Search Results (93)

This study investigated the coupling mechanism between interlayer twist angle and projectile size on the ballistic performance of bilayer phosphorene membranes, a topic essential for designing efficient nano-protective materials, yet still poorly understood. Using coarse-grained molecular dynamic simulations, we systematically explored how twist angles (0–90°) and projectile radii (2–10 nm) jointly influence impact response for membranes with a radius equal to 48 nm. We found that the effect of twist angle becomes significant only beyond a critical projectile size (~8 nm). Below this threshold, deformation remains local and twist-independent. However, for larger projectiles, the twist angle drastically alters wave propagation and failure modes. Specifically, a 90° twist induces severe wave reflection and interference, leading to a dramatic force amplification (up to 82%) and a 28% reduction in ballistic limit velocity, making it the most susceptible configuration. These results underline the critical role of twist–boundary–wave interaction in governing impact resistance and provide practical insights for the design of phosphorene-based nano-armor systems tailored to specific impact conditions. Full article

Carbon dioxide is naturally present in the Earth’s atmosphere and plays a role in regulating and balancing the planet’s temperature. However, due to various human activities, the amount of carbon dioxide is increasing beyond safe limits, disrupting the Earth’s natural temperature regulation system. Today, CO₂ is the most prevalent greenhouse gas; as its concentration rises, significant climate change occurs. Therefore, there is a need to utilize anthropogenically released carbon dioxide in valuable fuels, such as formic acid (HCOOH). Single-atom catalysts are widely used, where a single metal atom is anchored on a surface to catalyze chemical reactions. In this study, we investigated the potential of Cu@Phosphorene as a single-atom catalyst (SAC) for CO₂ reduction using quantum chemical calculations. All computations for Cu@Phosphorene were performed using density functional theory (DFT). Mechanistic studies were conducted for both bimolecular and termolecular pathways. The bimolecular mechanism involves one CO₂ and one H₂ molecule adsorbing on the surface, while the termolecular mechanism involves two CO₂ molecules adsorbing first, followed by H₂. Results indicate that the termolecular mechanism is preferred for formic acid formation due to its lower activation energy. Further analysis included charge transfer assessment via NBO, and interactions between the substrate, phosphorene, and the Cu atom were confirmed using quantum theory of atoms in molecules (QTAIM) and non-covalent interactions (NCI) analysis. Ab initio molecular dynamics (AIMD) calculations examined the temperature stability of the catalytic complex. Overall, Cu@Phosphorene appears to be an effective catalyst for converting CO₂ to formic acid and remains stable at higher temperatures, supporting efforts to mitigate climate change. Full article

The exceptional sensing properties of hydrogen-saturated zigzag phosphorene nanoribbons (ZPNRs-H) for sulfur-containing gases, namely SO₃, SO₂, and H₂S, were investigated using first-principles calculations based on density functional theory. The total energy, adsorption energy, and Mulliken charge transfer were assessed to evaluate the adsorption properties of the ZPNRs-H towards these gases. Notably, the ZPNRs-H exhibits physical adsorption for SO₂ and H₂S gas molecules, while demonstrating chemical adsorption for SO₃, characterized by a substantial adsorption energy and pronounced charge transfer. Furthermore, the adsorption of SO₃ significantly modulates the electronic density of states near the Fermi level of ZPNRs-H. The current–voltage (I–V) characteristics unveil a remarkable enhancement in conductivity post-SO₃ adsorption, underscoring the high sensitivity of ZPNRs-H towards SO₃. Our findings provide profound theoretical insights, heralding the potential of ZPNRs-H as a cutting-edge sensor for SO₃ detection. Full article

In this paper, the Poisson’s ratio of black phosphorene nanotubes was examined through the molecular dynamics simulation method. Our research discovered that for the armchair black phosphorene nanotubes, the radial strain and the wall thickness strain are negatively linearly correlated with the axial strain, and both the radial Poisson’s ratio and the thickness Poisson’s ratio are positive. For the zigzag black phosphorene nanotubes, the wall thickness strain is negatively, linearly correlated with the axial strain, while the radial strain has a cubic polynomial function relationship with the axial strain. The thickness Poisson’s ratio is positive, while the radial Poisson’s ratio is a quantity related to the axial strain. As the axial strain increases, the radial Poisson’s ratio progressively diminishes from a positive value and becomes negative upon reaching a specific critical axial strain threshold. During the tensile deformation along the axial direction of the zigzag black phosphorene nanotubes, the radial strain initially decreases before subsequently increasing. Notably, the diameter of the nanotube may even surpass its initial value, demonstrating a radial expansion in response to axial tension. Full article

