Electron-electron Interaction Research Articles

A Quantum Chemical Study on the Bonding Mechanism, Electronic Structure, and Optical Properties of Cellulose and Polyaniline Nanohybrid

A Quantum Chemical Study on the Bonding Mechanism, Electronic Structure, and Optical Properties of Cellulose and Polyaniline Nanohybrid

Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8GHz, RLmin = -46dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

TS-1 zeolite encapsulated Pt clusters with enhanced electronic metal-support interaction of Pt−O(H)−Ti for nearly-zero-carbon-emitting photocatalytic hydrogen production from methanol

Photocatalytic H2 production from methanol is sustainable, yet challenges remain in avoiding carbon-containing gaseous by-products. Titanium silicalite-1 (TS-1) zeolite possesses attractive photocatalytic performance, but lack of modification strategies due to its microporous framework. Herein, we developed a pre-anchoring strategy to confine ultra-small Pt clusters inside TS-1 with ultra-low loading (0.2 mol%), in which Pt were anchored in Ti−OH nests by electronic metal-support interaction (EMSI). The optimal catalyst achieved a remarkable H2 generation rate of 63.2 mmol g–1 h–1 in CH3OH solutions, along with the production of high-value chemical HCHO as the oxidation product with 96.9% selectivity. Investigations reveal that the EMSI between Pt and Ti facilitated the selective decomposition of CH3OH to H2 and HCHO, leading to a nearly zero-carbon-emission process. Accordingly, we propose a light-driven carbon-negative "CO2→CH3OH→H2" route, coupling CO2 utilization and green H2 production with CH3OH as the intermediate, therefore offering a new perspective for "liquid sunshine".

Polaronic Mass Enhancement and Polaronic Excitons in Metal Halide Perovskites.

In metal halide perovskites, the complex dielectric screening together with low energy of phonon modes leads to non-negligible Fröhlich coupling. While this feature of perovskites has already been used to explain some of the puzzling aspects of carrier transport in these materials, the possible impact of polaronic effects on the optical response, especially excitonic properties, is much less explored. Here, with the use of magneto-optical spectroscopy, we revealed the non-hydrogenic character of the excitons in metal halide perovskites, resulting from the pronounced Fröhlich coupling. Our results can be well described by the polaronic-exciton picture where electron and hole interactions are no longer described by a Coulomb potential. Furthermore, we show experimental evidence that the carrier-phonon interaction leads to the enhancement of the carrier's effective mass. Notably, our measurements reveal a pronounced temperature dependence of the carrier's effective mass, which we attribute to a band structure renormalization induced by the population of low-energy phonon modes. This interpretation finds support in our first-principles calculations.

Local microenvironment modulation of Pt0/Pt2+ nano-clusters inducing synchronous mass transfer effect to boost catalytic ozonation

Rational catalyst structure design is expected to solve the low O3 utilization and poor molecular mass transfer efficiency in heterogeneous catalytic ozonation (HCO). Herein, Pt/CMK-3 catalyst with confined space to enhance mass transfer was synthesized and employed for CH3SH removal. Unlike fully free diffusion in 0–2.0 wt% Pt/CMK-3 and bulk phase diffusion in 10.0 wt% Pt/CMK-3, removal efficiency of 5.0 wt% Pt/CMK-3 was significantly improved to 97.0%, which was attributed to the effective interfacial diffusion of O3 and CH3SH through local microenvironment modulation of Pt0/Pt2+ nanoclusters (NCs) inducing synchronous mass transfer. Experimental and DFT calculations confirmed the strong electronic interactions between O3 and Pt0 facilitated charge redistribution and preferential O3 activation. AIMD simulation demonstrated that the synchronous difference in mean-square displacements (MSD) and diffusion coefficient (Dc) of CH3SH (Dc=0.022) and O3 (Dc=0.0046) in the confined Pt/CMK-3 system could facilitate CH3SH migrate to Pt2+ through interfacial diffusion. Especially, the d-orbital electrons of Pt NCs interact sequentially with p-orbital electrons of CH3SH and O3 to maintain redox of Pt0/Pt2+. This study provides novel insights on effective mass transfer and kinetic properties of gaseous reaction between oxidant and pollutant by constructing unique interfacial diffusion behaviors.

