The Journal of Physical Chemistry C最新文献

Interatomic potentials (IPs) with wide elemental coverage and high accuracy are powerful tools for high-throughput materials discovery. While the past few years witnessed the development of multiple new universal IPs that cover wide ranges of the periodic table, their applicability to target chemical systems should be carefully investigated. We benchmark several universal IPs using equilibrium zeolite structures as testbeds by evaluating geometric parameters, energies, and relative stability. We select a diverse set of universal IPs encompassing two major categories: (i) universal analytic IPs, including GFN-FF, UFF, and Dreiding; (ii) pretrained universal machine learning IPs (MLIPs), comprising CHGNet, ORB-v3, MatterSim, eSEN-30M-OAM, PFP-v7, and EquiformerV2-lE4-lF100-S2EFS-OC22. We compare them with established tailor-made IPs, SLC, ClayFF, and BSFF using experimental data and density functional theory (DFT) calculations with dispersion correction as the reference. The tested zeolite structures comprise pure silica frameworks and aluminosilicates containing copper species, potassium, and an organic cation. We found that GFN-FF is the best among the tested universal analytic IPs, but its good performance is limited in silica zeolites without highly strained rings. Some universal MLIPs achieve the energies with a root mean squared error between MLIP and DFT energies below a previously tailor-made MLIP. Among the universal MLIPs, the eSEN-30M-OAM model outperformed the other universal IPs in predicting structures and energies close to experiments and DFT across all zeolite structures studied. These findings show that the modern pretrained universal MLIPs are practical tools in replacing high-throughput DFT calculations against equilibrium zeolite structures, although they inherit the inherent errors of DFT.

Heterogeneous catalysis involves a complex interplay of adsorption, charge transfer, and catalyst restructuring at solid–gas or solid–liquid interfaces. While first-principles methods such as KS-DFT and AIMD accurately describe chemisorbed species, they struggle to capture weakly bound or dynamic molecules subject to thermal fluctuations. Continuum models provide macroscopic insight into electrostatics and transport but often neglect the interfacial molecular structure, especially within the Stern layer. The challenge is even greater at gas–solid interfaces, where the gas phase is typically ignored, giving rise to a long-standing pressure gap between theory and experiment. This Perspective advocates a statistical-mechanical description of interfacial species using classical density functional theory (cDFT), in which physisorption and gas/liquid-phase inhomogeneity near catalytic surfaces are represented by molecular density distributions rather than fixed atomic configurations. More importantly, we emphasize the necessity of integrating KS-DFT with such microenvironmental models and propose several potential strategies for coupling electronic-structure calculations with continuum and statistical-mechanical approaches. By merging first-principles, continuum, and statistical-mechanical approaches within open-system, physics-informed frameworks, it becomes possible to bridge electrochemical and thermocatalytic regimes─from localized chemisorption to diffuse physisorption─and reveal the true complexity of catalytic interfaces.

The Fe-N/C catalysts have been identified as promising alternatives to Pt catalysts for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. The pores in these carbon materials significantly influence the oxygen reduction activity and mechanisms. In this study, electrochemical impedance spectroscopy (EIS) is utilized to study the interfacial structure of porous materials distinguished by pore size. The Fe-N/C and metal-free N/C porous catalysts are synthesized by using an SBA-15 mesoporous silica template, resulting in materials with ordered morphology and a range of pore sizes from micropores to narrow and wide mesopores. Hydrodynamic voltammetry experiments indicate that Fe-N/C catalysts with wide mesopores exhibit better ORR activity and enhanced mass transport compared with metal-free N/C and microporous catalysts. The EIS results show that these catalysts exhibit the lowest overall resistance and the highest adsorption capacitance at the half-wave potential (E_1/2), indicating optimal operating conditions for practical applications. The impedance response highly depends on pore size, with the lowest mass transport resistance observed in wide mesoporous materials. The addition of iron precursors creates Fe-Nx sites and produces wide mesopores in the carbon material despite using mesoporous templates. This study underscores the importance of a diverse range of pores in influencing the ORR activity and mechanisms.

