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ACS Nano · 2024 · IF 15.8

Constructing Interfacial Charge Transfer Channels and Electric Field in Violet Phosphorus-Based van der Waals Heterojunction for Phototherapy of Periodontitis

Qian Wu,Tian Deng,Juan Cheng,Yujie Yang,Yulan Wang,Yin Xiao,Yufeng Zhang

Periodontitis, a chronic oral disease instigated by bacteria, severely compromises human oral health. The prevailing clinical treatment for periodontitis involves mechanical scraping in conjunction with antibiotics. Phototherapy is employed to rapidly remove the bacteria and achieve periodontitis treatment, effectively circumventing the adverse effects associated with traditional therapies. Constructing 2D/2D van der Waals (VDW) heterojunctions is a key strategy for obtaining excellent photocatalytic activity. Herein, a 2D/2D violet phosphorus (VP)/Ti3C2 VDW heterojunction is designed using an interfacial engineering strategy. By constructing an electron transport “bridge” (P–Ti bond) at the heterogeneous interface as an effective transfer channel for photogenerated carriers, a compact monolithic structure between the VP and Ti3C2 phases is formed, and the spatial barrier for electron transfer at the interface is eliminated. Meanwhile, the strong directional built-in electric field induced by the intensive electron-coupling effect at the heterogeneous interface served as an internal driving force, which greatly accelerates the exciton dissociation and charge transfer in the photocatalytic process. These excited photogenerated electrons and holes are trapped by O2 and H2O on the surfaces of Ti3C2 and VP, respectively, and are subsequently catalytically converted to antibacterial reactive oxygen species (ROS). The VP/Ti3C2 VDW heterojunction eradicated 97.5% and 98.48% of Staphylococcus aureus and Escherichia coli, respectively, by photocatalytic and photothermal effects under visible light for 10 min. The VP/Ti3C2 nanoperiodontal dressing ointment effectively attenuated inflammatory response, reduced alveolar bone resorption, and promoted periodontal soft and hard tissue repair. Its periodontitis therapeutic effect outperforms the clinically used Periocline.

研究领域: 口腔医学 · 材料科学 · 生物医学工程
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NANOTECHNOLOGY · 2023 ·Vol. 34 ·期 28 ·285206 · IF 3.5

Violet phosphorus transmission and photoconductance spectroscopy

Bo Zhang,Eli Martel,Zhenyu Wang,Jinying Zhang,Thomas Szkopek

Violet phosphorus is a semiconducting allotrope of phosphorus with a layered crystalline structure consisting of orthogonally oriented layers of phosphorus chains composed of P2[P8]P2[P9] repeating units. Here, we report optical transmission spectroscopy and photoconductivity measurements of exfoliated flakes of violet phosphorus in the thin-film bulk limit. The violet phosphorus was synthesized by chemical vapour transport, and subsequently protected from oxidation with an inert gas environment. A peak photoconductive responsivity of R = 7 mA W−1 at photon energy 2.8 eV was observed. The spectral dependence of optical transmission and photoconductivity of violet phosphorus leads us to identify optical transitions at van Hove singularities corresponding to energies E1 = 1.80 ± 0.05 eV and E2 = 1.95 ± 0.05 eV. Density functional theory was applied to the calculation of violet phosphorus (vP) bandstructure, and a dipole transition analysis shows that optical transitions at the Z and A0 points of the Brillouin zone are in agreement with experimental observations. Exposure to ambient environmental conditions for several minutes is sufficient to significantly reduce vP photoconductivity, while longer exposure leads to blistering due to oxidation. Thus, a locally inert chemical environment is essential to accessing vP intrinsic optoelectronic properties.

研究领域: 材料科学 · 光学 · 凝聚态物理
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ADVANCED MATERIALS · 2024 · IF 27.4

Enhanced Photosensitizer Wettability via Anchoring Competition of Violet Phosphorus Quantum Dots for Breakthroughs in Photodynamic Film Sterilization

Zuwang Zhang,Chi Zhang,Na Wang,Yayun Hu,Lu Cui,Jianlong Wang,Lingyan Zhu,Jinying Zhang,Rong Wang

Wettability is important for photodynamic film sterilization since higher wettability enhances the capture of bacteria in contact with photosensitizers. Herein, a small number of violet phosphorus quantum dots (VPQDs) are anchored into hypericin bacterial cellulose films (VP/Hy-BC films) to improve wettability, reducing the water contact angle from 56.8° to 33.0°. This modification facilitated more effective interactions between the bacteria and photosensitizers, rapidly inactivating 7 log 10 CFU/mL of Staphylococcus aureus within 60 min. First-principles calculations and molecular dynamics simulations reveal that VPQDs, with their low spatial site resistance, reduced the intermolecular Hy self-aggregation force. This increased the solvent-accessible surface area of VP/Hy by ≈25.7%, thereby decreasing hydrophobic photosensitizer aggregation. Consequently, more active sites are exposed, remarkably improving the photoelectron transfer efficiency. VP/Hy-BC demonstrated exceptional efficacy in inhibiting bacterial proliferation; for instance, it extended beef shelf life by up to 10 days. The findings of this study will aid the development of health-conscious, eco-friendly, and efficient antimicrobial packaging films.

