bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Stabilizing and Enhancing Lithium-Ion Batteries with Chemically Inert 2D Materials
Authors: Hersam Mark C 
Published: July 2022

Efficient energy storage systems represent a critical technology across many sectors including consumer electronics, electrified transportation, and a smart grid accommodating intermittent renewable energy sources. Arguably, the most important advance in energy storage over the past three decades is the lithium-ion battery, which was recently recognized with the Nobel Prize in Chemistry. However, despite its many successes, issues related to safety, energy density, charging time, and operating temperature range have hindered the realization of the full potential of lithium-ion battery technology, particularly in large-scale applications such as grid-level storage and full electrification of transportation networks. Nanostructured materials were once thought to present compelling opportunities for next-generation lithium-ion batteries, but inherent problems related to high surface area to volume ratios at the nanometer-scale (e.g., undesirable surface chemical interactions between electrodes and electrolytes) have impeded their adoption for commercial applications. This talk will explore how the chemical inertness of select two-dimensional (2D) materials are driving a resurgence in nanostructured lithium-ion battery materials [1]. For example, conformal graphene coatings on lithium-ion battery cathode powders mitigate surface degradation and minimize the formation of the solid electrolyte interphase, thus improving cycling stability [2]. In addition, the high electrical conductivity of graphene reduces cell impedance, resulting in enhanced kinetics that enable high-rate capability and low-temperature performance down to –20 °C [3]. On the other hand, ionogel electrolytes based on ionic liquids and hexagonal boron nitride (hBN) nanoplatelets provide safe, high-rate operation at high temperatures up to 175 °C, which represents the highest operating temperature to date for solid-state lithium-ion batteries [4,5]. The strong interfacial interactions between hBN and ionic liquids further enable novel electrolyte architectures based on layered heterostructure ionogels that result in unprecedently high energy densities and rate performance for solid-state batteries [6].
[1] H. Bergeron, et al., Chemical Reviews, 121, 2713 (2021).
[2] K.-Y. Park, et al., Advanced Energy Materials, 10, 2001216 (2020).
[3] K.-Y. Park, et al., Advanced Materials, DOI: 10.1002/adma.202106402 (2021).
[4] W. J. Hyun, et al., ACS Nano, 13, 9664 (2019).
[5] W. J. Hyun, et al., Advanced Energy Materials, 10, 2002135 (2020).
[6] W. J. Hyun, et al., Advanced Materials, 33, 2007864 (2021).
(Invited, Digital Presentation) Single-Atom Quantum Magnetism in 2D Materials
Authors: Villarreal Renan 
Published: July 2022

With the advent of 2D materials, the playground to study spins in dilute and non-dilute phases has expanded. This is appealing for utilizing the additional degrees of freedom of electron systems such as spin and valley and, from the fundamental point of view, to better understand atomic scale magnetic phenomena in low dimensional materials. Dilute magnetism in 2D materials can lead to complex magnetic phenomena (e.g., Kondo effect, RKKY-interactions, quantum relaxation and coherence), with potential for applications in spintronics (e.g., spin FETs) and quantum technologies (e.g., single-atom quantum memories). We are investigating how to selectively incorporate substitutional magnetic atoms (3d transition metals and 4f rare earths) in 2D materials, using ultra low energy ion implantation, and we characterize their structural, electronic, and magnetic properties [1]. Ultra-low energy (ULE) ion implantation allows us to precisely tune the kinetic energy of the ions, providing control over the form of incorporation and concentration while preserving the structural and electronic properties of graphene. Our approach is based on a wide range of characterization techniques (structural and electronic), including scanning tunneling microscopy and spectroscopy (STM/STS), Raman spectroscopy, synchrotron-based X-ray photoelectron spectroscopy (XPS), angle-resolved photoemission spectroscopy (ARPES), X-ray magnetic circular dichroism (XMCD), among others. These experimental studies are complemented by density functional theory (DFT) and molecular dynamics (MD) simulations. The new insights provided by our work establish a framework for the controlled incorporation of magnetic dopants in 2D materials, using ULE ion implantation.
[1] P. C. Lin et al., ACS Nano 15(3), 5449-5458 (2021).
Development of Anode-Free Metal Batteries
Authors: Zhang Ji-Guang , Cao Xia , LE Phung M-L , Jin Yan , Kim Ju-Myung , Xu Wu 
Published: July 2022

