bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rechargeable Battery for Ultra Low Temperature Environments
Authors: Zhang Duhan , Chiang Yet-Ming 
Published: September 2023

Rechargeable energy storage systems that can efficiently operate at ultra-low temperatures down to -50°C or lower are needed to support Arctic zone development and aerospace exploration. Existing batteries today such as Li-ion and Pb-acid batteries all lose functions at colder temperatures. We have discovered a battery chemistry for which the amount of energy stored actually increases as temperature decreases, and storage cost commensurately decreases. Furthermore, this novel battery is composed of low-cost, widely available materials, and has a simple design that is self-assembling. In our study, we develop the zinc battery system composed of a pair of immiscible liquid electrodes that density-based self-assembly into a layered configuration without a membrane separator. This allows the zinc negative electrode to use low-cost iron or steel packaging that simultaneously serves as the current collector, while a reversible chlorine electrode serves as the positive electrode. The use of liquid electrolytes allows inherent stress relaxation suggesting high cycle life. We investigate anode and cathode solution chemistry, chlorine electrode redox kinetics including catalyst development, and integration of components into prototype batteries. Our progress shows promising battery cycling performance below 0°C, and indicates the technoeconomic feasible through technoeconomic analysis.
This abstract submission is for session A1-Triple I.
Reference:

Li, Zheng, et al. "Air-breathing aqueous sulfur flow battery for ultralow-cost long-duration electrical storage." Joule1.2 (2017): 306-327.

Landolt, D.; Ibl, N. (1972). "Anodic chlorate formation on platinized titanium". Journal of Applied Electrochemistry. Chapman and Hall Ltd. 2(3): 201–210. DOI:10.1007/BF02354977. S2CID 95515683.

Hale, Arthur (1918). The Applications of Electrolysis in Chemical Industry. Longmans, Green, and Co. p. 13. Retrieved 2019-09-15.
(Invited) Charge Carrier Relaxation, Recombination and Extraction Dynamics in Metal Halide Perovskite Nanocrystals
Authors: Samanta Anunay 
Published: September 2023

Charge Carrier Relaxation, Recombination and Extraction Dynamics in Metal Halide Perovskite Nanocrystals

Anunay Samanta

School of Chemistry, University of Hyderabad, Hyderabad 500046

(anunay@uohyd.ac.in)
The lead halide-based all-inorganic and hybrid perovskites are under intense investigation due to their immense potential in solar photovoltaic and light emitting applications.1,2 As realization of the full potential of these materials in various applications requires a clear understanding of the relaxation pathways and dynamics of the photo-generated charge carriers, we have been studying these key photo-processes in a wide range of perovskite nanocrystals.3-10 In this talk, we would like to present some of our recent results highlighting how a combination of femtosecond pump-probe and single-particle fluorescence techniques can be used to obtain valuable information on the nature and energy states of the photogenerated species, pathways and dynamics of relaxation of the charge carriers, location and nature of the trap states and their role in fluctuation of the photoluminescence of different caesium lead halide (CsPbX3) perovskite nanocrystals.

References

Dey, A. et. al. ACS Nano
2021, 15, 10775.

Green, M.A.; Ho-Baillie, A.; Snaith, H.J. Nature Photonics
2014, 8, 506.

Mondal, N; De, A.; Das, S.; Paul, S.; Samanta, A. Nanoscale
2019, 4, 9796.

Mondal, N; De, A.; Samanta, A. ACS Energy Letts.
2019, 4, 32.

Seth, S.; Ahmed, T.; Samanta, A. J. Phys. Chem. Lett.
2018, 9, 7007.

Mondal, N; De, A.; Samanta, A. J. Phys. Chem. Lett.
2018, 9, 3673.

Ahmed, T; Seth. S.; Samanta, A. ACS Nano
2019, 13, 13537.

De, A.; Das, A.; Samanta, A. ACS Energy Letts.
2020, 5, 2246.

Ahmed, T.; Paul, S.; Samanta, A. J. Phys. Chem. C
2022, 126, 9109.

