Physical Chemistry Chemical Physics最新文献

In this study, a Ni-based composite incorporating Ni₄N and La₂O₃ supported on carbon nanotubes (Ni–La–Ni₄N/CNT) was synthesized as an efficiency electrocatalyst towards the hydrogen evolution reaction in different electrolytes with the kinetics and energy consumption investigated in detail. The Ni–La–Ni₄N/CNT exhibits overpotentials of 124 mV and 200 mV at the current density of 10 mA cm⁻² in 1.0 M KOH and alkaline seawater, respectively. As quantitative comparison, the exchange current density (j°) based on Volmer–Heyrovsky–Tafel mechanism was calculated from various polarization curves, which indicated that the addition of NaCl in alkaline medium or using seawater alone reduced the reactivity of the catalyst. The activity of Ni–La–Ni₄N/CNT in alkaline seawater was equal to 91% of that in 1.0 M KOH. Furthermore, dynamic polarization resistance and corresponding current were obtained by the analysis of the equivalent circuit model with the extended Kalman filter algorithm. The analysis of the resistance power at 1 mW also shows that the current between the conditions in KOH and in seawater is 2.76 times. Adding alkaline substances to seawater can narrow it to 1.19 times. These strategies provide novel approaches for inspecting the activity changes of materials in different electrochemical environments.

The origin of the forces acting on a silica surface from an ice solidification interface was investigated to understand the solidification phenomenon and its impact on nanometer-scale structures using molecular dynamics simulations. The microscopic forces were determined by appropriately averaging the forces acting on the silica wall from the water molecules in time and space; the time evolutions of these microscopic forces during the solidification processes were investigated for three types of silica surfaces. The results indicate that the microscopic forces fluctuate more after the solidification interface makes contact with the wall surface. To visualize the changes in the microscopic forces and hydrogen bonds due to solidification, their differences compared to the liquid state were calculated. When the solidification interface is near the wall, the changes in these microscopic forces and hydrogen bonds due to solidification are correlated. This tendency is more significant for an amorphous wall and a wall with a structure than for a crystalline wall. The changes in the microscopic force depend on the water molecules that behave as acceptors when forming the hydrogen bonds with the wall and on the configuration of the silanol groups on the silica surfaces.

In this study, quantum chemical calculations were used to explore the synthesis of three chiral α-amino acids, specifically alanine, serine, and isovaline, from reactants found in interstellar space. Our focus is on the crucial step in the synthesis pathway that determines the chirality of the amino acids. The results indicate that in the case of alanine, the determination of enantiomer is primarily influenced by the direction of the collision of molecules or functional groups, which leads to the formation of a chirality center in a crucial intermediate. However, contrary to chemical expectations, the enantiodetermining/enantioselection step for serine and isovaline synthesis occurs prior to the creation of a chirality center.

Two-dimensional (2D) ferromagnetic (FM) semiconductors have been paid much attention due to the potential applications in spintronics. Here, the electronic and magnetic properties of 2D Janus Ni-trihalide monolayer Ni₂X₃Y₃ (X, Y = I, Br, Cl; X ≠ Y) are investigated by first-principle calculations. The properties of Ni₂X₃Y₃ (X, Y = I, Br, Cl; X ≠ Y) monolayers are compared by selecting the NiCl₃ monolayer as the reference material. Ni₂X₃Y₃ monolayers have two distinct magnetic ground states of ferromagnetic (FM) and antiferromagnetic (AFM). In the Ni₂X₃Y₃ monolayer, two different orbital splits were observed, one semiconductor state and the other semimetal state. The semimetal state of Ni₂X₃Y₃ can be tuned to semiconductor or metallic state when biaxial strain is applied. The magnetic anisotropy energy (MAE) of the Ni₂X₃Y₃ monolayer can display variations compared to that of the NiCl₃ monolayer, with the direction of easy magnetization being influenced by the specific halogen elements present. The easy magnetization direction of Ni₂X₃Y₃ can also be changed by applying biaxial strain. The T_c of Ni₂X₃Y₃ is predicted to be about 100 K according to the calculation of the E_AFM–E_FM model. The design of the Janus Ni₂X₃Y₃ structure has expanded the range of 2D magnetic materials, a significant contribution has been made to the advancement of spintronics and its applications.

