Silica fillers have been a cornerstone in chemical technology due to their versatility, availability, and ease of integration into various formulations. Recent advancements, including chlorine-free synthesis of alkoxysilanes, have paved the way for alternative materials like polymethylsilsesquioxane (PMSSO). This study explores the structural evolution and properties of a hydrophobic PMSSO xerogel, synthesized through hydrolytic polycondensation of methyltriethoxysilane (MTEOS). PMSSO exhibits exceptional hydrophobicity, high specific surface area, and compatibility with polymer matrices, making it a promising filler for applications in rubber products, lubricants, and cosmetics. We developed a straightforward synthesis method for producing PMSSO xerogel that avoids toxic solvents and organochlorosilanes, ensuring safety and sustainability. The reaction conditions, particularly the amount of alkali and neutralization parameters, were found to significantly influence the properties of the final xerogels, such as specific surface area. Optimization of the synthesis parameters allow for obtaining PMSSO xerogels with a specific surface area about 600 m2/g. These findings underscore PMSSO’s potential as a versatile, eco-friendly alternative to conventional silica fillers, offering tailored properties for diverse industrial applications.

In this manuscript, we present a scalable approach to the design of advanced organic redox-active materials by pyrolysis of simple low molecular weight precursors. A cascade of condensation reactions occurring under pyrolysis of 3,6-dihydroxyphthalodinitrile produced a covalent organic framework with phthalocyanine units. Spectroscopic characterization supported by DFT calculations revealed that the obtained material has a porous membrane-like structure, which is favorable for ionic transport. The potassium batteries using the designed organic redox-active material as a working electrode delivered a specific discharge capacity of similar to 100 mAh g(-1) at the high current density of 1 A g(-1) with the average discharge potential of similar to 3 V. These characteristics, in combination with the simple synthesis, pave the way to the practical implementation of the designed material in ultrafast, scalable and low-cost stationary batteries, which are urgently needed for electric grids operating with any considerable contribution from renewable energy sources due to their high variability. The proposed material design concept deserves further exploration and might lead to a big family of redox-active organic frameworks with superior electrochemical characteristics.

The Lindblad equation for dissipative open systems is applied for an investigation of relaxation of multiple-quantum (MQ) NMR coherences in two-spin systems. We choose two examples of two-spin systems. One of them is the zigzag proton chain in a single crystal of hambergite in such an orientation that one of the two intra-chain dipolar coupling constants becomes zero. Then, the chain consists of well-isolated pairs of spins, with the spins of each pair coupled by the dipole–dipole interaction. The second example of a two-spin system is a single crystal of gypsum in which protons belong to water molecules. The MQ NMR dynamics with relaxation was investigated for different preparation times of the MQ NMR experiment.