On the issue of the introduction of information and telecommunication technologies in criminal proceedings

Assessing the development of Russian criminal procedure science in modern conditions of digitalization, the author seeks to understand what impact the use of information and telecommunication technologies can have on the development of criminal proceedings, ensuring human and civil rights and freedoms. Discussing the threats of the rapid implementation of IT technologies by the criminal community, it is concluded that it is necessary not only to counter criminal encroachments, but also to digitalize criminal procedures through the introduction of electronic criminal proceedings, electronic interaction of subjects of criminal prosecution with individuals and legal entities using cyberspace (messengers, information platforms), and the use of video conferencing. Attention is focused on an integrated approach to the formation of an information society and scientific and technological development, and some aspects of this approach are presented, implemented in the educational and scientific activities of the Moscow Academy of the Investigative Committee named after A.Y. Sukharev. Using the example of the investigator’s exercise of the right to appeal against the prosecutor’s decisions using information and telecommunication technologies, the author’s position on optimizing the timing of the preliminary investigation, procedural control, prosecutorial supervision and taking response measures aimed at protecting the rights of participants in criminal proceedings is argued. Considering legislative measures for the digital transformation of criminal procedure law, the author comes to the conclusion that they are aimed at improving criminal proceedings by introducing a new form of proceedings, simplifying the work of subjects of criminal prosecution, and providing additional guarantees to «non-professional» participants in criminal proceedings by ensuring their access to justice .

Positive and Negative Effects under Light Illumination in Halide Perovskites

Metal halide perovskites (MHPs) have excellent characteristics and present great potential in a broad range of applications such as solar cells, light‐emitting diodes, and photodetectors. However, the light stability of devices remains an unresolved issue and has received great research attention. Under light illumination, MHPs exhibit various anomalous phenomena, such as photoluminescence (PL) enhancement, defect curing, PL blinking, and phase segregation. These phenomena are commonly considered intimately correlated with the performance and stability of MHP devices. In recent years, significant efforts have been made experimentally and theoretically toward understanding the physical origins of these anomalous effects. However, most research focuses on negative effects while the positive effects are mostly ignored. Herein, the positive effects and the negative effects of light soaking in MHPs are systematically discussed with a classification of the correlated physical mechanisms by specifically focusing on variation occurring in timescale from second to hour, corresponding to the unique ionic–electronic interaction. This intends to provide a new insight into ion effects on excellent properties of perovskites, and deep physical understanding of charge‐carrier and ion dynamics in perovskite, and theoretical guidelines for the fabrication of high‐quality and stability perovskite‐based photovoltaic and photoelectric devices.

Accumulated charge density at the interface boosts the urea oxidation reaction activity of Ni3N/Ni3S2 heterointerface

Optimizing the adsorption strength of multiple intermediates at one single active site at the same time is rather difficult. Heterointerface engineering provides more than one type of active sites to function, which may dramatically enhance the intrinsic urea oxidation reaction (UOR) activity of catalysts. Herein, a Ni3N (110)/Ni3S2 (010) heterointerface was fabricated. The electronic interactions between the two phases generates an accumulated charge density heterointerface and endows the heterointerface with more enhanced density of states, which facilitates the adsorption and desorption of more UOR intermediates, thus lowering the theoretical reaction barrier for the rate-controlling step of *CONHN to *CONN. The nickel moieties on Ni3N side tends to bond carbonyl and the nickel moieties on Ni3S2 side preferentially bond amnio. The cooperation of both nickel moieties contributes to the superb intrinsic UOR activity of Ni3N (110)/Ni3S2 (010) heterointerface. As a consequence, Ni3N (110)/Ni3S2 (010) heterointerface showcases outstanding UOR activity, reaching 105.66 mA·cm−2 at 1.6 V. This work provides an excellent UOR catalyst and helps to better understand the cooperation mechanism of the active sites at the heterointerface.

