compared to their lanthanide counterparts. We here analyze with computations at DFT level the exohedral functionalization of mono-actinidofullerenes for some typical addition and radical reactions, being able to explain their characteristic regioselectivity.
References

Chai, Y.; Cuo, T.; Jin, C.; Haufler, R. E.; Felipe Chibante, L. P.; Fure, J.; Wang, L.; Alford, J. M.; Smalley, R. E. J. Phys. Chem.
1991, 95, 7564-7568.

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

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

a) Cai, W.; Abella, L.; Zhuang, J.; Zhang, X.; Feng, L.; Wang, Y.; Morales-Martínez, R.; Esper, R.; Boero, M.; Metta-Magaña, A.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L.; Chen, N. J. Am. Chem. Soc.
2018, 140, 18039-18050; b) Yao, Y.-R.; Roselló, Y.; Ma, L.; Puente Santiago, A. R.; Metta-Magaña, A.; Chen, N.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L. J. Am. Chem. Soc.
2021, 143, 15309-15318; c) Yan, Y.; Morales-Martinez, R.; Zhuang, J.; Yao, Y.-R.; Li, X.; Poblet, J. M.; Rodriguez-Fortea, A.; Chen, N. Chem. Commun.
2021, 57, 6624-6627; d) Meng, Q.; Morales-Martínez, R.; Zhuang, J.; Yao, Y.-R.; Wang, Y.; Feng, L.; Poblet, J. M.; Rodriguez-Fortea, A.; Chen, N. Inorg. Chem.
2021, 60, 11496-11502.
Decatungstate Photocatalyzed Acylation of 2D Transition Metal Dichalcogenides
Authors: Sideri Ioanna K. , Canton-Vitoria Ruben , Tagmatarchis Nikos 
Published: September 2023

2D Transition metal dichalcogenides (TMDs) and their unique chemistry have flourished in the recent years owing to their pertinence in a broad series of front-row applications including electronic, opto-epectronic and energy storage /harvest devices for the semiconductors,1, 2 while also catalysis and photo /electrothermal applications for the metallic phases.3 Since their ability to protagonist in such applications is dependent on their chemical structure and processing, a great deal of research effort has been focused on TMDs’ functionalization. The nucleophilic nature of the metallic phase is responsible for the uneven flourish, regarding covalent functionalization, in favor of the metallic phase vs the semiconducting. In parallel, the main inspiration for such chemical transformations on 2D TMDs has been organic chemistry. However, until now there is no report based on a catalytic protocol for the covalent functionalization of TMDs. Following our previous report on the catalytic transformation of single walled carbon nanotubes,4 we herein present the decatungstate-photocatalyzed acylation of 2H-MoS2 and 2H-MoSe2, employing aliphatic and aromatic aldehydes (Figure 1). The successful protocol is accompanied by detailed optimization and spectroscopic characterization. The availability of the various aldehydes as means to realize chemical modifications of choice on the surface of 2H phase of TMDs and the mild reaction conditions protocol, shape an ideal methodology to advance the chemistry of 2D TMDs bringing them one step closer to industry applications.
References
[1] W. Choi, N. Choudhary, G. H. Han, J. Park, D. Akinwande, Y. H. Lee, Mater. Today 2017, 20, 3, 116-130.
[2] C. Stangel, E. Nikoli, N. Tagmatarchis, Adv. Energy Sustainability Res. 2022, 2200097.
[3] X. Yin, C. S. Tang, Y. Zheng, J. Gao, J. Wu, H. Zhang, M. Chhowalla, W. Chen, A. T. S. Wee, Chem. Soc. Rev., 2021, 50, 10087-10115.
[4] R. Canton-Vitoria, M. Quintana, N. G. Malliaros, N. Tagmatarchis, Adv. Mater. Interfaces 2022, 2201575.

