Red Phosphorus Nanoparticles Research Articles

In Situ Construction of Crumpled Ti3C2Tx Nanosheets Confined S-Doping Red Phosphorus by Ti-O-P Bonds for LIBs Anode with Enhanced Electrochemical Performance.

Red phosphorus (RP) with a high theoretical specific capacity (2596 mA h g-1) and a moderate lithiation potential (∼0.7 V vs Li+/Li) holds promise as an anode material for lithium-ion batteries (LIBs), which still confronts discernible challenges, including low electrical conductivity, substantial volumetric expansion of 300%, and the shuttle effect induced by soluble lithium polyphosphide (LixPPs). Here, S-NRP@Ti3C2Tx composites were in situ prepared through a phosphorus-amine-based method, wherein S-doped red phosphorus nanoparticles (S-NRP) grew and anchored on the crumpled Ti3C2Tx nanosheets via Ti-O-P bonds, constructing a three-dimensional porous structure which provides fast channels for ion and electron transport and effectively buffers the volume expansion of RP. Interestingly, based on the results of adsorption experiments of polyphosphate and DFT calculation, Ti3C2Tx with abundant oxygen functional groups delivers a strong chemical adsorption effect on LixPPs, thus suppressing the shuttle effect and reducing irreversible capacity loss. Furthermore, S-doping improved the conductivity of red phosphorus nanoparticles, facilitating Li-P redox kinetics. Hence, the S-NRP@Ti3C2Tx anode demonstrates outstanding rate performance (1824 and 1090 mA h g-1 at 0.2 and 4.0 A g-1, respectively) and superior cycling performance (1401 mAh g-1 after 500 cycles at 2.0 A g-1).

On-surface conversion reaction realizes advanced red phosphorus/carbon anode for high-performance lithium-ion batteries

Red phosphorus (RP), the one of the most prospective anodes in lithium-ion batteries (LIBs), has been severely limited due to the intrinsic defects of massive volume expansion and low electronic conductivity. The vaporization-condensation-conversion (VCC), which confines RP nanoparticles into carbon host, is the most widely used method to address the above drawbacks and prepare RP/C nanostructured composites. However, the volume effect-dominated RP caused by the inevitably deposition of RP vapor on the surface of carbon material suffers from the massive volume change and unstable solid electrolyte interface (SEI) film. Herein, we propose a simple interfacial modification method to eliminate the superficial RP and yield stable surface composed of ion-conducting Li3PS4 solid electrolyte, endowing RP/AC composites excellent cycling performance and ultrafast reaction kinetics. Therefore, the RP/AC@S composites exhibit 926 mAh/g after 320 cycles at 0.2 A/g (running over 181 days), with 81.6 % capacity retention and a corresponding capacity decay rate of as low as 0.059 %. When coupled with LiFePO4 cathode, the full cells present superior cycling performance (62.1 mAh/g after 500 cycles at 1 A/g) and excellent rate capability (81.1 mAh/g at 1.0 A/g).

A mild and efficient sonothermal tumor therapy enhanced by sonodynamic effect with biodegradable red phosphorus nanoparticles

Due to the shallow penetration depth of light in biological tissues, the effectiveness of photothermal therapy (PTT) in deep-seated tumors is limited. Conversely, ultrasonic wave has excellent tissue penetration depth. Using ultrasound (US) as an exogenous physical stimulus to trigger tumors thermotherapy is a promising alternative for deep-seated tumors to supersede conventional PTT. Here, we realized a mild sonothermal therapy (STT) using biodegradable red phosphorus nanoparticles (RP NPs) as sonothermal agents. Quite obvious sonothermal conversion of RP NPs is remarkable under low intensity US irradiation, with the temperature rise from 30 to 47 °C at tumor site. In terms of potential mechanism, under US excitation, the internal electrons of RP NPs undergo transition and release the energy by electrons and holes recombination process. This elicits the atom thermal vibration and raises the temperature around the RP NPs. Additionally, US irradiation can stimulate RP NPs to produce singlet oxygen (1O2) and reduce intracellular energy levels that leads to downregulation of the heat shock proteins (HSPs) expression, providing an “escort” to mild STT. This work offers a new paradigm for the strategies of STT enhanced by sonodynamic effect.

