Vibration of black phosphorus nanotubes via orthotropic cylindrical shell model

Black phosphorus nanotubes(BPNTs)may have good properties and potential applications.Determining thevibration property of BPNTs is essential for gaining insight into the mechanical behaviour of BPNTs and designingoptimized nanodevices.In this paper,the mechanical behaviour and vibration property of BPNTs are studied viaorthotropic cylindrical shell model and molecular dynamics(MD)simulation.The vibration frequencies of twochiral BPNTs are analysed systematically.According to the results of MD calculations,it is revealed that thenatural frequencies of two BPNTs with approximately equal sizes are unequal at each order,and that the naturalfrequencies of armchair BPNTs are higher than those of zigzag BPNTs.In addition,an armchair BPNTs witha stable structure is considered as the object of research,and the vibration frequencies of BPNTs of differentsizes are analysed.When comparing the MD results,it is found that both the isotropic cylindrical shell modeland orthotropic cylindrical shell model can better predict the thermal vibration of the lower order modes of thelonger BPNTs better.However,for the vibration of shorter and thinner BPNTs,the prediction of the orthotropiccylindrical shell model is obviously superior to the isotropic shell model,thereby further proving the validity ofthe shell model that considers orthotropic for BPNTs.

Interface and M^(3+)/M^(2+)Valence Dual-Engineering on Nickel Cobalt Sulfoselenide/Black Phosphorus Heterostructure for Efficient Water Splitting Electrocatalysis

The catalyst innovation that aims at noble-metal-free substitutes is one key aspect for future sustainable hydrogen energy deployment.In this paper,a nickel cobalt sulfoselenide/black phosphorus heterostructure(NiCoSe|S/BP)was fabricated to realize the highly active and durable water electrolysis through interface and valence dual-engineering.The NiCoSe|S/BP nanostructure was constructed by in-situ growing NiCo hydroxide nanosheet arrays on few-layer BP and subsequently one-step sulfoselenization by SeS2.Besides the conductive merit of BP substrate,holes in p-type BP are capable of oxidizing the Co^(2+)to high-valence and electron-accepting Co^(3+),benefiting the oxygen evolution reaction(OER).Meanwhile,Ni^(3+)/Ni^(2+)ratio in the heterostructure is reduced to maintain the electrical neutrality,which corresponds to the increased electron-donating character for boosting hydrogen evolution reaction(HER).As for HER and OER,the heterostructured NiCoSe|S/BP electrocatalyst exhibits small overpotentials of 172 and 285 mV at 10 mA cm^(-2)(η_(10))in alkaline media,respectively.And overall water splitting has been achieved at a low cell potential of 1.67 V at η_(10) with high stability.Molecular sensing and density functional theory(DFT)calculations are further proposed for understanding the rate-determine steps and enhanced catalytic mechanism.The investigation presents a deep-seated perception for the electrocatalytic performance enhancement of BP-based heterostructure.

基于black phosphorus纳米棒耦合的等离激元诱导透明

提出了基于black phosphorus(BP)纳米棒耦合的多频段等离激元诱导透明(PIT)电磁模型,通过FDTD和辐射双振荡器(RTO)模型从数值计算和理论研究两方面分析了模型的电磁特性.结果表明:由于不同长度的BP纳米棒之间的明-明耦合,可以在实现单频段PIT效应的基础之上,进一步产生双频段和三频段的PIT效应.其次,通过改变BP的弛豫速率ns,可以在单频段、双频段、三频段PIT模型中同时实现透明窗谐振频率的可调性.当ns增大时,各频段PIT窗口的谐振频率将会逐渐增大,发生蓝移.进一步研究了单频段PIT模型的传感特性,该模型随背景材料折射率变化的灵敏度(sensitivity)达到了6110.6 (nm/RIU),优值系数(FOM)达到了7.39 (1/RIU)这为多频带滤波、超灵敏传感器的设计提供了理论参考.

Black phosphorus:A novel nanoplatform with potential in the¯eld of bio-photonic nanomedicine

Single-or few-layer black phosphorus(FLBP)has attracted great attentions in scientic community with its excellent properties,including biodegradability,unique puckered lattice conguration,attractive electrical properties and direct and tunable band gap.In recent years,FLBP has been widely studied in bio-photonicelds such as photothermal and photodynamic therapy,drug delivery,bioimaging and biosensor,showing attractive clinical potential.Because of the marked advantages of FLBP nanomaterials in bio-photonicelds,this review article reviews the latest advances of biomaterials based on FLBP in biomedical applications,ranging from biocompatibility,medical diagnosis to treatment.