Ever increasing need for electrical vehicles (EVs) continually pushes the boundary of high-density energy storage systems. To date, the state of the art of lithium (Li) ion batteries (LIBs) consisting of graphite anode and high voltage Li intercalation cathodes cannot satisfy the energy demand from these applications. By replacing graphite anode with Li metal anode (LMA), specific energy density of Li metal batteries (LMBs) can increase by more than 50% because LMA has a much higher specific capacity (3820 mAh g-1) than that of graphite (372 mAh g-1). To further increase the energy density of Li batteries, the concept of “anode-free” Li batteries (AFLBs) has been explored. Similar approach can also be used in “anode-free” sodium (Na) batteries (AFSBs) to further improve their energy densities. In this work, we will report our recent work on the development of AFLBs and AFSBs. The common challenges in these batteries will be analyzed and compared first. Several approaches, including development of novel electrolytes, substrate treatment, optimization of testing protocol and environment conditions, have been adopted to increase the cycle life of these batteries. At last, future perspective and application of anode-fee metal batteries will be discussed.
References

Niu, C.; Liu, D.; Lochala, J. A.; Anderson, C. S.; Cao, X.; Gross, M. E.; Xu, W.; Zhang, J.-G.; Whittingham, M. S.; Xiao, J.; Liu, J., Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nature Energy
2021.

Zhang, J.-G., Anode-less. Nature Energy
2019,
4 (8), 637-638.

Pereira, N.; Amatucci, G. G.; Whittingham, M. S.; Hamlen, R., Lithium–titanium disulfide rechargeable cell performance after 35 years of storage. Journal of Power Sources
2015,
280, 18-22.

Boyle, D. T.; Huang, W.; Wang, H.; Li, Y.; Chen, H.; Yu, Z.; Zhang, W.; Bao, Z.; Cui, Y., Corrosion of lithium metal anodes during calendar ageing and its microscopic origins. Nature Energy
2021.
(Invited) Advanced Photoresponsive Materials from Porphyrins and Porphyrins: The Metal–Organic Framework Approach
Authors: Woell Christof 
Published: July 2022

For the fabrication of macroscopic devices exploiting the properties of organic chromophores, the availability of well-defined thin films of high optical quality is an important prerequisite. Optical absorption properties are often strongly affected by inter-chromophore interactions, and therefore periodic assemblies with low defect densities offer substantial advantages over amorphous compounds. In this context, crystalline reticular networks have recently attracted considerable interest. By appropriate functionalization, most organic chromophores can be converted to function as di- or higher-topic linkers, which can coordinate to metal or metal-oxo centers so as to yield stable, metal-organic frameworks, or MOFs. Of particular interest in this context are light-switchable MOFs. However, the conventional powder form of MOFs obtained using solvothermal approaches, exhibits substantial drawbacks with regard to optical applications, e.g. limited efficiency resulting from absorption and light scattering caused by the (micrometer-sized) powder particles. Providing MOFs in the form of thin films avoids these problems. We have developed a layer-by-layer (lbl) deposition method to produce well-defined, highly oriented and monolithic MOF thin films on a number of different substrates. The resulting films are referred to as SURMOFs [1]. The fabrication of hetero-multilayers containing well-defined hetero-interfaces is rather straightforward with this lbl method. A particularly attractive option it to exploit the porous nature of the MOFs in connection with the lbl method to integrate C60 into SURMOF-based devices, e.g. in the context of photoconductivity [2]. In the context on nonlinear optical properties, using sophisticated assembly strategies were recently used to fabricate non-centrosymmetric SURMOFs with high SHG activity [3].

References:

[1] R. Haldar, L. Heinke, Ch. Wöll, Advanced Materials (2020), DOI: 10.1002/adma.201905227
[2] X. Liu, M. Kozlowska, T. Okkali, D. Wagner, T. Higashino, G. Brenner-Weiß, S. M. Marschner, Z. Fu, Q. Zhang, H. Imahori, S. Bräse, W. Wenzel, C. Wöll, L. Heinke, Angew. Chem. Int. Ed. 2019, 58, 9590
[3] A. Nefedov, R. Haldar, Z. Xu, H. Kühner, D. Hofmann, D. Goll, B. Sapotta, S. Hecht, M. Krstić, C. Rockstuhl, W. Wenzel, S. Bräse, P. Tegeder, E. Zojer, Ch. Wöll, Adv. Mat. 2103287 (2021)
(Invited, Digital Presentation) In silico Photochemical Experiments with Non-Born-Oppenheimer Molecular Dynamics
Authors: Curchod Basile 
Published: July 2022