A Superior Two-Dimensional Phosphorus Flame Retardant: Few-Layer Black Phosphorus

The usage of flame retardants in flammable polymers has been an effective way to protect both lives and material goods from accidental fires. Phosphorus flame retardants have the potential to be follow-on flame retardants after halogenated variants, because of their low toxicity, high efficiency and compatibility. Recently, the emerging allotrope of phosphorus, two-dimensional black phosphorus, as a flame retardant has been developed. To further understand its performance in flame-retardant efficiency among phosphorus flame retardants, in this work, we built model materials to compare the flame-retardant performances of few-layer black phosphorus, red phosphorus nanoparticles, and triphenyl phosphate as flame-retardant additives in cellulose and polyacrylonitrile. Aside from the superior flame retardancy in polyacrylonitrile, few-layer black phosphorus in cellulose showed the superior flame-retardant efficiency in self-extinguishing, ~1.8 and ~4.4 times that of red phosphorus nanoparticles and triphenyl phosphate with similar lateral size and mass load (2.5~4.8 wt%), respectively. The char layer in cellulose coated with the few-layer black phosphorus after combustion was more continuous and smoother than that with red phosphorus nanoparticles, triphenyl phosphate and blank, and the amount of residues of cellulose coated with the few-layer black phosphorus in thermogravimetric analysis were 10 wt%, 14 wt% and 14 wt% more than that with red phosphorus nanoparticles, triphenyl phosphate and blank, respectively. In addition, although exothermic reactions, the combustion enthalpy changes in the few-layer black phosphorus (−127.1 kJ mol−1) are one third of that of red phosphorus nanoparticles (−381.3 kJ mol−1). Based on a joint thermodynamic, spectroscopic, and microscopic analysis, the superior flame retardancy of the few-layer black phosphorus was attributed to superior combustion reaction suppression from the two-dimensional structure and thermal nature of the few-layer black phosphorus.

Scalable method for preparing multi-walled carbon nanotube supported red phosphorus nanoparticles as anode material in lithium-ion batteries

Nanoscale red phosphorus (RP) has attracted plenty of interest as an anode material for lithium-ion batteries (LIBs). However, current methods for preparing RP nanocomposite are energy intensive and dangerous. Here, we report a scalable method for preparing multi-walled carbon nanotube supported RP nanoparticles (RP NPs/MWNT) composite. RP lump is dissolved in ethylenediamine. Then RP NPs were generated after adding HCl. Through this environmentally safe and low energy-consumption method, uniform RP NPs (5 nm) are deposited on MWNT, forming RP NPs/MWNT composite. Such small RP particles buffer volume expansion and MWNT accelerates electron transfer during cycling, therefore enabling RP NPs/MWNT to deliver a high initial reversible capacity of 1780.2 mAh g−1 and a high capacity retention of 88.6% at 200 mA g−1 after 100 cycles. Our method can be applied to synthesizing various RP nanocomposites for LIBs and is easy to set up, inexpensive, rapid, accessible to factory.

Laser-Ablated Red Phosphorus on Carbon Nanotube Film for Accelerating Polysulfide Conversion toward High-Performance and Flexible Lithium-Sulfur Batteries.

