bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) A Perovskite Solar Farm at Crete Enabled By the Utilization of 2D Layered Materials
Authors: Kymakis Emmanuel 
Published: July 2021

The development of perovskite photovoltaics has matured to a point of industry-scale production; however, their operational long-term stability still remains the main obstacle impeding their commercialization. The utilization of solution processable graphene and related two-dimensional materials (GRMs), at different sections of perovskite solar cells represents an effective approach to enhance both the power conversion efficiency and the lifetime stability of such photovoltaic technology. On top of that, their compatibility with large-scale, solution-processable methods such as sheet-to-sheet and roll-to-roll lay the ground for their direct integration in pilot manufacturing lines, significantly improves the capital expenditure of this technology. In this context, a wide range of GRMs have been used as replacements for conventional charge transport layers and interlayers not only to improve the charge dynamics of the devices but also to protect the perovskite layer against diffusion of external agents, such as oxygen and moisture and the metal ion migration.
In this talk, I will give an overview of our recent activities on the realization of highly efficient and stable perovskite solar cells and modules. I will give a holistic insight on how the hierarchical placement of GRMs in all the perovskite device can tune the transport layers work-function, passivate the interface/surface traps and most importantly protect the interfaces, resulting in a simultaneously improvement of the triangle of performance, stability and scalability of the perovskite PVs. Furthermore, I will discuss the implementation of a Solar Farm consisting of GRM enabled perovskite 0.5 sqm panels at the Hellenic Mediterranean University campus at Crete, in which outdoor field tests are currently performed. The latter is a pivotal information on the commercialization potential of this technology. I will also directly correlate the electrical measurements of the solar farm with environmental parameters, while at the same time, benchmark their outdoor performance against commercial PV panels installed at the same site.
Efficient Ternary Organic Solar Cells (>14%) Enabled By Non-Fullerene Acceptors
Authors: Privado María , Guijarro Fernando G , Sharma Ganesh D , de la Cruz Pilar , Langa Fernando 
Published: July 2021

Organic Solar Cells (OSCs) fabricated from a ternary active layer, comprised of a mixture of either two electron donors and one acceptor or one donor and two acceptors, are presently at the vanguard of competitive OSCs affording an increased PCE when compared to binary counterparts.
In this presentation, we´ll show our last work in ternary OSCs using two small molecule donors or two electron acceptors reaching efficiencies as high as 14%.
References

Privado, P. Malhotra, P. de la Cruz, R. Singhal, J. Cerdá, J. Aragó, E. Ortí, G. D. Sharma, F. Langa. Solar RRL
2020, 4, 1900471.

G. Guijarro, P. Malhotra, G. Gupta, R. Caballero, P. de la Cruz, R. Singhal, G. D. Sharma, F. Langa. J. Mater. Chem. C, 2020, 8, 4763.

G. Guijarro, R. Caballero, P. de la Cruz, R. Singhal, F. Langa, G.D. Sharma. Solar RRL
2020, 4, 2000460.

Privado, P. de la Cruz, G. Gupta, R. Singhal, G. D. Sharma, F. Langa Solar Energy
2020, 199, 530.

Rodríguez-Seco, L. Cabau, M. Privado, P. de la Cruz, F. Langa, G. D. Sharma, E. Palomares. ACS App. Energy. Mater. 2020. DOI: 10.1021/acsaem.0c02469
Luminescent Soft Crystals That Exhibit Color Changes in Response to Vapor
Authors: Kato Masako 
Published: July 2021

It is well-known that square-planar Pt(II) complexes exhibit characteristic luminescence when the complex units are stacked with Pt···Pt short contacts. Such assembled systems have interesting properties that the luminescence color can change sensitively in response to the surroundings such as temperature, pressure, and vapor. Therefore, the Pt(II) complexes are attractive as flexible and ordered sensing materials called soft crystals. In this presentation, the latest topics of vapochromic Pt(II) complexes are introduced.
1. Wide-range color tuning of luminescence based on the fine control of the Pt···Pt interactions.1) A series of assembled Pt(II) complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups (Figure 1). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield in the solid state at room temperature, originating from the triplet metal-metal-to ligand charge transfer (3MMLCT) state. Their emission colors cover the entire visible region from red to blue by changing the substituents. It is notable that blue 3MMLCT emission was realized firstly in this system. In addition, vapochromic response was observed based on the single-crystal-to-single-crystal transformation.
2. Fast and stable vapochromic response induced through nanocrystal formation of a luminescent platinum(II) complex on periodic mesoporous organosilica.2) A hybrid vapoluminescent system exhibiting fast and repeatable response was constructed using periodic mesoporous organosilica with bipyridine moieties (Bpy-PMO) and a Pt(II) complex bearing a potentially luminescent 2-phenylpyridinato ligand. An intense red luminescence appeared when the Pt(II)-complex immobilized Bpy-PMO was exposed to methanol vapor and disappeared on exposure to pyridine vapor. The ON-OFF vapochromic behavior occurred repeatedly in a methanol/ pyridine/heating cycle. Interestingly, a rapid response was achieved in the second cycle and cycles thereafter. The unique vapoluminescence triggered by the unprecedented protodesilylation on exposure to protic solvent vapor at room temperature is attributable to Bpy-PMO being a giant ligand and an effective vapor condenser. Consequently, this hybrid system presents a new strategy for developing sensors using bulk powdery materials.