Black phosphorus junctions and their electrical and optoelectronic applications

Black phosphorus(BP),an emerging two-dimensional material,is considered a promising candidate for next-generation electronic and optoelectronic devices due to in-plane anisotropy,high mobility,and direct bandgap.However,BP devices face challenges due to their limited stability,photo-response speed,and detection range.To enhance BP with powerful electrical and optical performance,the BP heterostructures can be created.In this review,the state-of-the-art heterostructures and their electrical and optoelectronic applications based on black phosphorus are discussed.Five parts introduce the performance of BP-based devices,including black phosphorus sandwich structure by hBN with better stability and higher mobility,black phosphorus homojunction by dual-gate structure for optical applications,black phosphorus heterojunction with other 2D materials for faster photo-detection,black phosphorus heterojunction integration with 3 D bulk material,and BP via Asdoping tunable bandgap enabling photo-detection up to 8.2μm.Finally,we discuss the challenges and prospects for BP electrical and optical devices and applications.

Two-Dimensional Black Phosphorus: An Emerging Anode Material for Lithium-Ion Batteries

Two-dimensional black phosphorus(2D BP),an emerging material,has aroused tremendous interest once discovered.This is due to the fact that it integrates unprecedented properties of other 2D materials,such as tunable bandgap structures,outstanding electrochemical properties,anisotropic mechanical,thermodynamic,and photoelectric properties,making it of great research value in many fields.The emergence of 2D BP has greatly promoted the development of electrochemical energy storage devices,especially lithium-ion batteries.However,in the application of 2D BP,there are still some problems to be solved urgently,such as the difficulty in the synthesis of large-scale high-quality phosphorene,poor environmental stability,and the volume expansion as electrode materials.Herein,according to the latest research progress of 2D BP in the field of energy storage,we systematically summarize and compare the preparation methods of phosphorene and discuss the basic structure and properties of BP,especially the environmental instability and passivation techniques.In particular,the practical application and challenges of 2D BP as anode material for lithium-ion batteries are analyzed in detail.Finally,some personal perspectives on the future development and challenges of BP are presented.

Electrochemical exfoliation of two-dimensional layered black phosphorus and applications

With the discovery of graphene,black phosphorus(BP)has been rediscovered as a two-dimensional(2 D)layered material.Since its first preparation in 2014,2 D BP has elicited immense interest,and has exhibited excellent properties,such as distinct pleated structures in layers,adjustable direct bandgap,high carrier mobility,moderate on/off ratio,large specific surface area,and various interesting in-layer anisotropies.However,the realization of these excellent properties depends on the preparation of highquality 2 D BP sheets.Electrochemical exfoliation methods are typically performed under mild conditions,thus,these methods are convenient,controllable,and can produce high-quality 2 D BP sheets.This review summarizes research progress in BP sheets preparation through anodic,cathodic,and electrolyte exfoliation in recent years.Different exfoliating methods affect the quality of 2 D BP sheets.Moreover,possible exfoliating mechanisms and the potential applications of different exfoliating methods are summarized and discussed in detail.Lastly,the shortcomings of existing research on electrochemical exfoliation are presented,and suggestions and prospects for future research on the electrochemical exfoliation of 2 D BP are proposed.

Black phosphorus-based field effect transistor devices for Ag ions detection

Black phosphorus （BP）, an attractive two-dimensional （2D） semiconductor, is widely used in the fields of optoelec- tronic devices, biomedicine, and chemical sensing. Silver ion （Ag＋）, a commonly used additive in food industry, can sterilize and keep food fresh. But excessive intake of Ag＋ will harm human health. Therefore, high sensitive, fast and simple Ag＋ detection method is significant. Here, a high-performance BP field effect transistor （FET） sensor is fabricated for Ag＋ detection with high sensitivity, rapid detection speed, and wide detection concentration range. The detection limit for Ag＋ is 10 l0 mol/L. Testing time for each sample by this method is 60 s. Besides, the mechanism of BP-FET sensor for Ag＋ detection is investigated systematically. The simple BP-FET sensor may inspire some relevant research and potential applications, such as providing an effective method for the actual detection of Ag＋, especially in wimessed inspections field of food.