S‐Scheme g‐C3N4/CdS Heterostructures Grafting Single Pd Atoms for Ultrafast Charge Transport and Efficient Visible‐Light‐Driven H2 Evolution

AbstractEmerging step‐scheme (S‐scheme) heterostructures hold unique superiority in steering directional charge transport and reinforcing redox capacity, yet rational modification of S‐scheme heterostructures by single atoms (SAs) for efficient photocatalytic H2 evolution is rarely reported. In this work, Pd SAs‐modulated organic–inorganic g‐C3N4/CdS S‐scheme heterostructures are designed and prepared by a one‐pot mechanochemical approach allowing for g‐C3N4 nanosheets/CdS nanoparticles to confine atomically dispersed Pd co‐catalysts. The g‐C3N4/CdS S‐scheme charge‐transfer pathway is corroborated by a combination of in situ irradiated X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and Kelvin probe force microscopy. Density functional theory (DFT) calculations, high‐angle annular dark‐field scanning transmission electron microscopy, and X‐ray absorption fine structure identify Pd‐S3 and Pd‐N2 atomic moieties underpinned by the electronic interaction between Pd SAs and g‐C3N4/CdS heterostructures, in which the d‐band center of Pd SAs is optimized for proton adsorption thermodynamically. Further, the g‐C3N4/CdS S‐scheme heterostructures alongside Pd SAs in concert boost the rapid migration of photogenerated electrons (1.05 ps) via Pd─S and Pd─N bond‐derived channels. A maximal H2 evolution rate of 85.66 mmol h−1 g−1 is achieved by 1 wt% Pd‐20 wt% g‐C3N4/CdS hierarchical composites. This work may guide the design of high‐efficiency S‐scheme‐based photocatalysts for solar‐to‐H2 conversion and beyond.

Study of new p-tolylpiperidin-4-one as an anti-Parkinson agent: Synthesis, spectral, XRD-crystal, in silico study, electronic and intermolecular interaction investigations by the DFT method

This study thoroughly investigated the potential of using 3,3-dimethyl-2,6-di-p-tolylpiperidin-4-one, (DMeTP) as an anti-Parkinson medicine against Parkinson's disease. To accomplish this, DMeTP was synthesized and characterized by various spectral techniques such as FT-IR, NMR, and Mass. The Hirshfeld analysis and finger plot were used in this study to reveal important insights about the intermolecular relations of the compounds. The theoretical analyses of the compound was carried out using Density Functional Theory (DFT) at the level of theory B3LYP/6–311++G (**). The frontier orbital and the molecular electrostatic potential studies proved the chemical stability of the DMeTP structure. Then, weak interactions like hydrogen and Vdw interactions were investigated throughout the topological study (AIM and RDG). The alpha-synuclein protein was used in a molecular docking analysis to uncover inhibitory properties against Parkinson's disease. Additionally, the pharmacokinetic and physicochemical characteristics of the DMeTP molecule were examined using the SwissADME online program.

Exploring the joint influence of SO2 and alkali metal on FeW mixed oxides catalyst for NOx elimination