1) D. Saito et al., Angew. Chem. Int. Ed. 2020, 59, 18723–18730.

2) H. Matsukawa et al., Sci. Rep.
2019, 9:15151.

Figure 1
(Invited) A Soft-Crystal Chemiluminescence System: Luminescence Property of Adamantylideneadamantane 1,2-Dioxetanes Conjugated with a Fluorophore
Authors: Matsuhashi Chihiro , Uekusa Hidehiro , Ichiyanagi Kouhei , Sato-Tomita Ayana , Ryu Meguya , Morikawa Junko , Maki Shojiro , Hirano Takashi 
Published: July 2021

Chemiluminescence (CL) produces photon by a chemical reaction of a CL substrate to give a product in the excited state. Because emitted photons are readily detectable, CL is a powerful tool to monitor a chemical event in an analyte. In the materials science, CL will be useful to analyze an event at the molecular level in a solid material for developing functional devises. For instance, CL has been used to measure mechanical forces applied to polymers.1 In this study, we have investigated CL reactions in molecular crystals, to create the chemistry of “soft crystals”2 as reaction fields. For this purpose, we investigated CL properties of adamantylideneadamantane 1,2-dioxetanes (Adox) conjugated with a fluorophore in the crystalline state. We report here characteristic CL properties of the Adox derivatives and talk about the molecular mechanism of the crystalline-state CL.3

Adox is one of stable 1,2-dioxetanes, and its thermal decomposition partially gives the excited singlet (S1) or triplet (T1) state of 2-adamantanone (AdCO).4 The S1 state of AdCO can fluoresce weakly with the maximum at 420 nm. A designed Adox derivative 1 has a non-π-conjugatively linked phthahlimide as a crystal structure modulator and the emitting moiety by accepting energy from the excited AdCO. We first prepared syn- and anti-isomers of the Adox derivative 1 and investigated their CL properties in crystals. The isomers showed contrastive CL properties by heating their crystal samples at 160 °C. Each crystal structure of the isomers has its own distinctive packing pattern of the Adox and phthalimide moieties, and the clear differences in CL intensities, emission maxima and reaction kinetics of the isomers are well correlated to the packing patterns. Thus, CL emission properties and reaction kinetics in the crystalline-state were precisely manipulated by the crystal structures. To understand the crystalline-state CL reactions in detail, we further investigated CL of modified Adox derivatives along with thermoanalytical studies. The results provide information on the origins of the characteristic CL behaviors and the reaction mechanism in soft crystals.
1) Chen, Y.; Spiering, A. J. H.; Karthikeyan, S.; Peters, G. W. M.; Meijer, E. W.; Sijbesma, R. P., Nat. Chem., 2012, 4, 559.
2) Kato, M.; Ito, H.; Hasegawa, M.; Ishii, K., Chem. Eur. J., 2019, 25, 5105.
3) Matsuhashi, C.; Ueno, T.; Uekusa, H.; Sato-Tomita, A.; Ichiyanagi, K.; Maki, S.; Hirano, T., Chem. Commun., 2020, 56, 3369.
4) Hummelen, J. C.; Luider, T. M.; Wynberg, H., Pure Appl. Chem., 1987, 59, 639.