Paul, S.; Samanta, A. J. Phys. Chem. Lett.
2022, 13, 5742.
(Invited) Photoluminescence-Based Circular Polarization Convertors for Multiplexing of Optical Information
Authors: Okazaki Yutaka , Shimizu Hayaki , Nakamura Kaito , Sagawa Takashi 
Published: September 2023

Polarized light has a great potential to provide a variety of optical information at once such as light intensity (brightness), wavelength (color), and polarization. In particular, circularly polarized (CP) light is expected to be used not only for 3D display but also for optical data encryption and anti-counterfeiting, because the polarization plane of CP light rotates during light propagation resulting in no angular dependence on information transmission. The previously reported approaches for creating CP light from unpolarized light can be roughly classified into the filtration using a circular polarizer, the selective reflection by chiral liquid crystals, and the circularly polarized luminescence (CPL) from chiral luminophores. Meanwhile, we have recently proposed a new approach for creating highly-pure CP light by converting linearly polarized luminescence (LPL) using luminescence-based CP convertor (Figure 1a).[1] The unique advantage of the luminescence-based CP convertor lies in the spectral conversion properties of the LPL films which allows multiplexing of optical information by simply laminating LPL films. In this presentation, we introduce the multilayer-type luminescence-based CP convertors (Figure 1b) fabricated by using two or three LPL films showing different PL wavelength.
In this study, we selected quantum rods (QRs) and π-conjugated luminescent polymers as one-dimensional (1D) luminophores. As a stretchable transparent polymer, poly(ethylene-co-vinyl acetate) (EVA) was used. LPL films were prepared by uniaxial stretching of the luminophore/EVA composite films. When yellow-, orange-, and red-color-emissive QRs were used as a luminophore, yellow-, orange-, and red-LPL were obtained as shown in Figures 1c-e. By laminating LPL film on the quarter-wave film with the angles between polarization plane of LPL and fast-axis of quarter-wave film were -45˚, 0˚, and +45˚, left-handed (LH-), parallel LP, and right-handed (RH-) CP light were produced, respectively. When the yellow-, orange-, and red-LPL films were laminated at three different angles (-45˚, 0˚, and +45˚) against the fast axis of the quarter-wave film, 3×3×3=27 different pieces of optical information were produced as shown in Figure 1f. Furthermore, time information on CP light can also be multiplexed theoretically by laminating several LPL films showing different fluorescence lifetimes. In this presentation, we will also discuss about time-multiplexing of optical information by multilayer-type luminescence-based CP light convertor consisting of multiple LPL films showing different PL lifetimes.
[1] Y. Okazaki et. al., J. Mater. Chem. C, 2022. DOI: 10.1039/d2tc03955a.

Figure 1
Developing Tin Anodes for Aqueous Batteries
Authors: Wang Jianbo , Catalina Sofia K. , Chueh William C. , Mefford J. Tyler 
Published: September 2023

Aqueous batteries based on metal anodes present an attractive alternative to lithium-ion for long-duration energy storage due to their low-cost, high-safety, and theoretically high energy density. Still, despite many efforts towards development and commercialization, metal anode systems remain hampered by irreversible hydrogen evolution (HER), detrimental shape change, and passivation during cycling. Recognizing the immediacy required to enable the renewable energy transition, our research is focused on developing alternative anode chemistry based on Tin (Sn) for aqueous batteries.
Sn metal has been used in aqueous battery systems as additives or current collectors to mitigate side reactions due to its high overpotential for HER. However, little attention was paid to its potential use as a redox active material in aqueous electrolytes. In this talk, we will discuss our efforts to develop Sn as an aqueous anode with high capacity and cyclability. We will first present our development of pouch cells to enable aqueous cells while minimizing the side reactions from cell components other than the active materials. Preliminary data demonstrate the feasibility of using Sn as anode active materials via a 4-electron process in aqueous systems. To investigate the mechanism and improve the Coulombic efficiency, we perform operando X-ray diffraction (XRD), rotating ring disk electrochemistry (RRDE), electrochemical quartz crystal microbalance (EQCM), and 117Sn nuclear magnetic resonance (Sn-NMR) on the Sn system. Lastly, we will show our improvement based on the mechanistic understanding that enables Sn-based full cells with high Coulombic efficiency, high areal capacity, high utilization rate and long capacity retention.
(Digital Presentation) Mathematical Approximations for Monitoring the State of Charge and Computing Electrolyte Volume in Vanadium Redox Flow Battery Systems
Authors: Santana Jordy , Villegas Victor , Espinoza Andaluz Mayken , Andersson Martin 
Published: September 2023