Figure 1
Intercalation and Functionalization in 2D Materials
Authors: Cha Judy J 
Published: September 2023

The large surface areas and interlayer gaps of 2D materials enable surface functionalization and intercalation as effective post-synthesis design knobs to tune the properties of 2D materials using ions, atoms, and organic molecules. For complete engineering control, detailed understanding of the interactions between the 2D materials and the molecules adsorbed on 2D materials surface or between the 2D materials and the intercalants is necessary.
I will first discuss surface functionalization to tune the electrical properties of 2D materials. We developed an experimental approach to quantitatively measure the doping powers of organic electron donors (OEDs) to monolayer MoS2. Using novel and previously studied OEDs, we demonstrate experimentally that the measured doping power is a sensitive function of molecule’s reduction potential, size, surface coverage, and orientation to 2D materials [1, 2].
I will then discuss electrochemical intercalation into 2D materials to induce novel phases that were previously undetected and to study heterointerface effects on the intercalation induced phase transition [3, 4]. We discover new structural phases in Td-WTe2 and T’-MoTe2 with lithium intercalation and these new phases are semiconducting even though the initial WTe2 and MoTe2 are semimetallic and lithium ions donate electrons to the host materials. In the lithium intercalation-induced phase transition from the 2H to 1T’ phase of MoS2, we show that the nucleation of the 1T’ phase proceeds via heterogeneous nucleation where the nature of heterointerface dictates the thermodynamics of the phase transition. For these studies, multi-modal, in-situ probes were necessary to track the changes in the structure-property relation of the layered materials as a function of intercalation.
[1] Advanced Electronic Materials 7, 2000873 (2021).
[2] Nano Letters 22, p.4501 (2022).
[3] ACS Applied Materials & Interfaces 13, p.10603-10611 (2021).
[4] Advanced Materials 34, 2200861 (2022).
(Invited) Two-Dimensional Neuromorphic Computing Materials and Devices
Authors: Hersam Mark C 
Published: September 2023

The exponentially improving performance of digital computers has recently slowed due to the speed and power consumption issues resulting from the von Neumann bottleneck. In contrast, neuromorphic computing aims to circumvent these limitations by spatially co-locating logic and memory. Beyond reducing power consumption, neuromorphic devices provide efficient architectures for image recognition, machine learning, and artificial intelligence [1]. This talk will explore how two-dimensional (2D) nanoelectronic materials enable gate-tunable neuromorphic devices [2]. For example, by utilizing self-aligned, atomically thin heterojunctions, dual-gated Gaussian transistors have been realized, which show tunable anti-ambipolarity for artificial neurons, competitive learning, spiking circuits, and mixed-kernel support vector machines [3]. In addition, field-driven defect motion in polycrystalline monolayer MoS2 enables gate-tunable memristive phenomena that serve as the basis of hybrid memristor/transistor devices (i.e., 'memtransistors' [4]) that concurrently provide logic and data storage functions [5]. The planar geometry of memtransistors further allows multiple contacts and dual gating that mimic the behavior of biological systems such as heterosynaptic responses [6]. Moreover, control over polycrystalline grain structure enhances the tunability of potentiation and depression, which enables unsupervised continuous learning in spiking neural networks [7]. Overall, this work introduces foundational circuit elements for neuromorphic computing by utilizing the unique quantum characteristics of 2D nanoelectronic materials [8].
[1] V. K. Sangwan, et al., Nature Nanotechnology,
15, 517 (2020).
[2] M. E. Beck, et al., ACS Nano, 14, 6498 (2020).
[3] M. E. Beck, et al., Nature Communications, 11, 1565 (2020).
[4] V. K. Sangwan, et al., Nature, 554, 500 (2018).
[5] X. Yan, et al., Advanced Materials, 34, 2108025 (2022).
[6] H.-S. Lee, et al., Advanced Functional Materials, 30, 2003683 (2020).
[7] J. Yuan, et al., Nano Letters, 21, 6432 (2021).
[8] X. Liu, et al., Nature Reviews Materials, 4, 669 (2019).
The Effect of Anionic and Cationic Charge Carriers on the Supercapacitive Behavior of Graphene Nanoribbons
Authors: Heiba Asmaa R. , Abou Shahba Rabab M. , Dhmees Abdelghaffar S , Taher Fatma A , El Sawy Ehab 
Published: September 2023