Vibrational circular dichroism (VCD) spectroscopy is a powerful technique for structural analysis of chiral molecules, but information available from VCD spectra of large molecular systems can be limited by severe overlap of vibrational bands. While common chiral molecules do not absorb in the 1900–2400 cm⁻¹ region, observation of VCD signals in this spectrally-isolated region is possible for molecules containing C–D, XY, and XYZ chromophores. Thus, a strategic introduction of these chromophores to a target molecule may produce VCD signals informative for molecular structures. VCD spectroscopy in the 1900–2400 cm⁻¹ region is a rather unexplored research field and its basic properties remain to be investigated. This perspective article discusses insight obtained so far on the usefulness and physicochemical aspects of VCD spectroscopy in this region with briefly summarizing previous experimental VCD studies including classic examples as well as our recent results. We show that anharmonic effects such as overtones and combination bands often complicate VCD patterns. On the other hand, some molecules exhibit characteristic VCD signals that can be well interpreted by harmonic DFT spectral calculations for structural analysis. This article also discusses several examples of the use of this region for studying solute–solvent interactions and for VCD signal augmentation.

Mirror symmetry breaking bifurcations, that occur in nonlinear chemical systems leading to final chiral states with very large enantiomeric excess, can be exploited as an efficient chiral signal selector for even the smallest chiral polarizations. This effect of the chiral polarization requires the system's capacity for overcoming thermal noise, which is manifested as fluctuating reaction rate constants. Therefore, we investigate the chiral selectivity across a range of tiny parity-violating energy differences (PVED) in the presence of inevitable non-equilibrium temperature fluctuations. We use a stochastic differential equation simulation methodology (Ito process) that serves as a valuable tool in open systems for identifying the thresholds at which the chiral force induces chiral selectivity in the presence of non-equilibrium temperature fluctuations. This approach enables us to include and analyze chiral selectivity in the presence of other types of fluctuations, such as perturbations in the rate of fluid flow into and out of the reactor and in the clamped input concentrations. These concepts may be of practical interest (i.e., spontaneous deracemizations) but are also useful for a better understanding of the general principles governing the emergence of biological homochirality.

The present work explores the photophysical, electrochemical, and fluorescence polarization properties of a group of π-conjugated phenylethynyl-2,1,3-benzothiadiazole derivatives (BTDs) bearing different electron-donating (ED) or electron-withdrawing (EW) substituents at the para position of the phenylethynyl moiety. The BTDs were synthesized through the Sonogashira cross-coupling reaction between 4-bromo-2,1,3-benzothiadiazole and the respective para-substituted phenylethynyl derivatives. The BTDs with the EW-substituents show relatively weak solvatochromic behavior, while the BTDs with the strong ED-substituents like methoxy and N,N-dimethylamino-based substituents (BTDPhOMe and BTDPhNMe₂) exhibit a pronounced solvatochromic behavior. The change in dipole moments in the excited states of the derivatives was calculated using Lippert–Mataga plots. The conclusions drawn on the spectral behavior of the molecules could be rationalized by TD-DFT calculations involving electron density difference (EDD) maps that correlate with the ICT characteristics of the molecules. The experimental and theoretical calculations reveal that the BTDs with the strong ED-substituents (strong push–pull type BTDs) have a strong ICT character in the excited state. These strong push–pull type BTDs show high fluorescence quantum yield (Φ_F) in apolar solvents and low Φ_F in polar solvents. In contrast, the BTDs with the weak ED-substituents (weak push–pull type BTDs) and EW-substituents (pull–pull type BTDs) have a weaker ICT character with low Φ_F in apolar and high Φ_F in polar solvent media. There is good a agreement among the HOMO–LUMO band gaps obtained from absorption spectroscopy and electrochemical studies and theoretical calculations. The fluorescence anisotropy measurement in the glycerol medium shows that the studied BTDs generally exhibit higher sensitivity towards microviscosity than the traditional DPH fluorescence anisotropy probe.