The use of a conducting interlayer between separator and cathode is one of the most promising methods to trap lithium polysulfides (LiPSs) for enhancing the performance of lithium-sulfur (Li-S) batteries. Red phosphorus nanoparticles (RPEN )-coated carbon nanotube (CNT) film (RPEN @CF) is reported herein as a novel interlayer for Li-S batteries, which shows strong chemisorption of LiPSs, good flexibility, and excellent electric conductivity. A pulsed laser ablation method is engaged for the ultrafast production of RPEN of uniform morphology, which are deposited on the CNT film by a direct spinning method. The RPEN @CF interlayer provides pathways for effective Li+ and electron transfer and strong chemical interaction with LiPSs. The S/RPEN @CF electrode shows a superior specific capacity of 782.3mAhg-1 (3C-rate) and good cycling performances (769.5mAhg-1 after 500 cycles at 1C-rate). Density functional theory calculations reveal that the morphology and dispersibility of RPEN are crucial in enhancing Li+ and electron transfer kinetics and effective trap of LiPSs. This work demonstrates the possibility of using the RPEN @CF interlayer for the enhanced electrochemical performances of Li-S batteries and other flexible energy storage devices.

Chalcogen-doped red phosphorus nanoparticles @ porous carbon as high-rate and ultrastable anode for lithium-ion batteries

A strategy of doping chalcogen-heteroatom in red phosphorus (RP) nanoparticles is adopted to improve the electrochemical performance of RP based composites as lithium storage materials. RP nanoparticles embedded in porous carbon with chalcogen-doping (S-, Se- and Te–P@PC) composites are synthesized via a facile evaporation-condensation approach. The large volume expansion of RP upon cycling is well mitigated by nanoscale feature and buffered by pore-closed carbon matrix. The extra fillings of chalcogen dopants lessen the specific surface areas of the doped composites, minimizing parasitic surface reactions of anode materials with electrolyte that can lead to high initial coulombic efficiencies. The high conductivity of Se dopant and the formed conductive Li–Se/Li–Se–P confer the Se–P@PC anode with improved electron/ion transport properties to deliver a superior fast-charging capability over 900 cycles. Moreover, a high-rate capacity of 908.5 mA h g−1 at 5.0 A g−1 and an impressive reversible capacity of 848.2 mA h g−1 even after 1800 cycles at 1.0 A g−1 of Se–P@PC surpass most of reported RP-based anode materials.

Eco-friendly and degradable red phosphorus nanoparticles for rapid microbial sterilization under visible light

Pathogens pose a serious challenge to environmental sanitation and a threat to public health. The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs, which further threatens public health. To address this issue, the use of non-chemical antibacterial means has become a new trend for environmental disinfection. In this study, we developed red phosphorus nanoparticles (RPNPs), a safe and degradable photosensitive material with good photocatalytic and photothermal properties. The red phosphorus nanoparticles were prepared using a template method and ultrasonication. Under the irradiation of simulated sunlight for 20 min, the RPNPs exhibited an efficiency of 99.98 % in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities. Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks. Both the RPNPs and their degradation products were nontoxic to fibroblast cells. Therefore, such RPNPs are expected to be used as a new type of low-cost, efficient, degradable, biocompatible, and eco-friendly photosensitive material for environmental disinfection.

Multichannel red phosphorus with a nanoporous architecture: A novel anode material for sodium-ion batteries

Red phosphorus (RP) has recently been considered as an anode material for sodium-ion batteries owing to its high theoretical capacity (2596 mA h g−1). Even though it possesses high capacity, it has the major drawback of low electronic conductivity and severe volume expansion during charging/discharging. Electrode materials with multichannel RP nanoporous (MRPN) architectures have been prepared via a facile solvothermal method. These anode active materials are in the range of 50–100 nm. The MRPN-3 shows an improved discharge capacity of 1814 mA h g−1 after 100 cycles at a current density of 200 mA g−1. Furthermore, it exhibits an admirable performance at a high current density, providing excellent long-term cyclability. In this paper, we show that electrode materials with hollow nanoporous architectures offer several advantages, such as providing an efficient electron/ion transport network, buffering the volume expansion of RP nanoparticles, and enabling superior kinetics of efficient sodium-ion storage.

Overcoming Multidrug-Resistant MRSA Using Conventional Aminoglycoside Antibiotics.