During the last years, several attempts have been carried out to provide clean energy storage as an alternative to overcome the energy demand. Vanadium redox flow batteries (VRFBs) appear as a suitable device that converts the chemical energy present in the electrolyte into electrical energy in a noiseless and clean manner. In the mentioned device, the electrolyte is polarized by using renewable energy, and later the stored energy is used in several applications from mobile to stationary scenarios. There are two fundamental design parameters to be considered in the sizing of a VRFB: the state of charge (SoC), and the electrolyte volume. The mentioned parameters are related to two independent parameters of great importance, the energy consumption per unit of time (power delivered by the device), and the amount of energy that can be stored in the system (energy capacity).
The purpose of the current study is, based on collected data and theoretical approximations, analyze the SoC and the required electrolyte volume for several applications. To estimate the SoC for the different VRFB, a Nernst-modified equation is used. In this case, the number of cells was a key part of achieving the desired results. A correction factor (λ) was introduced to visualize the trend of the generated curve family in a better manner. On the other hand, to calculate the volume of electrolyte, an equation derived from the definition of electric charge is implemented. Similarly, due to the power applications range covering the study, a correction factor (γ) was also introduced. Considering the obtained results, as the correction factor increases the load state in the system will tend to present higher values of open circuit voltage and nevertheless constant values of load state. Based on the energy capacity calculations, and considering common vanadium concentrations among the electrolytes, it was found that the higher the vanadium concentration the required electrolyte volume will tend to be minor. In addition, on a large scale, there is a greater convergence of the required electrolyte volume to values greater than 10 000 m3.

Figure 1. Trend of the open circuit voltage (OCV) when the state of charge (SoC) is increasing. Due to the wide range of output power analyzed in the current study, all the OCV presented values have been determined by using a correction factor (λ).

Figure 1
Photoinduced Processes in Molecular and Supramolecular Arrays Based on Porphyrins and Acridinium Units
Authors: Ruani Federica , Sánchez Resa Daniel , Edo-Osagie Amy , Jacquot de Rouville Henri-Pierre , Heitz Valérie , Armaroli Nicola , Ventura Barbara 
Published: September 2023

Multichromophoric arrays based on porphyrins are of high interest for their mimicry of naturally occurring photoinduced energy and electron transfer processes leading to energy collection and conversion. [1] Moreover, the rich photophysics and electrochemistry of porphyrins make them suitable components of molecular wires, switches or chemical sensors. [2] In this perspective, it is interesting to pursue the combination of porphyrins with units that can act as multiresponsive components by modifying their chemical and electronic structure upon chemical or redox stimuli. N-acridinium ions have been recently explored as a new class of switches that respond to various orthogonal stimulations (pH or electrochemical/photochemical inputs) that trigger their reversible conversion into the non-aromatic acridane form. [3] Few examples reporting the association of acridinium units and porphyrins indicate that these systems are characterized by fast photoinduced electron transfer reactions between the porphyrin donor and the acridinium acceptor. [4,5]
We recently investigated the photophysical properties of molecular and supramolecular arrays based on porphyrins and acridinium units, where the type of porphyrin (free-base or metallated) and/or the form of the switchable component (acridinium or acridane) has been varied (Figure 1). We found that the association of porphyrins and acridinium ions always leads to ultrafast electron transfer processes, and that these reactions can be altered by changing the temperature or by converting the acridinium electron acceptor into an acridane energy donor. Moreover, the combination of two Zn-porphyrins with two acridinium/acridane units results in switchable molecular receptors able to coordinate suitable hosts. The photophysics of the arrays and of the complexes, analyzed by means of steady-state and time-resolved luminescence techniques and ultrafast transient absorption spectroscopy, will be herein presented and discussed.
The work is supported by the H2020-MSCA-ITN-2017-765297 project “NOAH” and by the H2020-LC-SC3-2020-RES-RIA-101006839 project “CONDOR”.
[1] M. Beyler, L. Flamigni, V. Heitz, J.-P. Sauvage, B. Ventura, Photochem.
Photobiol.
2014, 90, 275-286.
[2] Beletskaya I, Tyurin VS, Tsivadze AY, Guilard R, Stern C. Chem. Rev.
2009, 109, 1659-1713.
[3] H.-P. J. de Rouville, J. Hu, V. Heitz, ChemPlusChem, 2021, 86, 110-129.
[4] A. Edo-Osagie, D. Sánchez-Resa, D. Serillon, E. Bandini, C. Gourlaouen, H.-P. Jacquot de Rouville, B. Ventura, V. Heitz, C. R. Chim.
2021, 24, 1-9.
[5] H. Kotani, K. Ohkubo, M. J. Crossley, S. Fukuzumi, J. Am. Chem. Soc., 2011, 133, 11092-11095.
Figure 1. Structures of the studied arrays and schemes of the occurring photoinduced processes: a) bisacridinium-Zn(II) porphyrin conjugate, b) bisacridinium-diphenylporphyrin conjugate, c) bis(acridinium/acridane)-Zn(II) porphyrin receptors.