Two‑Dimensional Black Phosphorus Nanomaterials:Emerging Advances in Electrochemical Energy Storage Science

Two-dimensional black phosphorus(2D BP),well known as phosphorene,has triggered tremendous attention since the first discovery in 2014.The unique puckered monolayer structure endows 2D BP intriguing properties,which facilitate its potential applications in various fields,such as catalyst,energy storage,sensor,etc.Owing to the large surface area,good electric conductivity,and high theoretical specific capacity,2D BP has been widely studied as electrode materials and significantly enhanced the performance of energy storage devices.With the rapid development of energy storage devices based on 2D BP,a timely review on this topic is in demand to further extend the application of 2D BP in energy storage.In this review,recent advances in experimental and theoretical development of 2D BP are presented along with its structures,properties,and synthetic methods.Particularly,their emerging applications in electrochemical energy storage,including Li−/K−/Mg−/Na-ion,Li–S batteries,and supercapacitors,are systematically summarized with milestones as well as the challenges.Benefited from the fast-growing dynamic investigation of 2D BP,some possible improvements and constructive perspectives are provided to guide the design of 2D BP-based energy storage devices with high performance.

Toward high-performance two-dimensional black phosphorus electronic and optoelectronic devices

Recently, black phosphorus （BP） has joined the two-dimensional material family as a promising candidate for elec- tronic and photonic applications due to its moderate bandgap, high carrier mobility, and unusual in-plane anisotropy. Here, we review recent progress in BP-based devices, such as field-effect transistors, contact resistance, quantum transport, stabil- ity, photodetector, heterostructure, and in-plane anisotropy. We also give our perspectives on future BP research directions.

Reduced Ti-MOFs encapsulated black phosphorus with high stability and enhanced photocatalytic activity

The generation of green hydrogen(H_2) energy is of great significance to solve worldwide energy and environmental issues. Reduced Ti based photocatalyst has recently attracted intensive attention due to its excellent photocatalytic activity, while the synthesis of reduced Ti based photocatalysts with high stability is still a great challenge. Here, we report a facile method for synthesis of reduced Ti metal organic frameworks(small amounts of Pt incorporated) encapsulated BP(BP/R-Ti-MOFs/Pt) hybrid nanomaterial with enhanced photocatalytic activity. The strong interaction between Ti and P reduces the valence state of the binding Ti^(4+)on the BP surface, forming abundant reduced Ti^(4+)within R-Ti-MOFs/BP. Such reduced Ti^(4+)render R-Ti-MOFs/BP efficient charge transfer and excellent light absorption capability, thus promote the photocatalytic H_2 production efficiency. Furthermore, the Ti-P interaction stabilizes both reduced Ti^(4+)and BP during the photocatalytic reaction, which greatly enhanced the stability of the obtained BP/R-TiMOFs/Pt photocatalyst.

The roles of black phosphorus in performance enhancement of halide perovskite solar cells

Hybrid organic-inorganic perovskite solar cells(PSCs) are considered to be the most promising thirdgeneration photovoltaic(PV) technology with the most rapid rate of increase in the power conversion efficiency(PCE). To date, their PCE values are comparable to the established photovoltaic technologies such as crystalline silicon. Intensive research activities associated with PSCs have been being performed,since 2009, aiming to further boost the device performance in terms of efficiency and stability via different strategies in order to accelerate the progress of commercialization. The emerging 2 D black phosphorus(BP) is a novel class of semiconducting material owing to its unique characteristics, allowing them to become attractive materials for applications in a variety of optical and electronic devices, which have been comprehensively reviewed in the literature. However, comprehensive reviews focusing on the application of BP in PSCs are scarce in the community. This review discusses the research works with the incorporation of BP as a functional material in PSCs. The methodology as well as the effects of employing BP in different regions of PSCs are summarized. Further challenges and potential research directions are also highlighted.