Figure 1
(Invited) Upconverted Emission in AC-Driven Electrochemiluminescent Device
Authors: Kobayashi Norihisa 
Published: July 2021

Electrochemiluminescence (ECL) is a phenomenon in which light is emitted from the excited state of a redox-active material generated by electrochemical reactions. Among light-emitting device, ECL devices have various advantages in terms of structure and simple fabrication, and they are therefore expected as next generation emitting devices.
Concerning to the ECL device, we have reported the improvement of emission response, ECL intensity and stability of the ECL device by employing alternating current (AC)-driven method [1, 2]. AC-ECL showed further improvement in ECL properties when TiO2 nanoparticles [3], suitable solvent [4] and DNA/Ru complex hybrid films were used [5] In this paper, we report that electrochemically triggered upconverted luminescence through triplet–triplet energy transfer (TTET) and subsequent triplet–triplet annihilation upconversion (TTA-UC) is observed for the first time in the electrochemiluminescence properties of a Ru complex/diphenylantracene (DPA) containing electrochemical device [6]. This mechanism will be discussed. Reference [1]. T. Nobeshima, T. Morimoto, K. Nakamura, N. Kobayashi, J. Mater. Chem., 20, 10630 (2010) [2]. T. Nobeshima, M. Nakakomi, K. Nakamura and N. Kobayashi, Adv. Opt. Mater., 1, 144 (2013) [3]. S. Tsuneyasu, K. Ichihara, K. Nakamura and N. Kobayashi, Phys. Chem. Chem. Phys., 18, 16317 (2016) [4]. S. Tsuneyasu, T. Ichikawa, K. Nakamura and N. Kobayashi, ChemElectroChem, 4, 1731 (2017) [5]. S. Tsuneyasu, R. Takahashi, H. Minami, K. Nakamura and N. Kobayashi, Sci. Report, 7, 8525 (2017) [6]. H. Minami, T. Ichikawa, K. Nakamura and N. Kobayashi, Chem. Commun., 55, 12611 (2019)
Representation of Vivid Colors of Cyan, Magenta, Yellow, and Green in Ag Deposition-Based Plasmonic Electrochromic Device By Precise Control of Shape and Density of Deposited Ag Nanoparticles
Authors: Kimura Shunsuke , Sugita Tomoko , Nakamura Kazuki , Kobayashi Norihisa 
Published: July 2021

Ag nanoparticles exhibit various colors depending on their localized surface plasmon resonance (LSPR). Based on this phenomenon, Ag deposition-based electrochromic devices can represent various optical states in a single device such as the three primary colors (cyan, magenta, and yellow), silver mirror, black and transparent.1 A control of the morphology of Ag nanoparticles can lead to dramatic changes in color, as their size and shape influence the LSPR band. For this purpose, the “voltage-step method” was applied to a Ag deposition-based EC device to obtain multiple colors by shifting the LSPR band. In this method, two different voltages are successively applied : the first voltage V
1 is applied for a very short time t
1 to initiate Ag nucleation, and the second voltage V
2 is applied for a time t
2 to promote growth of the Ag nuclei. As V
2 is more positive than the nucleation voltage, further nucleation is no longer possible during t
2. Therefore, the Ag nanoparticle growth and the resultant device color can be controlled by changing t
2.
In this study2, we aimed to improve the color quality of Ag deposition-based multicolor EC devices by precisely controlling the supply of Ag+ ions to the electrode surface. Initially, the effect of coloration by decreasing the concentration of Ag+ ions in the Ag deposition-based EC device was investigated. As a result of optimizing the driving voltage, a lower concentration device (10 mM Ag+ ion) showed vivid and bright colors of cyan and magenta. This improvement was due to the generation of fine Ag nanoparticles and the prevention of the connection of Ag particles. From the electrochemical investigation, it was suggested that the slow supply rate of Ag+ ions in the lower concentration device induced electrochemical deposition of fine and isolated Ag nanoparticles.
Consequently, to obtain more uniformly deposited Ag nanoparticles, the nucleation voltage of V
1 was set to a lower voltage in the 10 mM device. As a result, spherical Ag nanoparticles were successfully obtained, and the device showed yellow and green colors. By comparing the LSPR behavior of the device with that of Ag nanoparticles dispersed in solution and using FDTD calculations, the mechanism of the yellow and green colors was investigated in detail. Thus, it indicated that the yellow coloration with an absorption band in the 400–500 nm region was caused by LSPR absorption of isolated spherical Ag nanoparticles. Furthermore, it was also observed that the coexistence of isolated spherical particles and aggregations of Ag nanoparticles induced two types of LSPR bands, leading to a good green color.