Ultrahigh radiation hardness of complex lead halides: where are the limits?Victoria Ozerova a, Marina Ustinova a, Nikita Emelianov a, Sergey Vasil'ev a, Dmitry Kirukhin a, Ivan Zhidkov b, c, Sergey Aldoshin a, Pavel Troshin d, aa Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences (FRC PCP MC RAS), Academician Semenov ave. 1, Chernogolovka, Moscow Region, 142432, Russian Federationb Institute of Physics and Technology, Ural Federal University, Mira 19 Street, Yekaterinburg 620002, Russiac M. N. Mikheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences, S. Kovalevskoi 18 Street, Yekaterinburg 620108, Russiad Zhengzhou Research Institute, Harbin Institute of Technology, 26 Longyuan East 7th, Jinshui District, Zhengzhou, Henan Province, 450000, ChinaInternational Conference on Hybrid and Organic PhotovoltaicsProceedings of International Conference on Hybrid and Organic Photovoltaics (HOPV24)València, Spain, 2024 May 12th - 15thOrganizer: Bruno EhrlerInvited Speaker Session, Pavel Troshin, presentation 119DOI: https://doi.org/10.29363/nanoge.hopv.2024.119Publication date: 6th February 2024High radiation hardness is the primary requirement for application of lead halide perovskite semiconductors in X-ray detectors for medical diagnostics and solar panels for space missions. Multiple reports show that perovskite absorber films and solar cells indeed could successfully tolerate high electron, proton and neutron fluences as well as gamma rays and x-rays [1-2]. Among different types of ionizing radiation, gamma rays have very high penetration ability and hence could hardly be mitigated using simple shielding used to suppress the damage from proton and also electron fluences. Thus, the investigation of the radiation hardness of lead halide perovskites with respect to gamma rays is essentially important from fundamental point of view and also in the context of the emerging applications. Herein, we present the results of our systematic study of model lead halide perovskite materials: MAPbI3, FAPbI3, (CsMA)PbI3 and (CsMAFA)PbI3, where MA and FA are methylammonium and formamidinium cations, respectively [3]. We show that among the studied materials FAPbI3 is the only one which does not degrade after receiving the ultrahigh radiation doses up to 20 MGy and thus represents highly promising absorber material for radiation-tolerant solar cells. Other complex lead halides produce different aging products upon exposure to gamma rays including metallic lead and PbI2. Infrared near-field optical microscopy revealed the radiation-induced depletion of organic cations from the grains of MAPbI3 and their accumulation at the grain boundaries. Using a set of complementary techniques, we evidenced that multication (CsFA)PbI3 and (CsMAFA)PbI3 perovskites undergo a facile phase segregation to domains enriched with Cs, MA and FA cations. This new degradation pathway is quite similar to the gamma-ray-induced halide phase segregation we observed previously for Cs0.15MA0.10FA0.75Pb(Br0.17I0.83)3 material [4-5]. The revealed aging pathways could be successfully mitigated through the rational compositional engineering of complex lead halides using (1) partial lead substitution and (2) the formation of the mixed dimensional 2D/3D absorber materials. The perovskite solar cells maintained 80-90% of their initial performance after exposure to extreme doses of gamma rays approaching 1 MGy, which is unprecedented result for all types of photovoltaic cells. To summarize, our findings suggest that the radiation hardness of the rationally designed perovskite semiconductors could go far beyond the impressive threshold of 20 MGy we set herein for FAPbI3 films and 1 MGy we demonstrate for completed perovskite solar cells. Thus, the unique radiation hardness of complex lead halides opens many exciting opportunities for practical implementation of these materials in detectors for medical diagnostics and solar cells operating in harsh radiation environments. References:[1] Yang, J.; Bao, Q.; Shen, L.; Ding, L. Potential Applications for Perovskite Solar Cells in Space. Nano Energy 2020, 76, 105019[2] Romano, V.; Agresti, A.; Verduci, R.; D'Angelo, G. Advances in Perovskites for Photovoltaic Applications in Space. ACS Energy Lett. 2022, 7 (8), 2490–2514.[3] Ozerova, V. V.; Emelianov, N. A.; Kiryukhin, D. P.; Kushch, P. P.; Shilov, G. V.; Kichigina, G. A.; Aldoshin, S. M.; Frolova, L. A.; Troshin, P. A. Exploring the Limits: Degradation Behavior of Lead Halide Perovskite Films Under Exposure to Ultrahigh Doses of Gamma Rays up to 10 MGy. J. Phys. Chem. Lett., 2023, 14, 743[4] Boldyreva, A. G.; Akbulatov, A. F.; Tsarev, S. A.; Luchkin, S. Yu.; Zhidkov, I. S.; Kurmaev, E. Z.; Stevenson, K. J.; Petrov, V. G.; Troshin, P. A. γ-Ray-Induced Degradation in the Triple-Cation Perovskite Solar Cells. J. Phys. Chem. Lett. 2019, 10, 813[5] Boldyreva, A. G.; Frolova, L. A.; Zhidkov, I. S.; Gutsev, L. G.; Kurmaev, E. Z.; Ramachandran, B. R.; Petrov, V. G.; Stevenson, K. J.; Aldoshin, S. M.; Troshin, P. A. Unravelling the Material Composition Effects on the Gamma Ray Stability of Lead Halide Perovskite Solar Cells: MAPbI3 Breaks the Records. J. Phys. Chem. Lett. 2020, 11, 2630Acknowledgements:This work was partially supported at FRC PCP MC RAS by the Russian Science Foundation (project No. 22-13-00463). © FUNDACIO DE LA COMUNITAT VALENCIANA SCITOnanoGe is a prestigious brand of successful science conferences that are developed along the year in different areas of the world since 2009. Our worldwide conferences cover cutting-edge materials topics like perovskite solar cells, photovoltaics, optoelectronics, solar fuel conversion, surface science, catalysis and two-dimensional materials, among many others.MATSUSPreviously nanoGe Spring Meeting (NSM) and nanoGe Fall Meeting (NFM), MATSUS is a multiple symposia conference focused on a broad set of topics of advanced materials preparation, their fundamental properties, and their applications, in fields such as renewable energy, photovoltaics, lighting, semiconductor quantum dots, 2-D materials synthesis, charge carriers dynamics, microscopy and spectroscopy semiconductors fundamentals, etc.International Conference on Hybrid and Organic PhotovoltaicsInternational Conference on Hybrid and Organic Photovoltaics (HOPV) is celebrated yearly in May. The main topics are the development, function and modeling of materials and devices for hybrid and organic solar cells. The field is now dominated by perovskite solar cells but also other hybrid technologies, as organic solar cells, quantum dot solar cells, and dye-sensitized solar cells and their integration into devices for photoelectrochemical solar fuel production.Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and OptoelectronicsThe main topics of the Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP) are discussed every year in Asia-Pacific for gathering the recent advances in the fields of material preparation, modeling and fabrication of perovskite and hybrid and organic materials. Photovoltaic devices are analyzed from fundamental physics and materials properties to a broad set of applications. The conference also covers the developments of perovskite optoelectronics, including light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and OptoelectronicsThe International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics (NIPHO) is the best place to hear the latest developments in perovskite solar cells as well as on recent advances in the fields of perovskite light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.