Intrinsic charge transport behaviors in graphene-black phosphorus van der Waals heterojunction devices

Heterostructures from mechanically-assembled stacks of two-dimensional materials allow for versatile electronic device applications. Here, we demonstrate the intrinsic charge transport behaviors in graphene-black phosphorus heterojunction devices under different charge carrier densities and temperature regimes. At high carder densities or in the ON state, tunneling through the Schottky barrier at the interface between graphene and black phosphorus dominates at low temperatures. With temperature increasing, the Schottky barrier at the interface is vanishing, and the channel current starts to decrease with increasing temperature, behaving like a metal. While at low carder densities or in the OFF state, thermal emission over the Schottky barrier at the interface dominates the carriers transport process. A barrier height of ～ 67.3 meV can be extracted from the thermal emission-diffusion theory.

Electronic, optical property and carrier mobility of graphene, black phosphorus, and molybdenum disulfide based on the first principles

The band structure, density of states, optical properties, carrier mobility, and loss function of graphene, black phosphorus（BP）, and molybdenum disulfide（MoS_2） were investigated by the first-principles method with the generalized-gradient approximation. The graphene was a zero-band-gap semiconductor. The band gaps of BP and MoS_2 were strongly dependent on the number of layers. The relationships between layers and band gap were built to predict the band gap of few-layer BP and MoS_2. The absorption showed an explicit anisotropy for light polarized in（1 0 0） and（0 0 1） directions of graphene, BP,and MoS_2. This behavior may be readily detected in spectroscopic measurements and exploited for optoelectronic applications. Moreover, graphene（5.27 × 10~4 cm^2·V^（-1）·s^（-1））, BP（1.5 × 10~4 cm^2·V^（-1）·s^（-1））, and MoS_2（2.57×102 cm2·V-1·s-1）have high carrier mobility. These results show that graphene, BP, and MoS_2 are promising candidates for future electronic applications.

Molecular dynamics simulations of strain-dependent thermal conductivity of single-layer black phosphorus

Classical molecular dynamics(MD)simulations ae performed to investigate the effects of mechanical strain on the thermal conductivity of single-layer black phosphorus(SLBP)nanoribbons along different directions at room temperature.The results show that the tensile strain afects the thermal conductivity of nanoribbons by changing thephonon density of state(DOS)and mean free path(M FP).The thermal conductivity shows a sharp enhancement with the tensile strain applied along the armchai diection,while it increases slowly with the strain applied along the zigzag diection.This phenomenon cm be mainly explained by effects of the phonon DOS and MFP.The increasing strain along the armchai direction weakens DOS and strengthens MFP clearly.However,when it comes to the increasing strain along the zigzag deection'DOS enliances significantly while MFP decreases slightly.The findings explore the relationship between the tensile strain and the thermal conductivity reasonably and can provide a reliable method to estimate the MFP of black phosphorus.

Q-Switched Ytterbium-Doped Fiber Laser Using Black Phosphorus as Saturable Absorber

We demonstrate a Q-switched ytterbium-doped fiber laser （YDFL） using a newly developed multi-layer black phosphorous （BP） saturable absorber （SA）. The BP SA is prepared by mechanically exfoliating a BP crystal and sticking the acquired BP flakes onto a scotch tape. A small piece of the tape is then placed between two ferrules and incorporated in a YDFL cavity to achieve a stable Q-switched operation in a 1.0 μm region. The laser has a pump threshold of 55.1 mW, a pulse repetition rate that is tunable from 8.2 to 32.9 kHz, and the narrowest pulse width of 10.8 μs. The highest pulse energy of 328 nJ is achieved at the pump power of 97.6 mW. Our results show that multi-layer BP is a promising SA for Q-switching laser operation.

Visualized SERS Imaging of Single Molecule by Ag/ Black Phosphorus Nanosheets

Single-molecule detection and imaging are of great value in chemical analysis,biomarker identification and other trace detection fields.However,the localization and visualization of single molecule are still quite a challenge.Here,we report a special-engineered nanostructure of Ag nanoparticles embedded in multi-layer black phosphorus nanosheets(Ag/BP-NS)synthesized by a unique photoreduction method as a surfaceenhanced Raman scattering(SERS)sensor.Such a SERS substrate features the lowest detection limit of 10^(–20) mol L^(−1) for R6G,which is due to the three synergistic resonance enhancement of molecular resonance,photoinduced charge transfer resonance and electromagnetic resonance.We propose a polarization-mapping strategy to realize the detection and visualization of single molecule.In addition,combined with machine learning,Ag/BP-NS substrates are capable of recognition of different tumor exosomes,which is meaningful for monitoring and early warning of the cancer.This work provides a reliable strategy for the detection of single molecule and a potential candidate for the practical bio-application of SERS technology.