The coexistence of multiple substances in the flue gas, such as alkali metal and SO2, results in the NH3-SCR catalysts suffering from serious deactivation. Therefore, we systematically studied the effects of coexisting SO2 and Na on the FeW oxides for NOx elimination. This study elucidates that the joint influence mechanism of these substances on SCR activity was regulated by reaction temperatures. When the temperature was below 300 °C, the catalyst suffered a double whammy. The addition of SO2 in process of NH3-SCR resulted in a decrease in the activity of Na-poisoned FeW catalyst. It was largely due to the formation of inorganic SO42-, which not only consumed the NH3 but also blocked active sites. With the increase of reaction temperatures above 300 °C, the SO2 could interact with Na2O to construct a ternary electron interaction of SO42--Na+-FeW, contributing to the improvement of alkali metal resistance. This sulfate adjusted the D-band center energy of the catalyst closer to the Fermi level, thereby boosting the adsorption energies of NH3 and NO, increasing their adsorption abilities. Furthermore, sulfate binding broke the Na-O-Fe and Na-O-W bonds, resulting in the restoration of Fe-O-W and Fe-O-Fe active sites and accumulation of Na+ species. Precise characterizations and theoretical calculations shed light on the joint mechanism of SO2 and alkali metals which provide guidance to the design SCR catalyst with excellent resistance to SO2 and alkali metal poisoning.

Structural and electronic transport properties of Zn- and Ga-doped Bi2− x Sb x Te3− y Se y topological insulator single crystals

A comprehensive study of structural and magnetotransport properties of pristine Bi2−x Sb x Te3−y Se y (BSTS) single crystals and doped with Zn (BSTS:Zn) and Ga (BSTS:Ga) are presented here. Magnetic field dependent Hall resistivities of the single crystals indicate that the holes are the majority carriers. The field dependent resistivity curves at different temperatures of the crystals display cusp-like characteristics at low magnetic fields, attributed to two-dimensional (2D) weak antilocalization (WAL) effect. We fit the observed low-field WAL effects at low temperatures using 2D and three-dimensional (3D) Hikami-Larkin-Nagaoka (HLN) equations. The 2D HLN equation fits the data more closely than the 3D HLN equation, indicating a 2D nature. The 2D HLN equation fit to the low field WAL effects at various temperatures reveal a phase coherence length (l φ) that decreases as temperature increases. The variation of l φ with temperature follows T −0.41 power law for BSTS:Zn, suggesting that the dominant dephasing mechanism is a 2D electron–electron (e−e) interactions. For pristine BSTS and BSTS:Ga, l φ(T) is described by considering a coexistence of 2D e−e and electron–phonon (e−p) interactions in the single crystals. The temperature variation of the longitudinal resistance in BSTS:Ga is described by 3D Mott variable range hoping model. In contrast, the transport mechanisms of both pristine BSTS and BSTS:Zn are described by a combination of 2D WAL/EEI models and 3D WAL.

Quantum computational, charge density, optical, molecular reactivity and thermodynamical analysis of Di-Halogen substituted nicotinic acid derivatives

6-Chloro-3-fluoro-2-(trifluoromethyl) isonicotinic acid (6C3F2TINA) and 6-Chloro-5-fluoronicotinic acid (6C5FNA) are currently being studied using the DFT method for the detailed examination of structural and molecular character alterationsin gas as well as in several organic solvent media. Implementing electrostatic potential maps and Fukui functions analyses the reactive environment of compounds. The occurrence of the transfer of electrons and holes within the molecule is reported by a charge transfer study along with the heat maps. The orbital study investigates the electronic density and interactions within themolecules. Optical examination of compounds revealed an enhancement with the solvents. Thebonding typefound in molecules isdetermined by topographical investigation, which examines the concentration and localisationof electrons present in them. The UV–Vis spectra exhibit the absorption characteristics of these compounds. The thermodynamic investigation reveals the compound’s stability at various temperatures at 1 atm pressure.

