Black Phosphorous Nanosheets Research Articles

Effect of crystal defects on solar steam generation performance of black phosphorous nanosheets

What part do the crystal defects play in the solar steam generation performance of black phosphorous (BP) nanosheets, whether good or bad? Herein, through controlling the exfoliation environment, BP nanosheets with or without crystal defects (W-BP and D-BP) are successfully fabricated and integrated into the solar steam generator with polyurethane (PU) foam. Based on transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy technologies, crystal defects composed of phosphoric acid groups are found to be introduced into lattice structure of BP nanosheets. With simulated sunlight, the temperature variations are different in PU@collagen/D-BP (26.6 °C) and PU@collage/W-BP (20.9 °C) compared with the initial temperature. As a result, the steam generation rate of PU@collage/W-BP and PU@collage/D-BP are increased to 0.6809 kg/m2h and 0.8910 kg/m2h from 0.2594 kg/m2h (pure water). This work first reveals the inherent relationship between crystal defects and the performance of BP nanosheets based solar steam generation, providing key information for the in-depth application of BP nanosheets.

Barrier function of graphene for suppressing the smoke toxicity of polymer/black phosphorous nanocomposites with mechanism change

Recently, black phosphorous (BP) nanosheets as an emerging nanomaterial have presented significant fire safety improvement in polymer nanocomposites. However, as elemental phosphorus, fire safety improvement effect of BP nanosheets on polymer composites builds on the conversion of gaseous pyrolysis products into smoke particles, which inevitably promotes the formation and release of smoke particles. From the perspective of overall fire safety improvement, it is vital to simultaneously suppress the heat release and smoke production of polymer/BP composites. Herein, melamine-mediated graphene/black phosphorous nanohybrids (GNS/MA/BP) were fabricated through electrostatic-driving self-assembly process and introduced into polyether thermoplastic polyurethane (TPU). During combustion, the barrier function provided by thermally stable layered structure of graphene (GNS) enables more pyrolysis products of BP nanosheets to be kept within condensed phase and react with polymer matrix. Compared to pure TPU, the incorporated hierarchical nanostructure (GNS/MA/BP-2) decreases PHRR, THR, and total CO2 release of TPU composite by 54.7%, 23.5%, and 32.5%, respectively. Beside, in contrast to TPU-BP composite, the release rate of toxic smoke and CO gas of TPU-GNS/MA/BP-2 composite are reduced by 46.7% and 49.4%. With barrier function of graphene, the heat and smoke release behavior of polymer/BP nanocomposites is effectively suppressed.

Self-floating black phosphorous nanosheets as a carry-on solar vapor generator

Efficient solar vapor generation has provided a feasible way to solve the water shortage in undeveloped and arid areas. However, some photo-thermal materials need additional large-volume support materials being harmful to carry around to obtain float capacity, while suppressing the solar steam generation. Herein, the decrease approach of surface tension was presented for solving the moist-environment degradation behavior of black phosphorus (BP) nanosheets and obtaining the self-floating capacity, thus applying BP nanosheets in solar vapor generation field. With the in situ cross-linking polymerization, trichloro(1H,1H,2H,2H-perfluorooctyl) silane successfully modified BP nanosheets (F-BP). Due to the significantly decreased surface tension, F-BP nanosheets are capable of self-floating easily on water surface and spreading out spontaneously. With assistance of desirable photo-thermal conversion capacity, self-floating BP nanosheets convert the incident photon into local heat, showing excellent vapor generation performance. With simulated sun illumination (1 kW/m2), 238.7 g/m2 BP nanosheets present the evaporation rate of ~0.9437 kg/(m2·h) and efficiency of ~64.63 ± 2.3%. Meanwhile, the super-hydrophobicity successfully imparts BP nanosheets with resistance to the deterioration caused by salt precipitation. The carriable F-BP nanosheets are an ideal photo-thermal convertor to produce drinking water, successfully providing a feasible way to solve water shortage in limited condition.