As worldwide energy consumption continues to increase, so too does the demand for improved energy storage technologies. Supercapacitors have attracted a lot of attention due to their quick charging/discharging rate, high power density, and long-term cycling stability in comparison to conventional batteries.1 Graphene nanoribbons (GNRs) with ultrathin two-dimensional structures and unique properties received a lot of attention recently as potential materials for electrochemical energy storage and specifically supercapacitors.2,3 GNRs maintain graphene’s unique lattice structure in one dimension and provide more open-edge structures compared to graphene, thus allowing faster ion diffusion, which makes GNRs highly promising for energy storage systems.2,3 GNRs have unique characteristics such as exceptional electrical conductivity, a highly modifiable surface area, strong chemical stability, low toxicity, great mechanical behavior, and the ability to tune properties for the desired application.
This presentation provides an overview of the production of GNRs from carbon nanotubes and their application in supercapacitors. The physical/chemical structure of GNRs was evaluated using XRD, TEM, FT-IR, Raman spectroscopy, and XPS. Since the selection of the cation and anion has been reported to have a dramatic effect on the specific capacitance of the studied materials,4 the supercapacitive behavior of GNR was thoroughly investigated in various media (H2SO4, KOH, K2SO4 ), using different loadings and different evaluation systems (three and two-electrode systems). GNRs, in all of the tested media, showed good stability (retained 95% of their capacitance over 10,000 cycles at a high current density of 10 A/g), a wide potential window (up to 1.7 V), and a relatively high capacitance (≈ 400-800 F/g). The best medium for GNRs highest supercapacitance in correlation with their surface chemical structure will be discussed.

References:

E. A. Worsley, S. Margadonna, and P. Bertoncello, Nanomaterials, 12, 3600 (2022).

Z. Liu et al., Advanced Functional Materials, 32, 2109543 (2022).

Twinkle et al., Materials Today: Proceedings, 50, 1511–1515 (2022).

B. Pal, S. Yang, S. Ramesh, V. Thangadurai, and R. Jose, Nanoscale Adv., 1, 3807–3835 (2019).
In-Operando Raman Study on the Use of 2D and Suboxide Titanium Host Materials for Lithium-Sulfur Batteries
Authors: Pereira Rhyz , Ruffino Anthony , Masiuk Stefan , Cardoza Neal A. , Badr Hussein , Barsoum Michel W. , Spanier Jonathan , Kalra Vibha 
Published: September 2023

While Lithium-Sulfur (Li-S) batteries have promised high capacities and low-cost material inputs, their potential has yet to be realized due to inherent issues with sulfur cathodes. In particular the polysulfide shuttle effect and sulfur’s intrinsic insulating properties stand in the way of a commercial battery, the demands of which include high sulfur loading and high cycling stability. Engineering the sulfur cathode, via the use of promising new materials has been an avenue of research pursued in the hopes of mitigating the shuttle effect via polysulfide entrapment and introducing more conductive materials.
Of particular interest have been titanium oxide based materials which have shown polysulfide adsorption capabilities. However, the most common titanium oxide, anatase titanium (IV) oxide (TiO2) acts as an insulator, limiting its use in high sulfur loading batteries. Therefore, the use of more conductive titanium oxide materials is an attractive avenue of research. A previously reported freestanding titanium suboxide (TiO) carbon nanofiber cathode demonstrated excellent capacities (~790 mAh/g, ~2 mg/cm2). A rare lepidocrocite phase has also been observed via Raman spectroscopy in a newly discovered titanium carbide derived titanium oxide nanofilament (1D-NF). This material demonstrates properties that makes it attractive as a sulfur host material, having a high surface area of ~1700 m2/g, improved polysulfide reduction kinetics via the formation of polythionates, and polysulfide-cathode host interactions. The inclusion of these nanofilaments in sulfur cathodes yields capacities of ~800 mAh/g with ~1 mg/cm2 sulfur loading.
The proposed mechanism via which these titanium oxide based materials function has never been investigated in-operando, and herein we conduct an in-operando Raman study to understand the behavior of these materials. Principally we will investigate the Eg band whose vibration can be moderated by the interaction of terminal sulfur atoms acting as Lewis bases and titanium atoms acting as Lewis acids, due to their vacant valance electrons. This interaction has been observed via postmortem XPS. The use of in-operando Raman allows us to uniquely observe transient behavior of the host material as well as the impact of crystal structure on polysulfide host interactions.
Identifying Non-Stationarity in Non-Linear Harmonics of EIS Measurements of Li Batteries
Authors: Zabara Mohammed Ahmed , Katırcı Gökberk , Ülgüt Burak 
Published: September 2023