Self-supported Ru-Fe-Ox nanospheres as efficient electrocatalyst to boost overall water-splitting in acid and alkaline media

Developing electrocatalysts with high activity and durability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in both acidic and alkaline electrolytes remains challenging. In this study, we synthesize a self-supported ruthenium-iron oxide on carbon cloth (Ru-Fe-Ox/CC) using solvothermal methods followed by air calcination. The morphology of the nanoparticle exposes numerous active sites vital for electrocatalysis. Additionally, the strong electronic interaction between Ru and Fe enhances electrocatalytic kinetics optimization. The porous structure of the carbon cloth matrix facilitates mass transport, improving electrolyte penetration and bubble release. Consequently, Ru-Fe-Ox/CC demonstrates excellent catalytic performance, achieving low overpotentials of 32 mV and 28 mV for HER and 216 mV and 228 mV for OER in acidic and alkaline electrolytes, respectively. Notably, only 1.48 V and 1.46 V are required to reach 10 mA cm−2 for efficient water-splitting in both mediums, exhibiting remarkable stability. This research offers insights into designing versatile, highly efficient catalysts suitable for varied pH conditions.

Nonadiabatic dynamics of molecules interacting with metal surfaces: A quantum-classical approach based on Langevin dynamics and the hierarchical equations of motion.

A novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees of freedom with Langevin dynamics for the classical degrees of freedom, namely, low-frequency vibrational modes within the molecule. The approach extends previous mixed quantum-classical methods based on Langevin equations to models containing strong electron-electron or quantum electronic-vibrational interactions, while maintaining a nonperturbative and non-Markovian treatment of the molecule-metal coupling. To demonstrate the approach, nonequilibrium transport observables are calculated for a molecular nanojunction containing strong interactions.

Interplay of Landau Quantization and Interminivalley Scatterings in a Weakly Coupled Moiré Superlattice.

Double-layer quantum systems are promising platforms for realizing novel quantum phases. Here, we report a study of quantum oscillations (QOs) in a weakly coupled double-layer system composed of a large-angle twisted-double-bilayer graphene (TDBG). We quantify the interlayer coupling strength by measuring the interlayer capacitance from the QOs pattern at low temperatures, revealing electron-hole asymmetry. At high temperatures when SdHOs are thermally smeared, we observe resistance peaks when Landau levels (LLs) from two moiré minivalleys are aligned, regardless of carrier density; eventually, it results in a 2-fold increase of oscillating frequency in D, serving as compelling evidence of the magneto-intersub-band oscillations (MISOs) in double-layer systems. The temperature dependence of MISOs suggests that electron-electron interactions play a crucial role and the scattering times obtained from MISO thermal damping are correlated with the interlayer coupling strength. Our study reveals intriguing interplays among Landau quantization, moiré band structure, and scatterings.

Preparation and electrocatalytic oxygen evolution of bimetallic phosphates (NiFe)2P/NF

Abstract The energy and environmental crisis pose a great challenge to human development in the 21st century. The design and development of clean and renewable energy and the solution for environmental pollution have become a hotspot in the current research. Based on the preparation of transition metal phosphates, transition metals were used as raw materials, Prussian blue-like NiFe(CN)6 as a precursor, which was in situ grown on nickel foam (NF) substrate. After low temperature phosphating treatment, a bimetallic phosphide electrocatalyst (NiFe)2P/NF was prepared on NF substrate. Using 1 mol·L−1 KOH solution as a basic electrolyte, based on the electrochemical workstation of a three-electrode system, the electrochemical catalytic oxygen evolution performance of the material was tested and evaluated. Experiments show that (NiFe)2P/NF catalyst has excellent oxygen evolution performance. In an alkaline medium, the overpotential required to obtain the catalytic current density of 10 mA·cm−2 is only 220 mV, and the Tafel slope is 67 mV·dec−1. This is largely due to: (1) (NiFe)2p/NF nanocatalysts were well dispersed on NF substrates, which increased the number of active sites exposed; (2) the hollow heterostructure of bimetallic phosphates promotes the electron interaction between (NiFe)2P and NF, increased the rate of charge transfer, and the electrical conductivity of the material is improved; and (3) theoretical calculations show that (NiFe)2P/NF hollow heterostructure can effectively reduce the dissociation barrier of water, promote the dissociation of water; furthermore, the kinetic reaction rate of electrocatalytic oxygen evolution is accelerated. Meanwhile, the catalyst still has high activity and high stability in 30 wt% concentrated alkali solution. Therefore, the construction of (NiFe)2P/NF electrocatalysts enriches the application of non-noble metal nanomaterials in the field of oxygen production from electrolytic water.