The fabrication and application of single-site heterogeneous reaction centers are new frontiers in chemistry. Single-site heterogeneous reaction centers are analogous to metal centers in enzymes and transition-metal complexes: they are charged and decorated with ligands and would exhibit superior reactivity and selectivity in chemical conversion. Such high reactivity would also result in significant response, such as a band gap or resistance change, to approaching molecules, which can be used for sensing applications. As a proof of concept, the electronic structure and reaction pathways with NO and NO₂ of Au(I) fragments dispersed on phosphorene (Pene) were investigated with first-principle-based calculations. Atomic-deposited Au atoms on Pene (Au₁-Pene) have hybridized Au states in the bulk band gap of Pene and a decreased band gap of 0.14 eV and would aggregate into clusters. Passivation of the Au hybrid states with -OH and -CH₃ forms thermodynamically plausible HO-Au₁-Pene and H₃C-Au₁-Pene and restores the band gap to that of bulk Pene. Inspired by this, HO-Au₁-Pene and H₃C-Au₁-Pene were examined for detection of NO and NO₂ that would react with -OH and -CH₃, and the resulting decrease of band gap back to that of Au₁-Pene would be measurable. HO-Au₁-Pene and H₃C-Au₁-Pene are highly sensitive to NO and NO₂, and their calculated theoretical sensitivities are all 99.99%. The reaction of NO₂ with HO-Au₁-Pene is endothermic, making the dissociation of product HNO₃ more plausible, while the barriers for the reaction of CH₃-Au₁-Pene with NO and NO₂ are too high for spontaneous detection. Therefore, HO-Au₁-Pene is not eligible for NO₂ sensing and CH₃-Au₁-Pene is not eligible for NO and NO₂ sensing. The calculated energy barrier for the reaction of HO-Au-Pene with NO is 0.36 eV, and the reaction is about thermal neutral, suggesting HO-Au-Pene is highly sensitive for NO sensing and the reaction for NO detection is spontaneous. This work highlights the potential superior sensing performance of transition-metal fragments and their potential for next-generation sensing applications. Full article

The catalytic activity of monolayer and bilayer boron-doped edge black phosphorene nanoribbons (BPNRs) as electrocatalysts for the nitrogen reduction reaction (NRR) was investigated using first-principles calculations based on density functional theory (DFT). The results indicate that boron incorporation facilitates effective N₂ adsorption at specific BPNR edges, thereby achieving superior NRR electrocatalytic performance. Through NRR screening criteria, six candidate edges (B@ZZ₃-1, B@ZZ₄-1, B@AC₀-1, B@ZZ₀^AA-1, B@ZZ₁^AB-3, and B@ZZ₄^AA-3) were identified. Electronic property analysis revealed that boron doping significantly reduces the bandgap of BPNRs and enhances catalytic activity by promoting electron accumulation at boron sites. Free energy pathway calculations demonstrated that B@AC₀-1, B@ZZ₀^AA-1, and B@ZZ₁^AB-3 exhibit overpotentials of 0.19 V, 0.28 V, and 0.15 V, respectively, during the NRR process, outperforming other phosphorus-based catalysts in activity. Full article

Black phosphorus is a promising thermoelectric (TE) material because of its high Seebeck coefficient and high electrical conductivity. In this work, the TE performance of bulk black phosphorus and single-layer phosphorene under uniaxial strain is studied using first-principles calculations and Boltzmann transport theory. The results show relatively excellent TE performance along the armchair direction for both black phosphorus and phosphorene in our study. However, high lattice thermal conductivity is the key adverse factor for further enhancing the TE performance of phosphorus. The ZT value can only reach up to 0.97 and 0.73 for n- and p-type black phosphorus at 700 K, respectively. Owing to quantum size effects, black phosphorene has lower lattice thermal conductivity than black phosphorus. At the same time, two-dimensional (2D) phosphorene exhibits increased electronic energy compared with bulk black phosphorus, resulting in a larger bandgap and reduced electrical conductivity due to the quantum confinement effect. Thus, the TE performance of n-type phosphorene can be partially improved, and the ZT value reaches up to 1.41 at 700 K. However, the ZT value decreases from 0.73 to 0.70 for p-type phosphorene compared with bulk phosphorus at 700 K. To further improve the TE performance of phosphorene, a tensile strain is applied along the armchair direction. Subsequent work indicates that uniaxial strain can further optimize phosphorene’s TE properties by tuning hole relaxation time to improve electrical conductivity. Strikingly, the ZT values exceed 1.7 for both n- and p-type phosphorene under 4.5% tensile strain along the armchair direction at 700 K because of increased electrical conductivity and decreased lattice thermal conductivity. Full article