Single Cobalt Atom Anchored Black Phosphorous Nanosheets as an Effective Cocatalyst Promotes Photocatalysis

AbstractExploring novel cocatalysts with sufficient active sites and rapid photogenerated carrier separation remains challenge for boosting photocatalytic reactions. Recently, two‐dimensional (2D) black phosphorus (BP) has been developed and recognized to be an ideal platform for anchoring metal ions through lone pair electrons. Herein, we propose a new structure that cobalt atomically dispersed on BP nanosheets (BP−Co), and apply it as cocatalyst for photocatalytic H2 evolution and CO2 reduction under visible light (>420 nm) irradiation. Both scanning transmission electron microscope and X‐ray absorption near edge structure verified the existence of phosphorous‐coordinated Co sites. The interaction between Co and P brings greatly improvement on photocatalytic activities, and 18‐fold enhancement can be achieved on CdS when taking BP−Co as a noble‐metal‐free cocatalyst for H2 evolution, which is higher than that of Pt under the same conditions. Besides, BP−Co can also be used as an effective cocatalyst to promote photocatalytic CO2 reduction in the presence of photosensitizer [Ru(2, 2’‐bipyridy)3]Cl2 with a CO evolution rate of 88.6 μmol h−1, superior to those obtained from the state‐of‐the‐art cocatalysts. It is anticipated that the current work might provide basic understanding as well as new opportunities on 2D BP nanosheets for versatile photocatalytic reactions.

Black Phosphorus Based Multicolor Light-Modulated Transparent Memristor with Enhanced Resistive Switching Performance.

Light-modulated transparent memristors combining photoresponse and data storage are promising as multifunctional devices. Herein, a multicolor light-modulated transparent memristor based on black phosphorous (BP) is designed, fabricated, and investigated. BP is a class of emerging two-dimensional (2D) materials with a natural direct band gap and a broad light absorption. Herein, BP nanosheets (BP@PS NSs) coated with polystyrene (PS) are prepared and serve as the resistive switching (RS) layer in the ITO/BP@PS/ITO memristor, which shows >75% transmittance between 350 and 1100 nm. With the aid of PS, the BP@PS-based memristor has excellent RS characteristics such as no initial preforming, low operating voltage, and long retention time. According to the energy band model, the RS mechanism of the high and low resistance states contributes to the transformation from ohmic contact to Schottky contact. During light illumination ranging from ultraviolet (380 nm) to near infrared (785 nm), the Schottky barrier height is elevated further so that the resetting voltages and power consumption decrease. Moreover, the ON/OFF ratios are improved and the maximum enhancement is demonstrated to be more than 10 times. BP is a promising RS material in light-modulated memristors, and the novel device configuration provides insights into the development of multifunctional microelectronic devices based on 2D materials.

Black Phosphorous Nanosheets: A Novel Solar Vapor Generator

Solar vapor generation is a promising and whole new branch of photothermal conversion for harvesting solar energy. In this work, a novel solar vapor generator based on black phosphorous (BP) nanosheets is designed for steam generation, desalination, as well as dye removal, using polyurethane (PU) foam as a supporting material. Employing electrostatic layer‐by‐layer assembly, BP nanosheets and chitosan (CS) are alternately deposited onto the skeleton of the PU foam. After the deposition of BP nanosheets, the hydrophilicity of the PU composite foam is obviously improved, thus facilitating the capillary effect. Even with a spot of BP nanosheets (lower than 5.0 wt%), the as‐fabricated PU@(sodium alginate, SA/BP)6 foam exhibits a surface temperature of ≈70.9 °C and an evaporation rate of 1.082 kg m−2 h−1 under 1 sun irradiation. Due to the protection effect of CS, the photothermal conversion performance and water evaporation rate do not deteriorate during ten cycles of reusing. In addition, the water evaporation performance of PU@(SA/BP)6 is also investigated under different conditions, including sun irradiation intensity, metal ions, and dye. In brief, employing a facile and eco‐friendly fabrication process, BP nanosheets are first applied to seawater desalination and pollution removal, presenting a tremendous potential for practical solar vapor generation.