What happens to a molecule once it has absorbed UV or visible light? How does the molecule release or convert the extra energy it just received? Answering these questions clearly goes beyond a pure theoretical curiosity, as photochemical and photophysical processes are central to numerous domains like energy conversion and storage, radiation damages in DNA, or atmospheric chemistry. Different theoretical tools have been developed to address these questions by simulating the excited-state dynamics of molecules [1]. Two examples of such methods include ab initio multiple spawning (AIMS) and trajectory surface hopping (TSH). AIMS describes the dynamics of nuclear wavepackets using adaptive linear combinations of traveling frozen Gaussians [2]. TSH portrays the nuclear dynamics with a swarm of independent classical trajectories that can hop between potential energy surfaces for this task [3].
In this talk, I intend to briefly survey some of our recent work aiming at understanding the approximations underlying AIMS [4] and developing new approximate techniques based on the multiple spawning framework [5]. I will also discuss the application of nonadiabatic methods to unravel photochemical and photophysical processes of interest for photovoltaics.

References

[1] F. Agostini and B. F. E. Curchod, WIREs Comput. Mol. Sci. 2019, 9, e1417.
[2] B. F. E. Curchod and T. J. Martínez, Chem. Rev. 2018, 118, 3305.
[3] J. C. Tully, J. Chem. Phys. 1990, 93, 1061.
[4] B. Mignolet and B. F. E. Curchod, J. Chem. Phys. 2018, 148, 134110; B. Mignolet and B. F. E. Curchod, J. Phys. Chem. A 2019, 123, 3582; L. M. Ibele and B. F. E. Curchod, Phys. Chem. Chem. Phys. 2020, 22, 15183.
[5] B. F. E. Curchod, W. J. Glover, T. J. Martínez, J. Phys. Chem. A 2020, 124, 6133.
Rational Design of Dyes and Donor-Acceptor Type Molecules for Organic Solar Cells
Authors: Imahori Hiroshi 
Published: July 2022

Organic solar cells (OSCs) have received considerable attention as clean energy conversion devices because of their lightweightness, cost effectiveness, flexibility, and suitability for roll-to-roll printing. In dye-sensitized solar cells the core structure has included a dye-anchored TiO2 electrode for photoinduced charge separation, while in bulk heterojunction OSCs, the active layer of OSC devices has usually consisted of a mixture of conjugated polymers as donors and fullerene derivatives as acceptors.1,2 In particular, the power conversion efficiency (PCE) of OSCs based on fullerene derivative acceptors has reached over 10%. However, it is difficult to further increase the PCE of fullerene-based OSCs due to their inherent limitations including arduous energy-level tunability and low absorption profile. To enhance the photovoltaic performance of OSCs, nonfullerene acceptors (NFAs) with aromatic fused-ring structures have emerged rapidly in recent years to fabricate high-efficiency OPVs. Compared to traditional fullerene acceptors, NFAs possess several advantages, such as facile synthesis and high absorption profile. Most high-performance NFAs possess acceptor-donor-acceptor (A-D-A) type structures, in which fused multi-ring ladder structures are used as the D unit and 1,1-dicyanomethylene-3-indanone (IC) derivatives as the A unit.
In this talk I will give an overview of our recent studies on rational design and synthesis of novel dyes and nonfullerene acceptors. In paticular, several nonfullerene acceptors possessing different D units have been designed and synthesized to address the relationship between the structure and the photophysical and photovoltaic properties of the A-D-A type nonfullerene acceptors.3-6

[1] T. Umeyama and H. Imahori, J. Mater. Chem. A (Feature Article), 2, 11545-11560 (2014).
[2] T. Umeyama and H. Imahori, Acc. Chem. Res.
52, 2046-2055 (2019).
[3] T. Umeyama, K. Igarashi, D. Sasada, Y. Tamai, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, and H. Imahori, Chem. Sci., 11, 3250-3257 (2020).
[4] T. Umeyama, K. Igarashi, D. Sasada, K. Ishida,T. Koganezawa, S. Ohtani, K. Tanaka, and H. Imahori, ACS Appl. Mater. Interfaces, 12, 39236-39244 (2020).
[5] T. Umeyama, K. Igarashi, Y. Tamai, T. Wada, T. Takeyama, D. Sasada, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, and H. Imahori, Sus. Energy Fuels, 5, 2028-2035 (2021).
[6] 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, and H. Imahori, ACS Adv. Energy Mater., in press.
(Invited, Digital Presentation) Synthesis of Multi-Metallic Clusters Using a Dendrimer Reactor
Authors: Yamamoto Kimihisa 
Published: July 2022