Water-soluble compositions of D-α-tocopherol (TP) as an effective antioxidant obtained by its encapsulation into amphiphilic copolymer of N-vinylpyrrolidone with hexyl methacrylate and triethylene glycol dimethacrylate (VP–HMA–TEGDM) and linear polyvinylpyrrolidone (PVP) were studied by electron absorption spectroscopy, dynamic light scattering and by 1H high-resolution and pulsed field gradient (PFG) NMR. TP absorption band was at 292 nm in the absorption spectra of TP–VP–HMA–TEGDM and TP–PVP solutions, and the TP-loaded nanoparticles in water solution had average hydrodynamic radii, Rh, values about 65 and 57 nm, and diffusion coefficient, Dt, values were 3.7 × 10–8 and 4.3 × 10–8 cm2/s, respectively. The investigation of the self-diffusion by PFG NMR technique in addition reveals the presence of the phases of small sizes containing TP, which are invisible in DLS measurements. The investigation of the exchange between these phases shows that the retention time of TP in large associates is longer for TP–VP–HMA–TEGDM water solution compared to TP–PVP.

The evolution and relaxation of MQ NMR coherences on the preparation period were investigated experimentally on a single crystal of gypsum, CaSO4·2H2O. The theory describing the dynamics of MQ coherences on the preparation period of MQ experiment for a pair of spins was developed based on the Lindblad master equation. This theory predicts the appearance of MQ coherences of only zeroth and second orders, oscillatory exchange of their intensities and exponential decay with increasing of the preparation time. The proposed theory describes the experimental data well. It is shown that the frequency of oscillations depends on the orientation of the crystal in the external magnetic field and determined by the dipolar coupling between protons of the water molecules contained in the gypsum crystal. The relaxation time of MQ coherences of zeroth and second orders, Tr = 150 ± 15 μs, were independent of the crystal orientation, which suggest a common source of relaxation due to the dipole-dipole interactions with protons surrounding water molecule.