Mn-Doping-induced hierarchical petal growth of a flower-like 3D MOF assembled with black phosphorous nanosheets as an electrochemical aptasensor of human stress-induced phosphoprotein 1.

Herein, we report the preparation of Mn-doped Ni-based metal-organic frameworks (Mn-MOF) with 3D hierarchical flower-like superstructures through solvothermal synthesis. The Mn-MOF was assembled with 2D black phosphorous nanosheets (BPNSs) to achieve novel 2D/3D BPNSs/Mn-MOF nanocomposites, followed by the direct coupling of methylene blue (MB)-labeled DNA aptamer on the interface of the nanocomposites-modified glassy carbon electrode (GCE). The aptamer/BPNSs/Mn-MOF/GCE platform was utilized for the capture and efficient detection of stress-induced phosphoprotein 1 (STIP1). Experimental results confirmed that Mn-doping-induced the hierarchical petal growth of the flower-like 3D MOF and its assembly with BPNSs. GCE surface modifications with various components were studied by measuring electrochemical curves. The morphologies, microstructures and spectra of products were characterized. The optimal conditions used for electrochemical measurements were assessed. A smart aptasensor was explored by the aptamer/BPNSs/Mn-MOF/GCE that had multiple attractive merits, including synergistic effects of components, porous superstructures of hierarchical flower-like 3D Mn-MOF and specific aptamer-target recognition. The merits endowed this aptasensor with selective and sensitive signal responses to STIP1 over interferences. This aptasensor enabled the efficient detection of STIP1 in a broad range of 2 × 10-3-1 × 104 ng mL-1, accompanied by a low limit of detection of 1 pg mL-1. This aptasensor realized the successful determination of STIP1 in practical samples, exhibiting high reliability and practicability.

Natural antioxidant functionalization for fabricating ambient-stable black phosphorus nanosheets toward enhancing flame retardancy and toxic gases suppression of polyurethane

Herein, as a natural antioxidant, tannin (TA) is firstly used to functionalize black phosphorous (BP) nanosheets to improve the ambient stability and toxic suppression, thus decreasing the fire hazards of polymer materials. Compared to pure BP nanosheets, higher temperature for thermal oxidation decomposition is achieved for TA-BP nanosheets, directly confirming the ambient stability of TA-BP nanosheets. Meanwhile, from high resolution TEM and XPS results, TA-BP nanosheets after being exposed at air for 10 days present well-organized crystal structure and low POx bonds content. Cone calorimeter results illustrate that the incorporation of 2.0 wt% TA-BP nanosheets significantly decreases the peak value of heat release rate (−56.5 %), total heat release (−43.0 %), CO2 concentration (−57.3 %) of TPU composite. Meanwhile, with addition of low to 1.5 wt%, the release of highly-toxic CO gas is significantly suppressed, confirmed by lower peak value (0.52 mg/m3) and decreased total release amount (−55.1 %). The obviously enlarged tensile strength (36.7 MPa) and desirable elongation at break (622 %) are also observed. This strategy not only firstly adopts bio-based antioxidant to impart excellent environmental stability for BP nanosheets, but also promotes the promising potentials of BP nanosheets in the fire safety application of polymer composites.

Recent Advances in Chemical Functionalization of 2D Black Phosphorous Nanosheets.

Owing to their tunable direct bandgap, high charge carrier mobility, and unique in‐plane anisotropic structure, black phosphorus nanosheets (BPNSs) have emerged as one of the most important candidates among the 2D materials beyond graphene. However, the poor ambient stability of black phosphorus limits its practical application, due to the chemical degradation of phosphorus atoms to phosphorus oxides in the presence of oxygen and/or water. Chemical functionalization is demonstrated as an efficient approach to enhance the ambient stability of BPNSs. Herein, various covalent strategies including radical addition, nitrene addition, nucleophilic substitution, and metal coordination are summarized. In addition, efficient noncovalent functionalization methods such as van der Waals interactions, electrostatic interactions, and cation–π interactions are described in detail. Furthermore, the preparations, characterization, and diverse applications of functionalized BPNSs in various fields are recapped. The challenges faced and future directions for the chemical functionalization of BPNSs are also highlighted.