Figure 1
Porphyrins Derivatives Grafted on Chiral Nanoplatforms for Enantioselective Recognition
Authors: Oda Reiko , Anfar Zakaria , Scalabre Antoine , Okazaki Yutaka , Buffeteau Thierry , Stefanelli Manuela , Magna Gabriele , Monti Donato , Pouget Emilie , Nlate Sylvain , Paolesse Roberto 
Published: September 2023

There are many reports on biologically inspired helical structure obtained by polymers, foldamers and low molecular-weight molecules. Indeed, helices with controllable pitches at nanometrical level are attractive not only to mimic nature, but also for the wide range of applications in materials sciences, chemical and biomaterial sensing, and enantioselective catalysis. Here we report the synthesis of inorganic nanohelices based on the transcription of supramolecular helical assemblies,2 which can be used to induce chiroptical properties to a large variety of host molecules grafted on their surface, which can then be used as sensors for enantioselective recognition for the chiral guests.
[1] a) Oda, R., Huc, I., Schmuts, M. Candau, S. J., Mackintosh, F. C. Nature, 1999, 399, 566 ; b) Brizard, A., Aimé, C., Labrot, T., Huc, I., Berthier, D., Artzner, F., Desbat, B., Oda, R. J. Am. Chem. Soc., 2007, 129¸ 3754. c) R. Tamoto, N. Daugey, T. Buffeteau, B. Kauffmann, M. Takafuji, H. Ihara and R. Oda Chem commun, 2015, 51, 3518-3521
2 a) Delclos, T.; Aimé, C.; Pouget, E.; Brizard, A.; Huc, I.; Delville, M.-H.; Oda, R., Nano Letters 2008, 8 (7), 1929-1935 ; b) Okazaki, Y.; Cheng, J.; Dedovets, D.; Kemper, G.; Delville, M.-H.; Durrieu, M.-C. Ihara, H.; Takafuji, M.; Pouget, E.; Oda R.; Acs Nano, 2014. 8(7): 6863-6872; c) Y Okazaki, J Cheng, D Dedovets, G Kemper, MH Delville, MC Durrieu, H Ihara, M Takafuji, E Pouget, R Oda, ACS Nano, 2014 (6) PMID: 24883981

Figure 1
Calix[3]Pyrrole and Related Macrocycles: Synthesis and Properties
Authors: Inokuma Yasuhide 
Published: September 2023