CAS / MDL: 108-77-0 872-50-4
研究领域: 材料科学 · 微生物学 · 环境科学
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Processes · 2023 ·Vol. 11 ·期 12 ·3429 · IF 3.5

Functionalization of Violet Phosphorus Quantum Dots with Azo-Containing Star-Shape Polymer for Optically Controllable Memory

Fan Shu,Weilin Chen,Gang Liu

Quantum dots (QDs) are emerging as promising candidates for innovative memristive materials, owing to their distinct surface, quantum size, and edge effects. Recent research has focused on tailoring QDs with specific organic molecules to fine-tune charge transfer states between the host and grafted species, as well as enhancing their dispersibility and processability. Violet phosphorus (VP), a newly discovered two-dimensional phosphorus allotrope, offers excellent carrier dynamics, predictable modifiability, and superior oxidation resistance, making it a promising contender in this domain. In this study, we synthesized a rich azobenzene-containing star-shaped polymer diazonium salt (AzoSPD) to functionalize violet phosphorus quantum dots (VPQDs), with the dual objectives of enhancing organic dispersibility and introducing photo-switching capabilities. The synthesized AzoSPD–VPQDs exhibit intramolecular charge transfer characteristics under electrical stimuli of ambient conditions, displaying significant non-volatile rewriteable memory properties and a substantial switching ratio exceeding 2 × 103. Furthermore, the high resistance state (HRS) current can be enhanced by nearly 40 times under 465 nm illumination, enabling optoelectronic information sensing and storage within a single device. This work not only provides insights into enhancing the optoelectronic properties of QDs through functional organic molecular modification but also represents a pioneering exploration of the potential applications of VPQDs in novel memristors.Keywords:violet phosphorus quantum dots;star-shape polymer diazonium salt;memristor;charge transfer mechanism;photoelectric regulation

研究领域: 材料科学 · 纳米技术 · 光电材料
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2022 · IF 10.319

Constructing metal-free heterophotocatalyst using two-dimensional carbon nitride sheets and violet phosphorene for highly efficient visible-light photocatalysis

Yong Wang,Chengxin Zeng,Liting Wu,Yalin Dong,Yu Zhang,Dingyi Yang,Wen Hu,Jian Hao,Hongzhe Pan,Rusen Yang

Two-dimensional (2D) carbon nitride sheets (CNs) with nanoscale thickness have great potential in solar energy conversion owing to their intrinsic bandgap. However, their photocatalytic efficiency falls far below the practical requirements because the generated electron-hole pairs rapidly recombine. We construct a metal-free 2D p–n junction heterophotocatalyst from CNs and violet phosphorene (VP) using a simple electrostatic self-assembly method. The experimental results and density functional theory calculations show that the built-in electric field of the p–n junction promotes photogenerated carrier transport at the heterojunction interface, thereby promoting the separation of photogenerated electron-hole pairs. Under visible-light illumination, the visible-light photocatalytic hydrogen and CO production rates of the CNs/VP heterojunction were increased by 5.85 and 1.51 times, respectively, when compared to that of CNs . This study provides new insights into the design of metal-free heterogeneous photocatalysts with high catalytic activity.

研究领域: 材料科学 · 光催化 · 纳米材料 · 能源化学 · 半导体物理
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Environmental Science-Nano · 2025 · IF 5.1

Violet Phosphorus Nanosheets Exhibit Higher Toxicity in the Freshwater Microalgae Tetradesmus obliquus than Black Phosphorus Nanosheets

Haoxiang Zhang,Fan Zhang,Zhuang Wang,Willie Peijnenburg

The potential environmental risks of two-dimensional (2D) phosphorene nanomaterials are gaining attention as their promising applications continue to expand. Violet phosphorus (VP) has been demonstrated to be a more stable phosphorene nanomaterial compared to black phosphorus (BP). However, current research has primarily focused on the toxic effects of BP, with limited information available regarding the toxicity of VP. This study comparatively analyzed the ecotoxicity and mechanisms of action of environmentally relevant concentration exposures of the common green algae Tetradesmus obliquus to BP and VP nanosheets. The results revealed that VP exhibited a greater growth inhibitory effect on the algae compared to BP, which was linked to disruptions in cell membrane function. Both BP and VP induced intracellular oxidative stress responses, yet they did not cause oxidative damage to algal cells. Transcriptional responses suggested that the number of differentially expressed genes in the algae exposed to VP was 29 times higher than that in the algae exposed to BP. Metabolomic analysis indicated that the number of differentially expressed metabolites induced by VP exposure in the algae was twice as high as the changes induced by BP. Furthermore, integrated transcriptome and metabolome analyses highlighted significant differences between BP and VP in core pathways, key metabolites, and driving genes. The findings of this study underscore the importance of considering the impact of different types of phosphorene materials when assessing their environmental risks.