Self-assembly followed by radical polymerization of ionic liquid for interfacial engineering of black phosphorus nanosheets: Enhancing flame retardancy, toxic gas suppression and mechanical performance of polyurethane

As one of emerging layered nanomaterials, the potential of black phosphorous nanosheets (BP) for fabricating high performance polymer composites was seriously confined by incompatible interface. Herein, interfacial engineering between BP nanosheets and polyurethane (PU) matrix was rationally designed, where employing polymerized ionic liquid as linking bridge between robust BP nanosheets and soft TPU. The ionic liquid (IL) was firstly confined onto the surface of BP nanosheets with the combination of electrostatic-driving self-assembly process and in situ radical polymerization was then performed. The successful preparation of IL-functionalized BP (IL-BP) nanosheets was confirmed by a series of analytic methods, incluing TEM, XPS, FTIR, and so on. The resultant IL-BP nanosheets imparted well mechanical performance and flame retardancy to TPU composites. Compared to the mechanical enhancement reported by other literatures, the break strength of TPU/IL-BP-1.0 was significantly increased by 50%, attributing to strong interfacial regulation of polymerized IL and mechanically robust BP nanosheets, generated by the similar polarity. Meanwhile, significant decreases of 38.2% and 19.7% in peak values of heat release rate and total heat release were achieved for TPU/IL-BP-2.0. With the investigation of combustion residue and pyrolysis products, it was found that a mass of pyrolysis products reacted with IL-BP nanosheets to form mechanically robust protective char and solid products, being no longer used as fuel to support combustion. Meanwhile, the maximum concentration of CO2 and highly toxic CO of TPU/IL-BP-2.0 were effectively decreased by 36.9% and 26.5%, compared to the pure TPU. Such a design route effectively regulates the interfacial interaction between BP nanosheets and polymer matrix and offers a practical route for preparing high performance materials.

Dye-sensitized black phosphorus nanosheets decorated with Pt cocatalyst for highly efficient photocatalytic hydrogen evolution under visible light

Although black phosphorous (BP) and its derived materials have shown great potential for application in photocatalytic H2 evolution reaction (HER), their HER activity and stability still remains unsatisfied mainly due to the insufficient charge separation, the lack of surface active sites, and the defect-riched nature of BP. Herein, we report that BP nanosheets decorated with in situ grown Pt (BP NSs/Pt) could act as a highly efficient catalyst for photocatalytic H2 evolution in an Erythrosin B (ErB)-sensitized system under visible light irradiation (≥450 nm) in the presence of triethanolamine (TEOA) as sacrificial electron donor. It is found that BP NSs can provide large surface area for the confined growth of Pt nanoparticles with a high dispersion and a reduced size but also stabilize the loaded Pt nanoparticles by covalent bonds at the BP NSs/Pt interfaces. Moreover, BP NSs offer a fast electron transfer pathway to facilitate the photocatalytic HER over in situ grown Pt catalyst. As a result, BP NSs/Pt catalyst exhibits ∼6 times higher H2 evolution activity than free Pt nanoparticles and an apparent quantum yield (AQY) of 0.57% at 500 nm irradiation in ErB-TEOA system. This work indicates the potential of BP NSs as an effective 2D matrix to construct numerous high performance photocatalysts and photocatalytic systems.

Biodegradable Black Phosphorus-based Nanomaterials in Biomedicine: Theranostic Applications.