Tetradentate platinum(II) complexes have attracted considerable attention for their potential application as blue phosphorescent emitters in organic light-emitting diodes (OLEDs). Herein, two methoxy-functionalized complexes, Pt1-Cz-OMe and Pt2-Cz-OMe, were synthesized and characterized comprehensively. The introduction of a methoxy group shortens the Pt-ligand bond, thus enhancing the molecular compactness of the complexes and raising both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels. Consequently, the intraligand charge transfer (ILCT) component was significantly increased, and the photoluminescence quantum yields (PLQYs) of the obtained complexes Pt1-Cz-OMe and Pt2-Cz-OMe were enhanced to 95.3 and 91.0%, respectively. Finally, blue phosphorescence OLEDs with double light-emitting layers employing Pt1-Cz-OMe or Pt2-Cz-OMe as emitters exhibited remarkably high performances, especially at a low operating voltage (3.9 V at 1000 cd m^–2). These studies provide a new strategy for the design of excellent tetradentate platinum(II) complexes and high-performance blue phosphorescent OLEDs.

The graphene/ZnO (G/ZnO) interface is promising for photocatalysis due to its potential to enhance charge separation. Using density functional theory, we investigate the structural and electronic properties of G/ZnO interfaces in both parallel (basal-plane) and perpendicular (edge-contact) configurations on the nonpolar ZnO(101̅0) surface. In the case of the pristine ZnO(101̅0) surface, the Fermi level is located in the band gap, suggesting that the band bending from the bulk to the surface is small. In the case of the parallel G/ZnO(101̅0) interface, although the graphene has semimetallic density of states, the interaction is mainly due to van der Waals-like weak interaction and the Fermi level is located just below the conduction band minimum, indicating the induced band bending is still small. In contrast, in the case of perpendicular G/ZnO(101̅0) interfaces, the chemical bonds between the graphene edges and the ZnO surface are formed and electron transfer takes place from ZnO(101̅0) to graphene. This results in the shift of the Fermi level toward the valence band maximum and induces a large upward band bending from the n-type bulk ZnO to the interface. These findings highlight the importance of interface orientation and local energy level shifts in elucidating underlying charge transfer mechanisms for electronic and photocatalytic applications.

Here, we demonstrated directed self-assembly of quasi-2D cesium lead bromide perovskite nanoplates by liquid–air interfacial assembly. Due to their ionic crystal nature, perovskite nanocrystals are susceptible to degradation by most polar immiscible sublayer solvents (acetonitrile, diethylene glycol). We used glyceryl triacetate as a liquid substrate for nanoplate self-assembly. By tuning the interfacial energy and volume fraction of nanoplates, we achieved monolayer ensembles of nanoplates with face-down and edge-up ordering >100 μm² in area. Controlled ordering of these confined structures allowed us to access aligned electronic transition vectors in perovskite nanocrystal thin films. The dipole orientation factor, or proportion of horizontal dipoles, was modulated from Θ = 0.78 for face-down assemblies to Θ = 0.48 for edge-up assemblies, which corresponds to the majority in-plane and out-of-plane emissive modes, respectively. Control over nanoparticle ordering and dipole orientation in perovskite nanocrystals could lead to enhanced waveguides, light outcoupling, and photon coherence in photonic devices.