Metal–organic frameworks (MOFs) offer promising opportunities for modifying energetic materials due to their micro-porous structure and high performance. In this study, we present a novel green MOF named cyclodextrin-MOF (CD-MOF), which incorporates potassium ions, synthesized using a simple methanol vapor diffusion approach. The CD-MOF incorporates potassium ions and enhances propellant performance through intermolecular force optimization with nitrocellulose (NC). Molecular dynamics simulations reveal stronger interactions between the CD-MOF and NC. The loading of the CD-MOF within NC forms a stable structure with resistance to migration and defense against crystalline precipitation and water absorption. Notably, in static combustion and pyrolysis tests, the CD-MOF exhibits efficient flame and flash inhibition. The thermal degradation and cauterization of the CD-MOF resulted in the formation of a complex microporous material capable of absorbing flammable and harmful gases such as CO, NO, NO₂, and N₂O. These findings shed light on the superior performance of the CD-MOF compared to conventional inorganic salts, and the comprehensive characterization and molecular simulations provide insights into the unique properties and applications of the CD-MOF, emphasizing its significant contribution to the field of green propellants.

Two-dimensional (2D) materials formed by thin-films of metal oxides that grow on metal supports are commonly used in heterogeneous catalysis and multilayer electronic devices. Despite extensive research on these systems, the effects of charged defects at supported oxides on surface processes are still not clear. In this work, we perform spin-polarized density-functional theory (DFT) calculations to investigate formation and interaction of charged magnesium and oxygen vacancies, and Al dopants on MgO(001)/Ag(001) surface. The results show a sizable interface compressive effect that decreases the metal work function as electrons are added on the MgO surface with a magnesium vacancy. This surface displays a larger formation energy in a water environment (O-rich condition) even with additional Al-doping. Under these conditions, we found that a polar molecule such as CO is more strongly adsorbed on the low-coordination oxygen sites due to a larger contribution of the channeled electronic transport with the silver interface regardless of the surface charge. Therefore, these findings elucidate how surface intrinsic vacancies can influence or contribute to charge transfer, which allows one to explore more specific reactions at different surface topologies for more efficient catalysts for CO₂ conversion.

Here, we present an experimental investigation on the nonlinear optical (NLO) and optical limiting properties of metalloporphyrin compounds (Cu-1-OH, Zn-1-OH, Cu-1-E and Zn-1-E) using spatial self-phase modulation (SSPM) method in the visible range. It is found that all of the samples show a large self-defocusing effect at 532 nm, which is attributed to the thermal nonlinear optical effects with negative nonlinear refractive index coefficient n₂ due to the relatively high absorption at 532 nm. In contrast, at 780 nm where absorption is weak for both Zn- and Cu-porphyrins, Zn-porphyrins still exhibit visible self-defocusing while Cu-porphyrins do not show any nonlinear diffraction pattern. Such a phenomenon can be explained by the Kerr effect of Cu-porphyrins at 780 nm. As the thermal nonlinear optical effects (of negative n₂) at 780 nm are reduced due to the low absorption, the Kerr effect with positive n₂ becomes comparable and the overall nonlinearity is reduced. The Kerr effect of Cu-porphyrins is stronger than that of Zn-porphyrins because of the enhanced π-electron delocalization effect as Cu(II) has a variable number of valence electrons and incompletely filled d atomic orbitals. Finally, the optical limiting performance of Zn-porphyrins is demonstrated as a representative and its dependence on sample position is examined. This work not only enriches the understanding of the physical mechanism of optical limiting in porphyrin materials, but also provides a significant reference to improve the third-order NLO coefficient by adjusting the structure of compounds.