Non-linear Harmonic Analysis is a technique used to investigate the distortions in Electrochemical Impedance Spectroscopy (EIS) measurements. The distortions are in both non-linear and non-stationary nature that appear as high order harmonics in the frequency domain. Differentiating the origin of the harmonics is important in understanding their nature and relating them to electrochemical phenomena. Here, we will show how the harmonics are in direct relation to the initial non-stationary response (initial transient) of the excited system [1]. We will show by both experimental measurements and simulations of dummy cell circuits, representing the electrochemical interface, that the initial transient exhibits high order harmonics that show the highest value at the characteristic frequency of the process [1]. We also extend the analysis to include more complex systems of primary Lithium batteries [2]. It is observed that the same non-stationary initial transient behavior is persistent in the time constants of the electrochemical processes. It is concluded that the capacitive components of the electrochemical processes are responsible for such non-stationary behavior in electrochemical systems [2].
[1] G. Katırcı, M. A. Zabara, and B. Ülgüt, “Methods—Unexpected Effects in Galvanostatic EIS of Randles’ Cells: Initial Transients and Harmonics Generated,” J Electrochem Soc, vol. 169, no. 3, p. 030527, Mar. 2022, doi: 10.1149/1945-7111/ac5ad7.
[2] M. A. Zabara, G. Katırcı, and B. Ülgüt, “Non-linear harmonics in EIS of batteries with lithium anodes: Proper controls and analysis,” Electrochim Acta, vol. 429, Oct. 2022, doi: 10.1016/j.electacta.2022.140969.
Aluminum Alloys as Anodes for Aluminum Batteries
Authors: Bandiera Marco , Pavesi Arianna , Valota Giorgio , Abello Mary Angel , Trombetta Valentina , Bonfanti Andrea , Mancini Alessandro , Bertasi Federico 
Published: September 2023

The development of batteries based on metals alternative to Lithium (e.g. Na, Mg, Zn, Al) requires the investigation of new electrodes and electrolytes. [1,2].
This is particularly true in the case of non-aqueous Aluminum batteries which typically include a pure (>99.8%) Aluminum anode which: a) suffer of poor cycling stability and low coulombic efficiency; b) is particularly subjected to dendrite growth; c) can undergo to corrosion phenomena upon cycling; and d) show a poor compatibility toward chloroaluminated electrolytes [3].
In this regard, the development of Aluminum alloys, alternative to pure Al anodes, is a challenging task which is barely investigated in the field of Aluminum ion batteries and requires experience in both battery electrochemistry and Aluminum metallurgy and casting.
In this scenario, the proposed work investigates the synthesis and characterization of ternary Aluminum, alloys comprising Si, Ti and B as alloying elements, as anodes for Al-ion batteries [4]. Deposition/stripping measurements, impedance spectroscopy, metallographic analysis, EDXS and XRD techniques unveil the complex interplay existing between the microstructures of the alloys and the obtained electrochemical performance. It is demonstrated that a remarkable improvement in the: a) oxidation/reduction currents and overvoltages; and b) interfacial stability with the electrolyte; can be obtained, with respect to a conventional Al anode. Results allow to demonstrate that the investigation of Aluminum alloys can be crucial for the development of future Aluminum batteries.
[1] F Bertasi, C Hettige, F Sepehr, X Bogle, G Pagot, K Vezzù, E Negro, S J Paddison, S G Greenbaum, M Vittadello, V Di Noto, ChemSusChem, 2015, 8 (18), 3069-3076
[2] F Bertasi, F Sepehr, G Pagot, SJ Paddison, V Di Noto, Advanced Functional Materials 2016, 26 (27), 4860-4865
[3] Y Zhang, S Liu, Y Ji, J Ma, H Yu, Advanced Materials 2018, 30 (38), 1706310
[4] Italian Patent Application n° 102022000024522
Non-Fullerene Acceptors for Organic Photovoltaics
Authors: Imahori Hiroshi 
Published: September 2023