Отдельные аспекты трансформации правового регулирования договорных отношений, происходящей на фоне цифровизации (на примере Китайской Народной Республики и Российской Федерации)

Using the example of the development of contractual legal relations in the People’s Republic of China and the Russian Federation, the article shows certain aspects of the transformation of legal regulation and adaptation of civil legislation to the changing realities of economic reality in the context of digitalization. The author comes to the conclusion that there is a gradual adaptation of civil legislation to those processes associated with digitalization, active implementation and use of information technologies. In terms of regulating contractual relations, the People’s Republic of China has gone through a difficult path, which began with the reception of foreign experience. She achieved rationalization of legislation, not only by integrating the 1999 Contract Law, administrative rules, and judicial interpretations into the Civil Code, but also taking into account modern processes of electronic interaction between counterparties. The experience of the PRC may be useful for improving our civil legislation.

Metal-support interface engineering for stable and enhanced hydrogen evolution reaction

Hydrogen has emerged as a green and sustainable pathway towards achieving global decarbonization and net-zero emissions, intensely driving the need for efficient hydrogen production protocols. Electrocatalytic hydrogen evolution reaction (HER) holds great potential as a scalable, eco-friendly and safe avenue for efficient hydrogen production. However, the large-scale implementation of electrocatalytic HER is substantially challenged by the high-cost and unstable materials that are mainly fabricated from noble metals, e.g., Pt and Pd. Given this challenge, we adopted an interface engineering strategy to immobilize nanoscale Pt particles within the framework of nitrogen-doped CNTs, namely Pt@N-CNTs, where electronic metal-support interaction (EMSI) plays an important role in enabling orbital rehybridization and regulating the charge transfer through the metal-support interface, thereby considerably improving the electrocatalytic activity. With limited content of noble metals, our developed Pt@N-CNTs delivered superior HER performance with an ultralow overpotential of 5.8 mV at 10 mA cm−2 and demonstrated a high mass activity of 12.72 A mgPt−1 at an overpotential of 50 mV as well as excellent stability under harsh acidic conditions. At 500 mA cm−2, Pt@N-CNTs surprisingly exhibited an overpotential of 55.2 mV, outperforming that of commercial 20 wt% Pt/C catalysts (131.5 mV). Importantly, we established a straightforward, scalable, and time-saving microwave reduction strategy, alluding to its promising commercial viability. This work therefore sheds light on the development of high-performance electrocatalysts for hydrogen evolution and water electrolysis.

Structural and superconducting properties in the Te-doped spinel CuRh2Se4

In this paper, we discuss the impact of tellurium (Te) doping on the spinel superconductor CuRh2Se4. We conducted a comprehensive evaluation of the structural and superconducting properties of the system using various techniques, including X-ray diffraction (XRD), resistivity, magnetization, and specific heat measurements. Based on our XRD analysis, we found that the spinel superconductor CuRh2Se4-xTex (0 ≤ x ≤ 0.28) crystallizes in the space group Fd3̅m (227), while the layered compound CuRh2Se4-xTex (2.8 ≤ x ≤ 4.0) crystallizes in the space group P3̅m1 (164). The upper critical magnetic field can be increased from 0.95(2) T for CuRh2Se4 to 3.44(1) T for CuRh2Se3.72Te0.28 by doping with elemental Te. However, the layered compound CuRh2Se4-xTex (2.8 ≤ x ≤ 4.0) did not exhibit superconducting properties. Besides, the specific heat measurements of CuRh2Se4-xTex (x = 0, 0.1, 0.28) indicate that the Te element doping affects the electronic structure and interactions of the material and breaks the stability of the superconducting pairing, which leads to a decrease in the Tc. Finally, we show the electronic phase diagram of Tc with Te doping to summarise our findings.