The field of newly developed two-dimensional (2D) materials with low symmetry and structural in-plane anisotropic properties has grown rapidly in recent years. The phosphorene analog of group IV monochalcogenides is a prominent subset of this group that has attracted a lot of attention because of its unique in-plane anisotropic electronic and optical properties, crystalline symmetries, abundance in the earth’s crust, and environmental friendliness. This article presents a review of the latest research advancements concerning 2D group IV monochalcogenides. It begins with an exploration of the crystal structures of these materials, alongside their optical and electronic properties. The review continues by discussing the various techniques employed for the synthesis of layered group IV monochalcogenides, including both bottom-up methods such as vapor-phase deposition and top-down techniques like mechanical and/or liquid-phase exfoliation. In the final part, the article emphasizes the application of 2D group IV monochalcogenides, particularly in the fields of photocatalysis, photodetectors, nonlinear optics, sensors, batteries, and photovoltaic cells. Full article

The CsPbBr₃ perovskite exhibits strong environmental stability under light, humidity, temperature, and oxygen conditions. However, in all-inorganic perovskite solar cells (PSCs), interface defects between the carbon electrode and CsPbBr₃ limit the carrier separation and transfer rates. We used black phosphorus (BP) nanosheets as the hole transport layer (HTL) to construct an all-inorganic carbon-based CsPbBr₃ perovskite (FTO/c-TiO₂/m-TiO₂/CsPbBr₃/BP/C) solar cell. BP can enhance hole extraction capabilities and reduce carrier recombination by adjusting the interface contact between the perovskite and the carbon layer. Due to the coordination of the energy structure related to interface charge extraction and transfer, BP, as a new type of hole transport layer for all-inorganic CsPbBr₃ solar cells, achieves a power conversion efficiency (PCE) that is 1.43% higher than that of all-inorganic carbon-based CsPbBr₃ perovskite solar cells without a hole transport layer, reaching 2.7% (Voc = 1.29 V, Jsc = 4.60 mA/cm², FF = 48.58%). In contrast, the PCE of the all-inorganic carbon-based CsPbBr₃ perovskite solar cells without a hole transport layer was only 1.27% (Voc = 1.22 V, Jsc = 2.65 mA/cm², FF = 39.51%). The unencapsulated BP-based PSCs device maintained 69% of its initial efficiency after being placed in the air for 500 h. In contrast, the efficiency of the PSC without HTL significantly decreased to only 52% of its initial efficiency. This indicates that BP can effectively enhance the PCE and stability of PSCs, demonstrating its great potential as a hole transport material in all-inorganic perovskite solar cells. BP as the HTL for CsPbBr₃ PSCs can passivate the perovskite interface, enhance the hole extraction capability, and improve the optoelectronic performance of the device. The subsequent doping and compounding of the BP hole transport layer can further enhance its photovoltaic conversion efficiency in PSCs. Full article

Materials with high carrier mobility, represented by graphene, have garnered significant interest. However, the zero band gap arising from linear dispersion cannot achieve an ideal on–off ratio in field-effect transistors (FETs), limiting practical applications in certain fields. In contrast, parabolic dispersion usually exhibits extremely high carrier mobility and an appropriate band gap. In this work, we predicted a planar pentagonal lattice composed entirely of pentagons (namely penta-MX₂ monolayer), where M = Ni, Pd and Pt, X = group V elements. Using first-principles calculations, we demonstrated a parabolic dispersion within this framework, which results in intriguing phenomena, such as a direct band gap (0.551–1.105 eV) and extraordinary high carrier mobility. For penta-MX₂ monolayer, the carrier mobility can attain ~1 × 10⁸ cm² V⁻¹ s⁻¹ (PBE), surpassing those of black phosphorene, graphene and 2D hexagonal materials. This monolayer also displays anisotropic mechanical properties and significant absorption peaks in the ultraviolet spectrum. Remarkably, 2D penta-MX₂ monolayers are promising for successful experimental exfoliation, particularly when X is a nitrogen element, opening up new possibilities for designing two-dimensional semiconductor materials characterized by high carrier mobility. Full article

In this study, an omnidirectional and high-performance free-standing monopole patch radio-frequency antenna was fabricated using a urea-functionalized phosphorene/TiO₂/polypyrrole (UTP) nanocomposite. The UTP nanocomposite antenna was fabricated via ball milling of urea-functionalized phosphorene, chemical oxidative polymerization of the UTP nanocomposite, and mechanical pelletizing of the composite. Based on experiments, the proposed UTP nanocomposite-based antenna exhibited long-term stability in terms of electrical conductivity. After 12 weeks, a slight change in surface resistance was observed. The proposed antenna exhibited high radiation efficiency (78.2%) and low return loss (−36.6 dB). The results of this study suggest the potential of UTP nanocomposite antennas for applications in 5G technology. Full article