Multiple -quantum (MQ) NMR experiments were performed at a special orientation of a hambergite (Be 2 BO 3 OH) single crystal, which consists of alternating zigzag proton chains. At the chosen orientation, one of the dipolar coupling constants in the chain becomes zero and the system becomes a set of well -isolated dipolar coupled spin pairs. The relaxation of the spin pairs in the MQ NMR experiment was studied on the basis of the Lindblad equation. Fermi's golden rule was used to investigate the relaxation mechanism. The agreement of the calculated relaxation time with the experimental value (125 mu s) suggests that the dipole-dipole interactions with protons surrounding the pair are responsible for the relaxation of MQ coherences.

An approach to the development of peroral iron drug delivery systems for the therapy of iron deficiency anemia is proposed. The new systems are based on polymethylsilsesquioxane hydrogels with a variable structure as biocompatible and biodegradable supports. The hydrogels are found to exhibit a high sorption capacity toward a saturated solution of FeCl3∙6H2O (0.27 M), whereas the sorption capacity toward a saturated solution of iron D-gluconate (0.24 M) is lower and amounts to 30

The growing demand for cheap, safe, recyclable, and environmentally friendly batteries highlights the importance of the development of organic electrode materials. Here, we present a novel redox-active polymer comprising a polyaniline-type conjugated backbone and quinizarin and anthraquinone units. The synthesized polymer was explored as a cathode material for batteries, and it delivered promising performance characteristics in both lithium and potassium cells. Excellent lithiation efficiency enabled high discharge capacity values of >400 mA g−1 in combination with good stability upon charge–discharge cycling. Similarly, the potassium cells with the polymer-based cathodes demonstrated a high discharge capacity of >200 mAh g−1 at 50 mA g−1 and impressive stability: no capacity deterioration was observed for over 3000 cycles at 11 A g−1, which was among the best results reported for K ion battery cathodes to date. The synthetic availability and low projected cost of the designed material paves a way to its practical implementation in scalable and inexpensive organic batteries, which are emerging as a sustainable energy storage technology.

We report the synthesis and electrochemical study of three quinone-based ladder-type redox-active polymers. These materials were applied as electrode materials in potassium half-cells and delivered high specific discharge capacities of up to 268 mAh g-1 at 0.66 A g-1. Using concentrated diglyme-based electrolyte formulation allowed us to suppress capacity fading and enable stable charge-discharge cycling of the batteries. The designed materials represent promising electrode materials for emerging scalable organic potassium-ion battery technology.

Multiple quantum (MQ) dynamics was investigated in quasi-one-dimensional 1H zigzag spin chains in hambergite (Be2BO3OH) single crystals. Due to the non-linear arrangement of the spins, dipolar coupling strengths alternate along the chain. To solve the problem of MQ NMR experiments taking too much time due to extremely long 1H spin-lattice relaxation times, the samples were exposed to gamma irradiation to produce the defects accelerating the relaxation. The influence of the radiation dose was investigated. The experimental dependencies of MQ coherence intensities on the MQ excitation time in alternating spin chains were obtained and compared with the theory for inhomogeneous spin chains with nearest neighbor interactions developed earlier. The correspondence of the observed MQ dynamics to the alternating spin chain was demonstrated.

Cellulose HogC was produced by the modified traditional method with 35% yield from the stem of Sosnovsky hogweed and was characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffractometry, differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). For HogC, the degree of crystallinity (approximately 70%) and the glass transition temperature (105–108 °C) were determined. It was found that the whiteness characteristic in the case of HogC was 92% and this significate was obtained without a bleaching procedure using chlorine-containing reagents. In this paper, the possibility of hydrophobization of HogC films by treatment with radiation-synthesized telomers of tetrafluoroethylene is shown. It was found that the contact angle of the telomer-treated cellulose film surface depended on the properties of the telomers (the chemical nature of the solvent, and the initial concentration of tetrafluoroethylene) and could reach 140 degrees.