Ascribe to the unique two-dimensional planar nanostructure with exceptional physical and chemical properties, black phosphorous (BP) as the emerging inorganic twodimensional nanomaterial with high biocompatibility and degradability has been becoming one of the most promising materials of great potentials in biomedicine. The exfoliated BP sheets possess ultra-high surface area available for valid bio-conjugation and molecular loading for chemotherapy. Utilizing the intrinsic near-infrared optical absorbance, BPbased photothermal therapy in vivo, photodynamic therapy and biomedical imaging has been realized, achieving unprecedented anti-tumor therapeutic efficacy in animal experiments. Additionally, the BP nanosheets can strongly react with oxygen and water, and finally degrade to non-toxic phosphate and phosphonate in the aqueous solution. This manuscript aimed to summarize the preliminary progresses on theranostic application of BP and its derivatives black phosphorus quantum dots (BPQDs), and discussed the prospects and the state-of-art unsolved critical issues of using BP-based material for theranostic applications.

Ice‐Assisted Synthesis of Black Phosphorus Nanosheets as a Metal‐Free Photocatalyst: 2D/2D Heterostructure for Broadband H2 Evolution

AbstractA 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C3N4) is designed and synthesized for photocatalytic H2 evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C3N4 protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H2 production rate of BP/g‐C3N4 (384.17 µmol g−1 h−1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C3N4 (likely due to formed NP bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H2 evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.

Exploration of two-dimensional bio-functionalized phosphorene nanosheets (black phosphorous) for label free haptoglobin electro-immunosensing applications

We report on the development of an antibody-functionalized interface based on electrochemically active liquid-exfoliated two-dimensional phosphorene (Ph) nanosheets—also known as black phosphorous nanosheets—for the label-free electrochemical immunosensing of a haptoglobin (Hp) biomarker, a clinical marker of severe inflammation. The electrodeposition has been achieved over the screen-printed electrode (SPE) using liquid-assisted ultrasonically exfoliated black phosphorus nanosheets. Subsequently, Ph-SPEs bioconjugated with Hp antibodies (Ab), using electrostatic interactions via a poly-L-lysine linker for biointerface development. Electrochemical analysis demonstrates that the Ab-modified Ph-SPEs (Ab@Ph-SPE) exhibit enhanced electroconducting behavior as compared to the pristine electrodes. This Ab-functionalized phosphorene-based electrochemical immunosensor platform has demonstrated remarkable sensitivity and specificity, having a dynamic linear response range from 0.01–10 mg ml−1 for Hp in standard and serum samples with a low detection limit (∼0.011 mg ml−1) using the label-free electrochemical technique. The sensor electrodes were also studied with other closely relative interferents to investigate cross reactivity and specificity. This strategy opens up avenues to POC (point-of-care) and on-farm livestock disease monitoring technologies for multiplexed diagnosis in complex biological samples such as serum. The technique is simple in fabrication and provides an analytical response in less than 60 s.

2D black phosphorous nanosheets as a hole transporting material in perovskite solar cells

We demonstrate for the first-time liquid exfoliated few layers of 2D Black phosphorus (BP) nanosheets as a hole transporting material (HTM) for perovskite based solar cells. The photoelectron spectroscopy in air (PESA) measurements confirm the low laying valence band level of BP nanosheets (−5.2 eV) favourable for hole injection from CH3NH3PbI3 (MAPbI3). Our results show that ∼25% improvement in power conversion efficiency (PCE) of η = 16.4% for BP nanosheets + Spiro-OMeTAD as an HTM as compared to spiro-OMeTAD (η = 13.1%). When BP nanosheets are exclusively utilised as an HTM, a PCE of η = 7.88% is noted, an improvement over the 4% PCE values observed for HTM free devices. Photoluminescence (PL) quenching of MAPbI3 and impedance measurements further confirm the charge extraction ability of BP nanosheets. The structural and optical characterization of liquid exfoliated BP nanosheets is discussed in detail with the aid of transmission electron microscopy, Raman spectroscopy, absorption spectroscopy and photo-electron spectroscopy.