References

A.Tsuboi, K.Nakamura and N.Kobayashi, Chem. Mater., 2014, 26, 6477-6485

S.Kimura, T.Sugita, K.Nakamura and N. Kobayashi, Nanoscale, 2020 (in press)
Reserved Lithium-Ion Batteries for in Situ Lithiation of Vanadium Pentoxide Cathode
Authors: Parekh Mihit H. , Palanisamy Manikandan , Pol Vilas G. 
Published: July 2021

The race to substitute gasoline-powered vehicles with electric ones has resulted in the boom of electric vehicles’ sales by about 20 times since 2011 till the present. This has triggered a huge supply-demand scenario for lithium-ion batteries (LIBs) around the globe. Currently, LIBs rely heavily on cathodes such as LiNixMnyCozO2, LiFePO4, LiNiO2, LiCoO2, to maintain their place to meet energy expectations. Rarely, lithium-free compounds have been used as positive electrodes due to the irreversibility of redox reactions and the requirement of lithium metal anode. These have restricted the further development of new cathode materials for lithium-ion batteries. Some of the materials are Cr3O4, ZnO, TiO2, MnO2, and V2O5. These materials have high theoretical capacities, however, except V2O5, other materials have a low potential for insertion/extraction of Li+ ions and can possibly be reduced to the metal state during intercalation reactions. To ensure practicality and feasibility of such materials, it is important to focus on the lithiation strategies, viz., lithium additives, pre-lithiation of the anode,film-forming additives, and blended cathodes. However, these approaches cause cell voltage modification due to the presence of Li+ ion voids in the electrode. Fortunately, the pre-lithiation of the anode compensates for the initial loss of lithium ions in the formation of the solid electrolyte interface (SEI). However, the pre-lithiation technique is complex and uneconomical, resulting in it being infeasible in the commercial applications.
Here we report, in situ lithiation of the electrodes for the advancement of the lithium-free cathode research using lithium-electrode as a reservoir. The presence of a third reservoir electrode in LIB is brought only into the cell circuit initially during the SEI formation process and lithiation of the electrode. Here, V2O5 cathode with meso carbon microbeads (MCMB) was used to fabricate high specific capacity and high energy-density reserved lithium-ion batteries (RLIBs). The RLIB system delivered a high charge specific capacity of 245 mAh g-1 following two Li+ ions insertion/extraction. The tri-electrode system provided an initial high energy density of 980 Wh kg-1. A comparison of performance between V2O5 half-cell, V2O5-MCMB full-cell, and RLIB was made. There is a stark resemblance in the performance of RLIB performance with half-cell profile and in terms of capacity versus cycle number. Multiple module calorimetry provided the thermal heat signature to elucidate the safety features of the proposed RLIB system and compare it to the existing LIBs. Using this innovative concept of reservoir charging would be of key importance and valuable for applications in various sectors of society.

Figure 1
Full Parametrisation and Newman Modelling of the Mixed Niobium Oxide - NMC System: Unveiling the Limiting Factor and Tackling Problems with Solid State Diffusion Parametrisation
Authors: Houck Maurits E. , Zhang Wanwei , Geary Harry , Groombridge Alexander S. , De Volder Michael F. L. , Boies Adam M. 
Published: July 2021

Over the last decade, Mixed Niobium Oxide (MNO) materials have been widely researched as new lithium-ion battery anode material[1]. Their MO3-x perovskite-like host structure enables faster lithium-ion transport than graphite with higher specific capacities than LTO, while it also has excellent cycle life and voltage window respectively. Recent DFT modelling and in-situ material studies have greatly improved understanding at the material level[2]. However, for full scale implementation, more holistic parametrisation and modelling is needed to further interpret MNO behaviour in full cells, to perform sensitivity analysis for increased life and rate performance, and to design NMC/MNO battery systems. Here, we present one of the first full parametrisations and physics-based Newman models of the NMC/MNO system based on experimental data. The main governing mechanisms in the model are illustrated in Fig. 1.
In particular we focus on parametrisation and modelling of the particle size and solid-state lithium-ion diffusion coefficient. While these are shown to be crucial controlling factors in performance, there is considerable disagreement on definitions and measurement methods of the solid-state lithium-ion diffusion coefficient in literature. Values attained through DFT, PFG-NMR, GITT, EIS and Cyclic Voltammetry differ by orders of magnitude[3,4,5], and there is a knowledge gap between diffusion coefficients determined at the crystal level and at the cell level[6]. Literature on solid-state lithium-ion diffusion theory and measurement techniques is reviewed, and a better approach to parametrisation of solid-state lithium-ion diffusion is presented to improve cell modelling.
The resulting model helps in a more complete understanding of the NMC/MNO system and provides insights in why the NMC/MNO cell has superior properties compared to other cell configurations. It reveals what processes control NMC/MNO cell performance parameters such as polarisation, and therefore directs further research. Finally, it is shown how the model can be used to design new battery applications.