Global multidrug‐resistant (MDR) bacteria are spreading rapidly and causing a great threat to human health due to the abuse of antibiotics. Determining how to resensitize MDR bacteria to conventional inefficient antibiotics is of extreme urgency. Here, a low‐temperature photothermal treatment (PTT, 45 °C) is utilized with red phosphorus nanoparticles to resensitize methicillin‐resistant Staphylococcus aureus (MRSA) to conventional aminoglycoside antibiotics. The antibacterial mechanism is studied by the proteomic technique and molecular dynamics (MD) simulation, which proves that the aminoglycoside antibiotics against MRSA can be selectively potentiated by low‐temperature PTT. The catalytic activity of 2‐aminoglycoside phosphotransferase (APH (2″))—a modifying enzyme—is demonstrated to be obviously inhibited via detecting the consumption of adenosine triphosphate (ATP) in the catalytic reaction. It is also found that the active site of aspartic acid (ASP) residues in APH (2″) is thermally unstable from the results of molecular dynamics simulation. Its catalytic ability is inhibited by preventing the deprotonating procedure for the target —OH of gentamycin. The combined therapy also exhibits great biocompatibility and successfully treats MRSA infections in vivo. This low‐temperature PTT strategy has the potential to be an exogenous‐modifying enzyme inhibitor for the treatment of MDR bacterial infection.

Correction: Colloidal synthesis of porous red phosphorus nanoparticles as a metal-free electrocatalyst for the hydrogen evolution reaction.

Correction for 'Colloidal synthesis of porous red phosphorus nanoparticles as a metal-free electrocatalyst for the hydrogen evolution reaction' by Cheng-Ying Chan et al., Chem. Commun., 2020, 56, 2937-2940, DOI: .

Colloidal synthesis of porous red phosphorus nanoparticles as a metal-free electrocatalyst for the hydrogen evolution reaction.

Porous red phosphorus nanoparticles, P-RPNPs, were synthesized via a new colloidal approach and used as metal-free electrocatalysts in the hydrogen evolution reaction (HER). P-RPNPs were highly efficient in acidic media, required an overpotential of only 218 mV to reach 10 mA cm-2, and exhibited superior long-term durability.

Fabrication of red phosphorus anode for fast-charging lithium-ion batteries based on TiN/TiP2-enhanced interfacial kinetics

Red phosphorus (RP) is an ideal anode for fast-charging lithium-ion batteries due to its high capacity (2596 ​mA ​h ​g−1) and suitable lithiation potential (0.7 ​V vs. Li/Li+). We embedded amorphous soft RP nanoparticles in the hard and micro-sized TiN nanosheet as well as CNT via high-energy ball milling, thus, TiP2 layer was fabricated at the interface of RP and TiN. This in-situ formed conductive TiP2 substantive layer enhances Li+ diffusion, improves the interfacial stability of RP, and inhibits the side reaction between P and electrolytes. Thus the RP/TiN/CNT electrode shows excellent fast-charging and long-term cycling performances, such as, a high fast-charging retention of 92.6% from the 5th to 200th cycles with charging current density of 8 ​A ​g‒1 (= 3 ​C rate, about 3 ​min) and discharging current density of 0.15 ​A ​g‒1, and a 96.9% capacity retention from 3rd to 850th cycles at 2.3 ​A ​g‒1.

Uniform, Scalable, High-Temperature Microwave Shock for Nanoparticle Synthesis through Defect Engineering

Summary Here we demonstrate a thermal shock synthesis method triggered by microwave irradiation for the rapid synthesis of nanoparticles on reduced graphene oxide (RGO) substrate. With properly controlled reduction, RGO has high electrical conductivity while maintaining functional groups, leading to an extremely efficient microwave absorption of ∼70%. The high utilization of microwaves results in the ability to raise the temperature to 1,600 K in just 100 ms, which is followed by rapid quenching to room temperature. The defects on the RGO are crucial for achieving this record-high microwave-induced temperature as these defects play a fundamental role in absorbing the radiation as well as the self-quenching mechanism. By loading precursors onto RGO, we can utilize rapid temperature change to synthesize nanoparticles. The nanoparticles are ∼10 nm with uniform distribution. This facile, rapid, and universal synthesis technique has the potential to be employed in large-scale production of nanomaterials and suggests a new direction for nanosynthesis.