As a novel two-dimensional (2D) material, black phosphorene (BP) finds wide applications in gas adsorption and detection devices due to its distinctive optical, thermoelectric, and surface properties. However, numerous studies have demonstrated that BP exhibits strong selectivity towards gas adsorption and displays significant affinity towards gas molecules containing the element N, thereby greatly impeding its utilization in gas detection. To partially compensate for this deficiency, this study investigates the impact of halogen atom decoration on the adsorption behavior of BP towards CO₂, H₂O, and O₂ molecules. Furthermore, a comparison is made between the variations in gas adsorption energy with and without decorated halogen atoms. The results showed that the adsorbates of CO₂, H₂O, and O₂ molecules and halogen atoms (Cl, Br) adsorbed at the top (T) site of BP was much stronger than those at the bridge (B) and the hollow (H) sites of the P-P bond of BP, owing to their low adsorption energies. After the t position of BP is modified by the halogen (Cl, Br) atom, the optimal adsorption of CO₂ changes from −0.85 eV to −1.70 eV (Cl) and −1.64 eV (Br), and the optimal adsorption of H₂O changes from −0.72 eV to −1.48 eV (Cl) and −1.23 eV (Br), respectively. The adsorption properties were significantly enhanced. That is to say, the gas adsorption properties of BP have been largely improved by halogen Cl (Br) atoms decorating. Full article

In this paper, we report a titanium dioxide/polypyrrole/phosphorene (TiO₂/PPy/phosphorene) nanocomposite as an active material for supercapacitor electrodes. Black phosphorus (BP) was fabricated by ball milling to induce a phase transition from red phosphorus, and urea-functionalized phosphorene (urea-FP) was obtained by urea-assisted ball milling of BP, followed by sonication. TiO₂/PPy/phosphorene nanocomposites can be prepared via chemical oxidative polymerization, which has the advantage of mass production for a one-pot synthesis. The specific capacitance of the ternary nanocomposite was 502.6 F g⁻¹, which was higher than those of the phosphorene/PPy (286.25 F g⁻¹) and TiO₂/PPy (150 F g⁻¹) nanocomposites. The PPy fully wrapped around the urea-FP substrate provides an electron transport pathway, resulting in the enhanced electrical conductivity of phosphorene. Furthermore, the assistance of anatase TiO₂ nanoparticles enhanced the structural stability and also improved the specific capacitance of the phosphorene. To the best of our knowledge, this is the first report on the potential of phosphorene hybridized with conducting polymers and metal oxides for practical supercapacitor applications. Full article

Favipiravir (FP) and ebselen (EB) belong to a diverse class of antiviral drugs known for their significant efficacy in treating various viral infections. Utilizing molecular dynamics (MD) simulations, machine learning, and van der Waals density functional theory, we accurately elucidate the binding properties of these antiviral drugs on a phosphorene single-layer. To further investigate these characteristics, this study employs four distinct machine learning models—Random Forest, Gradient Boosting, XGBoost, and CatBoost. The Hamiltonian of antiviral molecules within a monolayer of phosphorene is appropriately trained. The key aspect of utilizing machine learning (ML) in drug design revolves around training models that are efficient and precise in approximating density functional theory (DFT). Furthermore, the study employs SHAP (SHapley Additive exPlanations) to elucidate model predictions, providing insights into the contribution of each feature. To explore the interaction characteristics and thermodynamic properties of the hybrid drug, we employ molecular dynamics and DFT calculations in a vacuum interface. Our findings suggest that this functionalized 2D complex exhibits robust thermostability, indicating its potential as an effective and enabled entity. The observed variations in free energy at different surface charges and temperatures suggest the adsorption potential of FP and EB molecules from the surrounding environment. Full article

Based on two-dimensional green phosphorene, we designed two molecular electronic devices with zigzag (Type 1) and whisker-like (Type 2) configurations. By combining density functional theory (DFT) and non-equilibrium Green’s function (NEGF), we investigated the electronic properties of Types 1 and 2. Type 1 exhibits an interesting negative differential resistance (NDR), while the current characteristics of Type 2 show linear growth in the current–voltage curve. We studied the electronic transport properties of Type 1 under uniaxial strain modulation and find that strained devices also exhibit a NDR effect, and the peak-to-valley ratio of device could be controlled by varying the strain intensity. These results show that the transport properties of green phosphorene with different edge configuration are different, and the zigzag edge have adjustable negative differential resistance properties. Full article