Novel QCM humidity sensors using stacked black phosphorus nanosheets as sensing film

This work describes the fabrication of humidity sensors by depositing black phosphorous (BP) nanosheets (prepared by liquid exfoliation of bulk BP) onto a quartz crystal microbalance (QCM) in the form of a thin film. The surface morphology of the prepared BP nanosheets is characterized using a field-emission scanning electron microscope and transmission electron microscopy. The humidity sensing characteristics of the BP-based QCM sensors (such as frequency response, stability, humidity hysteresis, and repeatability) are investigated by using an oscillating circuit method. Experimental results indicate that the BP-based QCM sensors exhibit a well-defined logarithmic frequency response to humidity, and the sensitivity of the sensor is strongly related to the amount of BP nanosheets used in the deposition process. Additionally, the BP-based QCM sensors exhibit high stability over the wide relative humidity range of 11.3%–84.3% RH. The BP-based QCM sensors also exhibit little humidity hysteresis and fast dynamic response and recovery times. This work demonstrates that BP is a promising candidate material for humidity detection when combined with a QCM transducer.

Nonvolatile Charge Injection Memory Based on Black Phosphorous 2D Nanosheets for Charge Trapping and Active Channel Layers

2D van der Waals atomic crystal materials have great potential for use in future nanoscale electronic and optoelectronic applications owing to their unique properties such as a tunable energy band gap according to their thickness or number of layers. Recently, black phosphorous (BP) has attracted significant interest because it is a single‐component material like graphene and has high mobility, a direct band gap, and exhibits ambipolar transition behavior. This study reports on a charge injection memory field‐effect transistor on a glass substrate, where few‐layer BPs act as the active channel and charge trapping layers, and Al2O3 films grown by atomic layer deposition act as the tunneling and blocking layers. Because of the ambipolar properties of BP nanosheets, both electrons and holes are involved in the charge trapping process, resulting in bilateral threshold voltage shifts with a large memory window of 22 V. Finally, a memory circuit of a resistive‐load inverter is implemented that converts analog signals (current) to digital signals (voltage). Such a memory inverter also shows a clear memory window and distinct memory on/off switching characteristics.

Field-effect transistor biosensors with two-dimensional black phosphorus nanosheets

A black phosphorous (BP)-based field-effect transistor (FET) biosensor was fabricated by using few-layer BP nanosheets labeled with gold nanoparticle-antibody conjugates. BP nanosheets were mechanically exfoliated and used as the sensing/conducting channel in the FET, with an Al2O3 thin film as the dielectric layer for surface passivation. Antibody probes were conjugated with gold nanoparticles that were sputtered on the BP through surface functionalization. The sensor response was measured by the change in the BP's electrical resistance after antigens were introduced. The adsorbed antigens through specific antigen-antibody binding interactions induced a gate potential, thereby changing the drain-source current. The as-produced BP biosensor showed both high sensitivity (lower limit of detection ~10ng/ml) and selectivity towards human immunoglobulin G. Results from this study demonstrate the outstanding performance of BP as a sensing channel for FET biosensor applications.

Liquid‐Exfoliated Black Phosphorous Nanosheet Thin Films for Flexible Resistive Random Access Memory Applications

Black phosphorous (BP) is a unique layered p‐type semiconducting material. The successful use of BP nanosheets in field‐effect transistors fueled research on BP atomic layers that focuses on, e.g., the exploration of their optical and electronic properties, and promising applications in (opto)electronics. However, BP films are prone to degradation in ambient conditions, which prevents their commercial application. Here, a route to the application of BP films as an environmental stable nonvolatile resistive random access memory is presented. The BP films, which are prepared from exfoliated BP nanosheets in selected solvents, show solvent‐dependent degradation upon ambient exposure, inducing the formation of an amorphous top degraded layer (TDL). The TDL acts as an insulating barrier just below the Al electrode. This property that was only obtained by degradation, confers a bipolar resistive switching behavior with a high ON/OFF current ratio up to ~3 × 105 and excellent retention ability over 105 s to the flexible BP memory devices. The TDL also prevents propagation of degradation further into the film, ensuring excellent memory performance even after three month of ambient exposure.