Black phosphorus-based heterostructures for photocatalysis and photoelectrochemical water splitting

Semiconductor-based photocatalytic and photoelectrochemical(PEC) processes can convert solar energy into high-density chemical energy or for the treatment of environmental pollutants, which are ideal ways to deal with environmental and energy crises. The development of high-efficiency photocatalysts and photoelectrodes is the key to the in-depth development and practical application of the two technologies.Black phosphorus(BP) has excellent physicalcochemical properties such as adjustable band gap, high carrier mobility, large specific surface area and anisotropy, making it one of the most promising catalysts.BP-based heterostructure can not only realize the effective separation of photogenerated carriers but also improve the stability of BP, and is widely used in photocatalytic and PEC reactions. In this review, we first introduce the crystal structure, band structure, anisotropy, and preparation of BP with different dimensions(bulk, zero-dimension and two-dimension). Then, according to the transfer path of the photogenerated carriers and the components, the BP-based heterostructures are divided into type I heterojunction, type II heterojunction, Z-scheme heterojunction, S-scheme heterojunction, BP/carbonbased material heterostructure, BP/metal heterostructure and multi-component heterostructure.Highlighted are the diverse photocatalytic applications of BP-based heterostructure, such as water splitting and CO_(2)reduction, N_(2)fixation, pollutant degradation, photothermal and photodynamic therapy.Finally, some concluding views and opinions are stated on the challenges and opportunities faced by the further development of BP-based heterostructures in photocatalysis and PEC water splitting.

Heterobifunctional PEG-grafted black phosphorus quantum dots: “Three-in-One”nano-platforms for mitochondria-targeted photothermal cancer therapy

Black phosphorus(BP)nano-materials,especially BP quantum dots(BPQDs),performs outstanding photothermal antitumor effects,excellent biocompatibility and biodegradability.However,there are several challenges to overcome before offering real benefits,such as poor stability,poor dispersibility as well as difficulty in tailoring other functions.Here,a“three-in-one”mitochondria-targeted BP nano-platform,called as BPQD-PEG-TPP,was designed.In this nano-platform,BPQDs were covalently grafted with a heterobifunctional PEG,in which one end was an aryl diazo group capable of reacting with BPQDs to form a covalent bond and the other end was a mitochondria-targeted triphenylphosphine(TPP)group.In addition to its excellent near-infrared photothermal properties,BPQD-PEG-TPP had much enhanced stability and dispersibility under physiological conditions,efficient mitochondria targeting and promoted ROS production through a photothermal effect.Both in vitro and in vivo experiments demonstrated that BPQD-PEG-TPP performed much superior photothermal cytotoxicity than BPQDs and BPQD-PEG as the mitochondria targeted PTT.Thus this“three-in-one”nanoplatform fabricated through polymer grafting,with excellent stability,dispersibility and negligible side effects,might be a promising strategy for mitochondria-targeted photothermal cancer therapy.

Black Phosphorus/Nanocarbons Constructing a Dual-Carbon Conductive Network for High-Performance Sodium-Ion Batteries

Black phosphorus has been recognized as a prospective candidate anode material for sodium-ion batteries(SIBs)due to its ultrahigh theoretical capacity of 2596 mA·h/g and high electric conductivity of≈300 S/m.However,its large volume expansion and contraction during sodiation/desodiation lead to poor cycling stability.In this work,a BP/graphite nanoparticle/nitrogen-doped multiwalled carbon nanotubes(BP/G/CNTs)composite with a dual-carbon conductive network is successfully fabricated as a promising anode material for SIBs through a simple two-step mechanical milling process.The unique structure can mitigate the eff ect of volume changes and provide additional electron conduction pathways during cycles.Furthermore,the formation of P–O–C bonds helps maintain the intimate connection between phosphorus and carbon,thereby improving the cycling and rate performance.As a result,the BP/G/CNTs composite delivers a high initial Coulombic efficiency(89.6%)and a high specific capacity for SIBs(1791.3 mA·h/g after 100 cycles at 519.2 mA/g and 1665.2 mA·h/g after 100 cycles at 1298 mA/g).Based on these results,the integrated strategy of one-and two-dimensional carbon materials can guide other anode materials for SIBs.