Red phosphorus filled biomass carbon as high-capacity and long-life anode for sodium-ion batteries

Red phosphorus is a promising anode material for sodium-ion batteries due to its low cost and superior theoretical capacity of 2596 mAh g−1. However, intrinsically inferior conductivity and huge volume changes during sodiation/desodiation processes hinder its practical application. Herein, we report an integrated red phosphorus/N-doped biomass carbon composite via filling red phosphorus nano-particles into the nano-pores of N-doped carbon derived from a renewable coconut shell biomass. In the rational structural design, N-doped biomass carbon serves as hard template for embedding red phosphorus nano-particles, buffers the volume expansion of red phosphorus during sodiation processes, and enhances the conductivity of composite. The composite delivers a high reversible capacity of 2481 mAh g−1 at 50 mA g−1 with a higher 89% initial coulombic efficiency. When the current density increases by 100 times to 5000 mA g−1, the capacity can remain 855 mAh g−1. Moreover, the composite maintains a reversible capacity of 1857 mAh g−1 at 500 mA g−1 after 100 cycles, and 845 mAh g−1 at 2000 mA g−1 after 500 cycles. This work introduces abundant biomass into application of high performance electrode materials for sodium-ion batteries.

Constructing metal-free and cost-effective multifunctional separator for high-performance lithium-sulfur batteries

As numerous efforts have been devoted to the construction of nano-structured sulfur electrodes, the rational design of multi-functional separator is attracting an increasing research enthusiasm recently as another promising approach towards high-performance lithium-sulfur (Li-S) batteries. Herein, red phosphorus nanoparticles are employed, for the first time, to establish a metal-free and cost-effective multifunctional separator, which not only efficiently immobilizes the lithium polysulfides but also facilitates the ion conduction for fast and durable sulfur redox reactions. The computational and experimental results reveal that red phosphorus is capable of chemically confining the polysulfides through a combination of the Lewis acid-base interaction and sulfur-chain catenation, while the highly conductive Li3PO4 is generated during the cell operation and facilitates ion transportation. Attributed to these unique features, the cells based on the as-developed separator exhibit a high sulfur utilization of 1287 mAh g−1 at 0.1 C, superb rate capability of 809 mAh g−1 at up to 2 C, and excellent cycling performance with 82% capacity retention after 500 cycles at 1 C. This facile and low-cost strategy not only offers an effective pathway towards enhancement in battery performance, but could also inspire new thinking on developing metal-free functional agents for improved sulfur electrochemistry.

Quasi-type-II amorphous red phosphorus@TiO2 hybrid films for photoanodic applications

Owing to its optimal energy band position, red phosphorus (RP) has been considered as a promising elemental semiconductor for achieving simultaneous light-induced water oxidation and reduction. However, the photoelectrochemical performance of RP is limited by rapid charge recombination, low-charge carrier mobility, and poor water oxidation and film-forming capabilities. In this study, we explored the material strategies to address these limitations by developing a facile process to fabricate amorphous RP@TiO2 core-shell hybrid films. We found that the amorphous RP@TiO2 hybrid films annealed at low temperatures (e.g., 200–300 °C) in nitrogen exhibited significantly enhanced anodic photocurrent as compared to pure RP and pure TiO2 films due to a combined effect of enhanced visible light absorption and efficient heterointerface charge separation. Through a systematic characterization combining electronic, optical and electrochemical measurements, we found that the high density of Ti3+/oxygen vacancy complexes in amorphous TiO2 created a defect band above the valence band of RP but below the water oxidation potential, thereby inducing a quasi-type-II band alignment in the amorphous RP@TiO2 hybrid films; such electronic structure endowed amorphous TiO2 with a “hole leaky” feature to separate and transport the photogenerated holes from RP nanoparticles to exhibit an enhanced photoanodic performance.