Multiple quantum (MQ) NMR dynamics in an inhomogeneous spin chain, where the distances between the various pairs of neighboring spins can be different, has been studied in the approximation of nearest-neighbor dipole–dipole interaction (DDI). Though the fermion spectrum after performing the Jordan-Wigner transformation is not known, this article shows that the MQ NMR spectrum consists of MQ coherences of orders 0 and ±2 only, and their intensities are determined by the system’s fermion spectrum. As an example application of the theory developed, we calculate MQ NMR spectra of uniform, alternated and doubly alternated (with three different dipolar coupling constants) spin chains.

The formation of hybrid nanostructures consisting of InP@ZnS colloidal quantum dots and mesotetra(3-pyridyl)porphyrin molecules adsorbed on the quantum dots has been studied. In such nanostructures, strong quenching of quantum dot luminescence and an increase in the emission intensity of porphyrin are observed due to nonradiative resonance energy transfer from colloidal quantum dots to porphyrin.

We report the synthesis and electrochemical study of three quinone-based ladder-type redox-active polymers. These materials were applied as electrode materials in potassium half-cells and delivered high specific discharge capacities of up to 268 mAh g -1 at 0.66 A g -1 . Using concentrated diglyme-based electrolyte formulations allowed us to suppress capacity fading and enable stable charge-discharge cycling of the batteries. The designed materials represent promising anode materials for emerging scalable organic potassium-ion battery technology.

We report the synthesis and electrochemical characterization of octahydroxytetraazapentacenedione (OHTAPQ). The potassium batteries using OHTAPQ as electrode material delivered the specific capacity of 190 mAh g(-1) at the current density of 0.6 A g(-1). The use of the concentrated (2.2 M KPF6) diglyme-based electrolyte suppressed significantly the capacity fading of the potassium half-cells with OHTAPQ electrodes thus enabling their stable operation for 1200 charge-discharge cycles. Furthermore, OHTAPQ delivered the specific discharge capacity of 82-103 mAh g(-1) at high current densities of 9-21 A g(-1), which leads to high power densities approaching 41000 W kg(-1). Thus, we demonstrate that the rationally designed organic electrode material enables high-capacity and high-power potassium batteries, which can be considered as a more environment-friendly and scalable alternative to the mainstream lithium-ion battery technology.

Herein, two novel copolymers of dihydrophenazine with diphenylamine (PDPAPZ) and phenothiazine (PPTZPZ) are synthesized and investigated as cathode materials for dual‐ion batteries. Both polymers demonstrate high average discharge potentials (3.5–3.6 V) in lithium cells. The PDPAPZ//Li cells demonstrate impressive rate capability: specific capacities of 101 and 82 mAh g−1 are reached under galvanostatic charging and discharging at the high current densities of 5 and 20 A g−1, respectively. The capacity retention of 86% and 34% after 100 and 25 000 cycles, respectively, features decent operational stability of the batteries. Furthermore, an encouraging energy density of 398 Wh kg−1 is achieved in potassium PDPAPZ//K cells. The obtained values place PDPAPZ on par with the best organic cathode materials for fast lithium and potassium batteries.

Polydiphenylamine (PDPA)-based cathodes exhibited record energy densities among all known polymer-based cathodes for dual-ion batteries.

1H NMR in quasi-one-dimensional spin chains is investigated experimentally on the single crystal of hambergite, Be2BO3OH. The orientations at which the change of the spin chain direction with respect to the external magnetic field results in the occurrence of homogeneous and alternating chains are found. The dependence of the lineshape on the orientation in magnetic field for alternating spin chain is obtained and the data are analyzed using a simple model taking into the dipolar interactions with the nearest neighbors. The analogies with the lineshapes typical for spin systems with a small number of spin and known linear spin chain are discussed.

The free induction decay (FID) is investigated for zigzag (alternating) spin chains in the approximation of the nearest neighbor interactions. The dependence of the FID on the ratio of dipolar coupling constants (the parameter of dimerization) is also studied. Possible comparison of the obtained results with the experimental data for proton zigzag chains in a single crystal of hambergite is discussed.