CAS / MDL: 596-09-8 62669-70-9
研究领域: 环境毒理学 · 纳米生物学 · 水生生态学 · 分子生态毒理学 · 环境科学 · 藻类生理学 · 组学分析
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NEW JOURNAL OF CHEMISTRY · 2024 · IF 2.7

Nano-violet phosphorus/nano-crystalline cellulose composite film for fire-retardant coating

Lihui Zhang,Ting Du,Bingjia Wang,Yiping Tang,Changji Yin,Zixi Chang,Chunbao Du,Yuan Cheng,Gang Zhang

As fire safety issues receive increasing attention, the development of efficient flame-retardant materials has become particularly important. This study explores the preparation methods of nano-violet phosphorus (NVP) and nanocellulose (NCC) composite films and their superior performance in flame retardancy applications. NVP was successfully prepared using a liquid-phase exfoliation method and was then non-covalently self-assembled with NCC to form novel composite film with good uniformity. The microstructure, mechanical properties, and flame-retardant performance of the composite film were comprehensively characterized. The results indicated that the NVP/NCC composite film with only 1wt.% NVP exhibited significantly enhanced self-extinguishing capability (<2s) and the peak heat release rate (23.31 kW m-2) and total heat release (1.78 MJ m-2), indicating its effectiveness in delaying the combustion process under flame exposure. The introduction of NVP made the decomposition rate of composite film more gentle and the decomposition behavior more stable in aerobic environment. In addition, the presence of NVP delayed the dehydration process of NCC, and promoted the carbonization reaction, thereby reducing the release of H2O, thus forming a protective carbon layer and removing active free radicals, significantly improving the thermal stability and safety of the composite. This work provides important theoretical foundations and practical guidance for the development of new flame-retardant materials.

CAS / MDL: 9067-32-7 90-80-2
研究领域: 材料科学 · 消防安全工程 · 复合材料
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Small · 2023 ·Vol. 20 ·期 9 ·2306758 · IF 13.3

Pressure-Driven Polymorphic Transition, Emergent Insulator-To-Metal Transition, and Photoconductivity Switching in Violet Phosphorus

Chen Li,Ke Liu,Dequan Jiang,Huacai Yan,En Chen,Yingying Ma,Haoming Cheng,Ting Wen,Binbin Yue,Yonggang Wang

Polymorphic phase transition is an essential phenomenon in condensed matter that the physical properties of materials may undergo significant changes due to the structural transformation. Phase transition has thus become an important means and dimension for regulating material properties. Herein, this study demonstrates the pressure-induced multi-transition of both structure and physical properties in violet phosphorus, a novel phosphorus allotrope. Under compression, violet phosphorus undergoes sequential polymorphic phase transitions. Concomitant with the first phase transition, violet phosphorus exhibits emergent insulator–metal transition, superconductivity, and dramatic switching from positive to negative photoconductivity. Remarkably, the resistance of violet phosphorus shows a sudden drop of around 10 7 along with the phase transition. In addition, piezochromism from translucent red to opaque black and suppression of photoluminescence are observed upon compression. Of particular interest is that the sample irreversibly transforms into black phosphorus with a pronounced discrepancy in physical properties from the pristine violet phosphorus after decompression. The abundant polymorphic transitions and property changes in violet phosphorus have significant implications for designing novel pressure-responsive electronic/optoelectronic devices and exploring concealed polymorphic transition materials.

研究领域: 凝聚态物理 · 材料科学 · 高压物理 · 半导体物理 · 光学材料 · 相变动力学
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NANO LETTERS · 2023 · IF 10.8

Partially Oxidized Violet Phosphorus as an Excellent Lubricant Additive for Tribological Applications

Yunze Li,Kai Gao,Yi Zhang,Jianguo Jiao,Lin Zhang,Guoxin Xie

As a novel two-dimensional material, violet phosphorus (VP) has attracted a considerable amount of attention due to its high carrier mobility, anisotropy, wide band gap, stability, and easy stripping properties. In this work, the microtribological properties of partially oxidized VP (oVP) and the mechanism of reducing friction and wear as additives in oleic acid (OA) oil were studied systematically. When adding oVP to OA, the coefficient of friction (COF) decreased from 0.084 to 0.014 with the steel-to-steel pair, and the ultralow shearing strength tribofilm consisting of amorphous carbon and phosphorus oxides that formed resulted in the reductions of COF and wear rate individually by 83.3% and 53.9%, respectively, compared with those of pure OA. The results extended the application scenarios for VP in the design of lubricant additives.

CAS / MDL: 7723-14-0
研究领域: 材料科学 · 摩擦学 · 化学
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