The crystal structure and nanoparticle morphology of cobalt (Co)-based materials directly determine their performance in Fischer–Tropsch synthesis, catalytic conversion, and related fields. MnO, as an additive, can optimize morphology by regulating the surface energy and exposed crystal planes of Co. However, there is currently a lack of systematic theoretical studies on the differences in surface energy between FCC and HCP Co phases and the corresponding response patterns to MnO adsorption. In this study, density functional theory (DFT) was employed to calculate the surface energies of key exposed crystal planes for FCC and HCP Co, and the equilibrium morphologies of both phases were constructed using Wulff theory. Furthermore, the study investigated the surface-energy reconstruction of each crystal plane upon MnO adsorption and analyzed the evolution characteristics of Wulff morphologies. The results indicate that the addition of MnO can enhance the stability of the nanoparticle surfaces. In particular, we found that, as the MnO/Co ratio increased, the exposure of the (311) and (110) crystal planes in FCC Co, which are highly active for the Fischer–Tropsch reaction and rich in B5 and 5F active sites, increased significantly. In HCP Co, the exposure fraction of the (10_11) facet decreases, whereas that of the (10_12) facet increases. Therefore, by regulating the MnO loading, it is possible to control the exposure of cobalt crystal facets, thereby enhancing the Fischer–Tropsch synthesis rate. This study elucidates the surface-energy differences between the two cobalt crystal structures and the mechanism by which MnO adsorption modulates them. By employing Wulff theory, a quantitative correlation model of “crystal structure–surface energy–morphology” is established, providing theoretical support for the selection of cobalt-based crystal forms, precise morphological control, and optimization of promoter dosage.

Organic crystals are known to be brittle materials, which may limit their application in different fields. Cause and effect relationships are usually reported for structures and properties, while molecular composition is usually taken out of scope. Isostructural crystals of both hexachlorobenzene and hexabromobenzene exhibit plasticity on the (001) crystal face, remaining brittle on the (101̅) face. Hexabromobenzene is less prone to plastic deformation in comparison to chlorine substituted benzene. In this work, we examine differences in molecular behavior from crystallographic, topological, and computational points of view, highlighting the influence of the halogen atom on intermolecular interactions, which determine different plasticities in these two crystals. The obtained results show that halogen–halogen interactions play a crucial role in mechanical properties, preserving the hexabromobenzene structure with a more stiff structure because of stronger interlayer bonds, which should be distorted because of the molecular layer slip. The concept of the modeling slip plane process is introduced to supplement traditional computational techniques. The influence of both absolute and relative intermolecular energies is highlighted within each structure because both systems have not only a bending face but a brittle one, too.

Chemical doping is an effective and feasible approach to enhancing ferroelectric photovoltaic (PV) effects, providing unique functionalities that are attractive for optoelectronic applications. In this study, we investigate the PV properties of BaTiO₃ ferroelectric single crystals doped with Mn. We found that the sample with a mixed valence of Mn²⁺ and Mn³⁺ (Mn^3+/2+) exhibits a PV response larger than those with Mn³⁺ or Mn⁴⁺ alone, owing to the electron transition from Mn²⁺-3d-derived electron-filled gap states. Transient absorption spectroscopy measurements combined with density functional theory calculations reveal that the filled gap states of the Mn^3+/2+ sample act as sources of nonthermalized electrons in the conduction band, giving rise to a ballistic current, while vacant gap states capture thermalized electrons at the conduction band minimum. These experimental and theoretical investigations uncover the roles of gap states in the PV effect and the photocarrier dynamics associated with the redox of transition metal cations in ferroelectric oxides.

Lithium–sulfur batteries (LSBs) have a high theoretical energy density (2600 mA hg^–1), but problems such as low sulfur conductivity, the polysulfide shuttle effect, and slow Li₂S oxidation kinetics have seriously affected their development. Based on the first-principles calculation framework, this study explores the anchoring ability and catalytic conversion mechanism of Janus configuration single-layer MSSe (M = Hf/Zr/V) when acting as a sulfur support for lithium–sulfur batteries. With the simulation calculation of structural stability, adsorption characteristics, conductivity, charge transfer, and Li₂S oxidation reaction kinetics, it is confirmed that VSSe has outstanding characteristics as a potential sulfur carrier and can significantly inhibit the shuttle effect of soluble polysulfides. The VSSe monolayer maintains metallicity before and after the adsorption of LiPSs, ensuring continuous electronic conductivity. At the same time, the synergistic mechanism of the adsorption–catalytic process in MSSe (M = Hf/Zr/V) is revealed, providing new ideas for building a new sulfur support that has both outstanding anchoring efficiency and efficient catalytic transformation.