References

[1] Deng, Q. et al., Small 2019, 15, 1804884.
[2] Yuan, T. et al., Energy
Fuels 2020, 34, 11, 13321–13334.
[3] Koçer, C. P. et al., Chem. Mater. 2020, 32, 3980–3989.
[4] Griffith, K. J. et al., J. Am. Chem. Soc 2019, 141, 16706–16725.
[5] Lee, YS. et al., Sci. Rep. 2017, 7, 16617.
[6] Levi, M. D. et al., Condens. Matter Phys. 2002, 5, 329–362.

Figure 1
Sensing and Catalysis Using Functionalized Oxoporphyrinogens
Authors: Hill Jonathan P. , Chahal Mandeep , Payne Daniel 
Published: July 2021

Simple oxoporphyrinogen (OxP) derivatives are excellent colorimetric sensors for a variety of analytes including anions, acidity and enantiomeric excess. More recently, this family of compounds has grown to include rim-functionalized compounds, which also exhibit colorimetric properties. In this work, we have prepared differently rim-functionalized OxPs and we will present their properties with respect to sensing, including selective anion binding, ion pair sensing and
coupled sensing of other important polluting species. The sensing properties of OxPs rely on intermolecular hydrogen bonding interactions which, in turn, imply their possible applications in organocatalysis. These properties will be described with an emphasis on the identity of macrocyclic substituents, and how catalytic activity of the OxP macrocycles is established. Structural aspects of OxPs influencing their sensing and organocatalytic activities will be discussed.
Porphyrin-Hexabenzocoronene-Conjugates and Fullerenes
Authors: Jux Norbert , Lungerich Dominik , Hoelzel Helen , Ruppel Michael , Martin Max 
Published: July 2021

We will present architectures based on porphyrins and hexaarylbenzenes/ hexabenzocoronenes and fullerene C60. Special emphasis lies on crystal packing phenomena.
We report on the synthesis, characterization, and properties of some of these novel systems.[1-4]

References

[1] D. Lungerich, J. F. Hitzenberger, M. Marcia, F. Hampel, T. Drewello, N. Jux, Angew. Chem. Int. Ed..
2014,
53, 12231-12235.
[2] D. Lungerich, J. F. Hitzenberger, W. Donaubauer, T. Drewello, N. Jux, Chem. Eur. J.
2016, 22, 16755-16759.
[3] M. M. Martin, D. Lungerich, P. Haines, F. Hampel, N. Jux, Angew. Chem. Int. Ed.
2019, 59; 8932-8937.
[4] M. M. Martin, D. Lungerich, F. Hampel, J. Langer, T. K. Ronson, N. Jux, Chem. Eur. J.
2019; doi.org/10.1002/chem.201904005

Figure 1
Polymerization of Self-Assembled Tetraazaporphyrins
Authors: Eichhorn S. Holger , Tahir M Nazir , Abdulhamied Elmahdy , Selivanova Maria , Rondeau-Gagné Simon 
Published: July 2021

Polymerization of self-assembled supramolecular structures considerably increases their often limiting thermal and chemical stability, which widens their potential application in commercial products. Particularly interesting for self-assembled materials is the topochemical polymerization of diacetylenes to polydiacetylenes because it can be initiated photochemically and thermally without the need for additives, it proceeds with minimal structural changes, and it generates new functionality since polydiacetylene is a 1-dimensional organic semiconductor and absorbs visible light. Polydiacetylenes have been generated in single crystals, gel phases, thin films, and membranes but their formation in mesophases, such as liquid crystals, has been surprisingly little studied although higher ordered mesophases should support the topochemical polymerization of diacetylenes (1,3-butadiyne groups) and may give access to large domains of uniformly aligned materials.
Presented here are tetraazaporphyrins that contain eight alkyl chains with diacetylene groups to probe their mesomorphism and conversion into multifunctional polydiacetylene materials. While incorporation of diacetylene groups supports columnar mesomorphism, successful photopolymerization required the presence of directing amide groups that suppressed columnar in favour of nematic mesomorphism. Still, polymerization of the nematic mesophase generated a soluble nematic polydiacetylene of significantly higher molecular weight (Mn = 77 kDa or 25 monomer units by GPC) than what has been obtained in gel phases of related compounds. Formation of polydiacetylene was confirmed by Raman spectroscopy and its nematic structure was verified by UV-vis spectroscopy, polarized optical microscopy, and X-ray diffraction. Both, its nematic structure and the incorporation of eight side-chains per discotic unit provide the polydiacetylene with sufficient solubility for casting thin films on substrates. AFM studies of films casted onto silicon wafers revealed a grid-like structure of connected nanofibers.
Tahir et al. Langmuir 2019, 35, 15158