Dendrimers are highly branched organic macromolecules with successive layers or “generations” of branch units surrounding a central core. Organic inorganic hybrid versions have also been produced, by trapping metal ions or metal clusters within the voids of the dendrimers. Their unusual, tree-like topology endows these nanometer-sized macromolecules with a gradient in branch density from the interior to the exterior, which can be exploited to direct the transfer of charge and energy from the dendrimer periphery to its core.
We show that tinchloride, SnCl2 and FeCl3 complexes to the imines groups of a spherical polyphenylazomethine dendrimer in a stepwise fashion according to an electron gradient, with complexation in a more peripheral generation proceeding only after complexation in generations closer to the core has been completed. By attaching an electron-withdrawing group to the dendrimer core, we are able to change the complexation pattern, so that the core imines are complexed last. By further extending this strategy, it should be possible to control the number and location of metal ions incorporated into dendrimer structures, which might and uses as tailored catalysts, building blocks, or fine-controlled clusters for advanced materials. The metal-assembly in a discrete molecule can be converted to a size-regulated metal particle with a size smaller than 1 nm as a molecular reactor. Due to the well-defined number of metal clusters in the subnanometer size region, its property is much different from that of bulk or general metal nanoparticles. The chemistry of metal clusters on the sub-nanometer scale is not yet well understood because metal clusters, especially multi-metallic clusters, are difficult to synthesize with control over size and composition. The template synthesis of multi-metallic sub-nanoclusters is achieved using a phenylazomethine dendrimer as a macromolecular template.
Molecular Engineering of Low-Bandgap Porphyrins for Highly Efficient Organic Solarcells
Authors: Cuesta Virginia , Vartanian Maida , de la Cruz Pilar , Sharma Ganesh D , Langa Fernando 
Published: July 2022

Organic solar cells (OSCs) based on solution-processed bulk heterojunction (BHJ) active layers have emerged as promising solutions for the conversion of solar energy into electrical energy in building and indoor applications due to their unique advantages, such as being lightweight and semitrans-parent and the possibility of being processed by low-cost roll-to-roll methods. The BHJ active layer employed for OSCs consists of a blend of an electron-donating material and an electron-accepting material creating internal donor-acceptor heterojunctions, and their optical and electrochemical properties are very important for the realization of a high-power conversion efficiency (PCE).
The optical and electrochemical properties of porphyrins can be adjusted by molecular design and functionalization on the b or meso positions of the porphyrin ring as well as by introduction of different central metal ions.
Although the pioneering use of porphyrins in OSCs was disappointing, as reported efficiencies were very low;the situation has changed over the last five years as Zn-porphyrins with ABAB structures linked to acceptor units, having relatively long-lived singlet excited states, have been successfully used as donors or acceptors, resulting in increased efficiencies.
Here, I´ll present our recent work in design, synthesis, and application of porphyrin-based small molecules for highly efficient OSCs with VOC>1V and PCE>15%.
References

V. Cuesta, M. Vartanian, P. de la Cruz, R. Singhal, G. D. Sharma and F. Langa, J. Mater. Chem. A,2017, 5, 1057.

S. Arrechea, A. Aljarilla, P. de la Cruz, M. K. Singh, G. D. Sharma, F. Langa. J. Mater. Chem. C,

2017, 5, 4742.

M. Vartanian, R. Singhal, P. de la Cruz, S. Biswas, G. D. Sharma and F. Langa, ACS Appl. Energy

Mater. 2018, 1, 1304.

M. Vartanian, P. de la Cruz, F. Langa, S. Biswas, G. D. Sharma. Nanoscale, 2018, 10, 12100.

M. Vartanian, R. Singhal, P. de la Cruz, G. D. Sharma, F. Langa, Chem. Commun,
2018, 54, 14144.

V. Cuesta, R. Singhal, P. de la Cruz, G. D. Sharma, F. Langa, ACS Appl. Mater. Interfaces, 2019, 11, 7216 .

Cuesta, R. Singhal, P. de la Cruz, G. D. Sharma, F. Langa, ChemSusChem
2021, 14, 3439.