Calix[4]pyrrole is a porphyrinogen-like macrocycle in which four pyrrole units are linked by four sp3-hybridized carbon atoms at the α-positions. While such tetrapyrrolic macrocycles are readily synthesized by acid-catalyzed condensation reactions of pyrrole monomer and carbonyl compound, analogous macrocycles composed of three pyrrole units are always not observed. Calix[3]pyrrole is a ring-contracted analogue of calix[4]pyrrole, and has been missing in porphyrin-related chemistry. In this presentation, the first synthesis of calix[3]pyrrole and its furan-embedded analogues is reported, and their unique reactivity derived from their macrocyclic ring strain will be discussed.
Synthesis of calix[3]pyrrole started with a linear trimer of 3,3-dimethylpentane-2,5-dione. Intramolecular cyclization of the linear hexaketone was accomplished in 5 steps to give a cyclic hexaketone precursor. Paal–Knorr type pyrrole formation reaction of cyclic hexaketone gave calix[3]pyrrole in 41% yield (Scheme 1). Using similar strategies, analogous calix[3]-type macrocycles, namely, calix[1]furan[2]pyrrole, calix[2]furan[1]pyrrole, and calix[3]furan, were successfully synthesized. Single crystal X-ray diffraction analysis of calix[3]pyrrole revealed its strained structure, and the theoretical calculations showed the strain energy of calix[3]pyrrole is 22.1 kcal/mol per unit higher than that of calix[4]pyrrole. Such strain energy tends to decrease as the number of pyrrole unit decreased.
Calix[3]pyrrole exhibited unique reactivity derived from macrocyclic ring strain under acidic (Rothemund–Lindsey) conditions that are frequently used for porphyrin synthesis. When calix[3]pyrrole was dissolved in 10 mM solution of trifluoroacetic acid in dichloromethane, calix[6]pyrrole was quantitatively formed within 30 seconds (Scheme 1). Similar strain-induced ring expansion was observed for calix[1]furan[2]pyrrole, but full conversion took approximately 5 minutes. On the other hand, calix[2]furan[1]pyrrole and calix[3]furan did not show ring expansion. Detailed mechanistic analysis revealed that protonation at a pyrrole unit in calix[3]pyrrole triggers irreversible ring-cleavage to give a linear tripyrrane moiety which undergoes cyclodimerization under acidic conditions.
The strain-induced ring expansion reaction of calix[3]pyrrole solved a long-standing question in porphyrin-related chemistry. Tripyrrolic macrocycles such as calix[3]pyrrole are, even formed, not isolable from pyrrole condensation reaction using acid, because the strain-induced conversion to calix[6]pyrrole is too fast. Besides, this reaction provided a novel approach to ring-expanded calix-type macrocycles.

Figure 1
Synthesis and Properties of a Fused Antiaromatic Hydrocarbon By Oxidative Transformation of Carbacorrole Analogue
Authors: Ishida Masatoshi 
Published: September 2023

Polycyclic aromatic hydrocarbons (PAHs) containing fused pyrrole moieties are known as unique nitrogen-doped pi-conjugated molecules, e.g., azacoronenes, which possess a large π-conjugated planar structure and show rich redox properties. The related molecules are thus expected to be applied to redox-responsible optoelectronic materials. Furthermore, PAH-based compounds containing [4n]π-electron antiaromatic segments, such as pentalene and indacene are contributed to the ambipolar semiconducting material applications due to the distinct high HOMO and low LUMO energy levels.
In this work, we have synthesized and characterized a novel N-doped poly-antiaromatic hydrocarbon (PAH) by the oxidative transformation of a dibenzocarbacorrole isomer, namely, dibenzocorrorin (1). X-ray crystal structure of the fused product (2) revealed a highly planar pi-conjugated structure containing a unique diaza-dicyclopentaazulene moiety. The distinct 12pi antiaromatic resonance structure led to the emergence of a near-infrared band beyond 1000 nm in the absorption spectrum and facile redox properties determined in the cyclic voltammetry. Furthermore, crystalline compound 2 showed carrier mobility in the single-crystal organic field effect transistor.
Molecular Electrochemical Reduction of COx-to-Methanol with Cobalt Phthalocyanines Combined Electrochemical and Spectroscopic Studies
Authors: Robert Marc 
Published: September 2023

Reduction of carbon dioxide has as main objective the production of useful organic compounds and fuels - renewable fuels - in which solar energy would be stored. Molecular catalysts can be employed to reach this goal, either in photochemical or electrochemical (or combined) contexts. They may in particular provide excellent selectivity thanks to easy tuning of the electronic properties at the metal and of the ligand second and third coordination sphere. Hybridization of the catalysts with conductive or semi-conductive materials may lead to enhance stability and new catalytic properties, as well as the development of devices (electrolyzers).
Recently, we have found that Co phthalocyanine adsorbed at carbon nanotubes can convert CO2 to CO, and CO to methanol, opening the path to a cascade process for the production of CH3OH. Upon combining electrochemical and spectroscopic studies (IR, XAS), we have uncovered the reasons for such remarkable reactivity. Our most recent results will be discussed, including the insertion of this catalyst into a flow cell.
References
1. E. Boutin, M. Robert et al., Angew. Chem. Int. Ed. 2019, 58, 16172-16176
2. E. Boutin, M. Robert et al. Chem. Eur. J. 2022, e202200697
3. B. Liu, M. Robert et al., submitted