Efficient gel route to embed phosphorus into MOF-derived porous FePx as anodes for high performance lithium-ion batteries

Rational design of phosphorus-rich materials with high P content and controllable microstructure is crucial for high-performance lithium ion batteries (LIBs). Herein, for the first time, a rapid MOFs-gel technique is skillfully employed for the facile and scalable synthesis of red phosphorus (red-P) nanoparticles inlaid Fe-benzenetricarboxylic (BTC) composite. During the subsequent phosphorization process, Fe-BTC was transformed into porous FePx, finally achieving a porous phosphorus-rich FePx@P composite with controllable amounts of red-P nanoparticles embedded in porous FePx matrix. Due to the unique structure and synergistic effect between components in the composite, the FePx@P composite with an optimized loading content of 61.2 wt% P exhibits excellent electrochemical performance for LIBs anodes (1283.9 mAh g−1 under 100 mA g−1 after 80 cycles and 418.2 mAh g−1 at 2 A g−1 after 1600 cycles). The abundant pores inside the FePx matrix can store sufficient electrolyte for fast ion transfer, as well as provide enough space for alleviating the volume change during charge/discharge process. The porous FePx matrix with much better conductivity wires up the inside red-P, facilitating charge transfer processes, while the controllable amounts of red-P nanoparticles with higher specific capacity can store more Li+ ions for higher energy storage. The skillful synthesis route is inspiring for the synthesis of other related materials for various fields.

Nanoconfinement of red phosphorus nanoparticles in seaweed-derived hierarchical porous carbonaceous fibers for enhanced lithium ion storage

Red phosphorus has come to our attention as the anode material for lithium-ion batteries with high theoretical specific capacity of 2596 mAh g−1 due to its earth-abundant and low-cost. However, it suffers from low electroconductivity and large volume expansion, resulting in serious capacity fading. In this study, we confined red phosphorus nanoparticles into the hierarchical porous carbonaceous fibers to enhance its cycling stability. Red phosphorus nanoparticles preferentially filled in the micropores and gradually extended to the larger pores. The optimized electrochemical performance benefits from hierarchical pores filled with the appropriate content of red phosphorus, where the small micropores are used to confine the red phosphorus nanoparticles and the large mesopores are beneficial for the increased contact of electrolyte. This can remit excessive volume change and facilitate the contact area of electrolyte effectively. Thus, the P@HPCF-3/2 displays outstanding cycle performance with a superior high reversible capacity (1300 mAh g−1 after 100 cycles at 1 A g−1).

Red phosphorus nanoparticles embedded in porous N-doped carbon nanofibers as high-performance anode for sodium-ion batteries

In this paper, red phosphorus nanoparticles (~ 97.7nm, 51wt% content) homogeneously embedded in porous nitrogen-doped carbon nanofibers (denoted as P@C) are prepared using a feasible electrospinning technique for the first time. Meanwhile, red P@C with the character of free-standing membrane is directly used as binder- and current collector-free anode for sodium-ion batteries, exhibiting a highly reversible three-electron transfer reaction (3Na+ + P + 3e- ↔ Na3P) with excellent rate capability (1308mAhg-1 at 200mAg-1 in comparison of 343mAhg-1 at 10,000mAg-1) and remarkable cyclic stability (~ 81% capacity retention after 1000 cycles). Furthermore, a soft package Na-ion full battery with red P@C anode and Na3V2(PO4)2F3/C cathode is assembled, displaying a high operation voltage of ~ 3.65V and an outstanding energy density of 161.8Whkg-1 for the whole battery. This is owing to the distinctive structure of very small amorphous phosphorus nanoparticles uniformly confined in porous N-doped carbon nanofibers, which can effectively facilitate the electronic/ionic transportation and retard the active materials pulverization/fracture caused by volume fluctuation upon prolonged cycling. The simple and scalable synthesis route as well as the promising electrochemical performance shed new insights into the quest for high energy and long life phosphorus-based Na-storage anode materials.