H. Dahiya, V. Cuesta, P. de la Cruz, F. Langa, G. D. Sharma ACS Appl. Energy Mater. 2021, 4, 4498.
Ordered Arrangement of Charged Porphyrins in π-Electronic Ion-Pairing Assemblies
Authors: Maeda Hiromitsu 
Published: July 2022

π-Electronic ions with appropriate geometries and peripheral substituents provide assemblies through the interactions between charged building subunits, resulting in fascinating electronic properties. Structures and properties of the assemblies can be controlled by the combined negatively and positively charged species in the assemblies. Thus far, diverse π-electronic ions along with ion-responsive π-electronic systems have afforded dimension-controlled ion-pairing assemblies as crystals, supramolecular gels, and thermotropic liquid crystals.[1] Highly ordered arrangement of charged species has been found to be a key factor to exhibit the enhanced performance as fascinating electronic materials. In fact, ion pairs of porphyrin–AuIII complexes as π-electronic cations, prepared with the combination of various anions including π-electronic anions, formed dimension-controlled assemblies as thermotropic liquid crystals, whose ionic components were highly organized by
i
π–
i
π interactions (mainly electrostatic and dispersion forces).[2] Furthermore, π-electronic ion pairs comprising porphyrin-based π-electronic anions[3] have exhibited characteristic assembling modes via
i
π–
i
π interactions and resulting electronic properties such as solid-state absorption, which was correlated with the arrangement of constituent charged π-systems, and photoinduced electron transfer.[4]
References
[1] Recent reviews: (a) Haketa, Y. et al. Mol. Syst. Des. Eng.
2020, 5, 757; (b) Yamasumi, K. et al. Bull. Chem. Soc. Jpn.
2021, 94, 2252. [2](a) Haketa, H. et al. iScience
2019, 14, 241; (b) Tanaka, H. et al. Chem. Asian J.
2019, 14, 2129; (c) Tanaka, H. et al. Chem. Asian J.
2020, 15, 494; (d) Fumuto, N. et al. Org. Lett.
2021, 23, 3897; (e) Kuno, A. et al. Chem. Eur. J.
2021, 27, 10068. [3](a) Sasano, Y. et al. Dalton Trans.
2017, 46, 8924. (b) Sasano, Y. et al. Chem. Eur. J.
2019, 25, 6712. [4] Sasano, Y.; Tanaka, H. et al. Chem. Sci.
2021, 12, 9645.
Probing the Nitrite Reductase Activity of Heme-Copper Respiratory Oxidase
Authors: Varotsis Constantinos , Pinakoulaki Eftychia 
Published: July 2022

Heme-copper oxidases, in particular cytochrome ba
3, is capable of reducing NO to N2O and oxidizing CO to CO2, although with a low activity. Despite the very low (20%) overall sequence homology to other structurally known cytochrome c oxidases, the four redox centers of cytochrome ba
3 display high similarity with those of other oxidases. Extensive studies, at ambient temperatures, have shown that the heme a
3-CuB binuclear center of fully reduced (FR) and mixed valence (MV) cytochrome ba
3 is subjected to peculiar thermodynamic and kinetic properties, with significant deviations, relative to the mesophilic aa
3-type oxidases. These properties include an increased hydrophobicity, a high affinity of CuB for exogenous ligands such as CO (K > 104 M-1) and a slow intramolecular ligand transfer to heme a
3 (k = 8 s-1). As a result, cytochrome ba
3 is the only documented oxidase where the binding of CO to CuB is exergonic and accounts for 25-30% of the total enzyme concentration. Furthermore, the proximal and the distal environment of heme a
3 shows a high structural flexibility evidenced from the multiple heme a
3 Fe2+-CO conformers detected in both the FR and MV forms of the enzyme. Time-resolved step-scan FTIR studies showed that after photolysis of CO from heme a
3
2+ the ligand is almost quantitatively transferred to CuB
1+ and the transiently formed CuB
1+-CO complex exhibits an unusual long lifetime of 20 ms (pD 8.50). In addition, the midpoint redox potentials of hemes b and a
3 have been reported in three different studies being inverted, with values of 210/213 and 430/285 mV (versus Normal Hydrogen Electrode (NHE)), respectively. Resonance Raman and FTIR studies of the ligand binding properties of heme-copper oxidases will be presented.
References.

Discrete Ligand Binding and Electron Transfer Properties of ba
3-Cytochrome c Oxidase from Thermus thermophilus: Evolutionary Adaption to Low Oxygen and ...C Koutsoupakis, T Soulimane, C. Varotsis Accounts of chemical research 52 (5), 1380-139, 2019.

The structure of a ferrous heme-nitro species in the binuclear heme a3/CuB center of ba
3-cytochrome c oxidase as determined by resonance Raman spectroscopy Loullis, MR Noor, T Soulimane, E Pinakoulaki Chemical Communications 51 (2), 286-289, 2015.