Non-fullerene acceptors (NFA) have attracted much attention in organic photovoltaics because of their excellent light-harvesting property and facile tuning of HOMO-LUMO levels. In particular, ITIC and Y6 type NFAs have exhibited very high power conversion efficiency exceeding 15%. In this talk I will give an overview of our initiatives on NFAs.
[1] T. Umeyama, K. Igarashi, D. Sasada, Y. Tamai, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, H. Imahori, Chem. Sci., 11, 3250-3257 (2020).
[2] T. Umeyama, K. Igarashi, D. Sasada, K. Ishida,T. Koganezawa, S. Ohtani, K. Tanaka, H. Imahori, ACS Appl.
Mater. Interfaces, 12, 39236-39244 (2020).
[3] T. Umeyama, K. Igarashi, Y. Tamai, T. Wada, T. Takeyama, D. Sasada, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, H. Imahori, Sus.
Energy Fuels, 5, 2028-2035 (2021).
[4] T. Umeyama, T. Wada, K. Igarashi, K. Kato, A. Yamakata, T. Takeyama, Y. Sakamoto, Y. Tamai, H. Ohkita, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Imahori, ACS Appl. Energy Mater., 4, 14022-14033 (2021).
[5] S. Li, R. Nishikubo, T. Wada, T. Umeyama, H. Imahori, A. Saeki, Polymer J., in press.
(Invited) Machine Learning and Fast Experimental Screening-Assisted Development of Organic Solar Cell
Authors: Saeki Akinori 
Published: September 2023

Non-fullerene, a small molecular electron acceptor, has substantially improved the power conversion efficiency of organic photovoltaics (OPVs).[1] However, the large structural freedom of π-conjugated polymers and molecules makes it difficult to be explored with limited resources. Machine learning, which is based on the rapidly growing artificial intelligence technology, is a high-throughput method to accelerate the speed of material design and process optimization; however, it suffers from limitations in terms of prediction accuracy, interpretability, data collection, and available data (particularly, experimental data). This recognition motivates the present review, which focuses on utilizing the experimental dataset for ML to efficiently aid OPV research. The author discusses the trends in ML-OPV publications, the NFA category, and the effects of data size and explanatory variables (fingerprints or Mordred descriptors) on the prediction accuracy and explainability, which broadens the scope of ML and would be useful for the development of next-generation solar cell materials.[2]
Despite the advance of ML, the predictive accuracy of ML currently remains insufficient for the design of OPV semiconductors that exhibit a complex connectivity between chemical structure and PCE. In this study, we examined the impact of data selection and the introduction of artificially generated failure data on ML predictions of NFA solar cells. The authors demonstrated that an ML model empowered by artificially generated failure data (~0% PCE by insoluble polymers based on an inappropriate choice of solubilizing side alkyl chains) led to improved predictions.[3] This approach was validated through the synthesis and characterization of twelve polymers (benzothiadiazole, thienothiophene, or tetrazine coupled with benzodithiophene; benzobisthiazole coupled with dioxo-benzodithiophene). Our work offers a facile approach to mitigate the difficulties of the ML-driven development of OPV materials that is also readily applicable to other material science fields.
Reference
[1] Kranthiraja, A. Saeki, Adv. Funct. Mater. 31 (2021) 2011168
[2] Miyake, A. Saeki, J. Phys. Chem. Lett. 12 (2021) 12391.
[3] Miyake, K. Kranthiraja, F. Ishiwari, A. Saeki, Chem. Mater. 34 (2022) 6912.