Borophene: Two-dimensional Boron Monolayer: Synthesis, Properties, and Potential Applications.

Borophene, a monolayer of boron, has risen as a new exciting two-dimensional (2D) material having extraordinary properties, including anisotropic metallic behavior and flexible (orientation-dependent) mechanical and optical properties. This review summarizes the current progress in the synthesis of borophene on various metal substrates, including Ag(110), Ag(100), Au(111), Ir(111), Al(111), and Cu(111), as well as heterostructuring of borophene. In addition, it discusses the mechanical, thermal, magnetic, electronic, optical, and superconducting properties of borophene and the effects of elemental doping, defects, and applied mechanical strains on these properties. Furthermore, the promising potential applications of borophene for gas sensing, energy storage and conversion, gas capture and storage applications, and possible tuning of the material performance in these applications through doping, formation of defects, and heterostructures are illustrated based on available theoretical studies. Finally, research and application challenges and the outlook of the whole borophene's field are given.

Peptide Self-Assembly Controlled Photoligation of Polymers.

Highly efficient chemical ligations that operate in water under mild conditions are the foundation of bioorthogonal chemistry. However, the toolbox of suitable reactions is limited. Conventional approaches to expand this toolbox aim at altering the inherent reactivity of functional groups to design new reactions that meet the required benchmarks. Inspired by controlled reaction environments that enzymes provide, we report a fundamentally different approach that makes inefficient reactions highly efficient within defined local environments. Contrasting enzymatically catalyzed reactions, the reactivity controlling self-assembled environment is brought about by the ligation targets themselves─avoiding the use of a catalyst. Targeting [2 + 2] photocycloadditions, which are inefficient at low concentrations and readily quenched by oxygen, short ß-sheet encoded peptide sequences are inserted between a hydrophobic photoreactive styrylpyrene unit and a hydrophilic polymer. In water, electrostatic repulsion of deprotonated amino acid residues governs the formation of small self-assembled structures, which enable a highly efficient photoligation of the polymer, reaching ∼90% ligation within 2 min (0.034 mM). Upon protonation at low pH, the self-assembly changes into 1D fibers, altering photophysical properties and shutting down the photocycloaddition reaction. Using the reversible morphology change, it is possible to switch the photoligation "ON" or "OFF" under constant irradiation simply by varying the pH. Importantly, in dimethylformamide, the photoligation reaction did not occur even at 10-fold higher concentrations (0.34 mM). The self-assembly into a specific architecture, encoded into the polymer ligation target, enables a highly efficient ligation that overcomes the concentration limitations and high oxygen sensitivity of [2 + 2] photocycloadditions.

Molecular Photoswitching of Main-Chain α-Bisimines in Solid-State Polymers.

Photoisomerization of chromophores usually shows significantly less efficiency in solid polymers than in solution as strong intermolecular interactions lock their conformation. Herein, we establish the impact of macromolecular architecture on the isomerization efficiency of main-chain-incorporated chromophores (i.e., α-bisimine) in both solution and the solid state. We demonstrate that branched architectures deliver the highest isomerization efficiency for the main-chain chromophore in the solid state─remarkably as high as 70% compared to solution. The macromolecular design principles established herein for efficient solid-state photoisomerization can serve as a blueprint for enhancing the solid-state isomerization efficiency for other polymer systems, such as those based on azobenzenes.

Optoelectronic and Optomechanical Properties of Few-Atomic-Layer Black Phosphorus Nanoflakes as Revealed by In Situ TEM.

The optoelectronic signatures of free-standing few-atomic-layer black phosphorus nanoflakes are analyzed by in situ transmission electron microscopy (TEM). As compared to other 2D materials, the band gap of black phosphorus (BP) is related directly to multiple thicknesses and can be tuned by nanoflake thickness and strain. The photocurrent measurements with the TEM show a stable response to infrared light illumination and change of nanoflakes band gap with deformation while pressing them between two electrodes assembled in the microscope. The photocurrent spectra of an 8- and a 6-layer BP nanoflake samples are comparatively measured. Density functional theory (DFT) calculations are performed to identify the band structure changes of BP during deformations. The results should help to find the best pathways for BP smart band gap engineering via tuning the number of material atomic layers and programmed deformations to promote future optoelectronic applications.

Optomechanical Properties of MoSe2 Nanosheets as Revealed by In Situ Transmission Electron Microscopy.

Free-standing few-layered MoSe2 nanosheet stacks optoelectronic signatures are analyzed by using light compatible in situ transmission electron microscopy (TEM) utilizing an optical TEM holder allowing for the simultaneous mechanical deformation, electrical probing and light illumination of a sample. Two types of deformation, namely, (i) bending of nanosheets perpendicular to their basal atomic planes and (ii) edge deformation parallel to the basal atomic planes, lead to two distinctly different optomechanical performances of the nanosheet stacks. The former deformation induces a stable but rather marginal increase in photocurrent, whereas the latter mode is prone to unstable nonsystematic photocurrent value changes and a red-shifted photocurrent spectrum. The experimental results are verified by ab initio calculations using density functional theory (DFT).

Expeditious Electrochemical Synthesis of Mesoporous Chalcogenide Flakes: Mesoporous Cu2 Se as a Potential High-Rate Anode for Sodium-Ion Battery.

Nanostructured copper selenide (Cu2 Se) attracts much interest as it shows outstanding performance as thermoelectric, photo-thermal, and optical material. The mesoporous structure is also a promising morphology to obtain better performance for electrochemical and catalytic applications, thanks to its high surface area. A simple one-step electrochemical method is proposed for mesoporous chalcogenides synthesis. The synthesized Cu2 Se material has two types of mesopores (9 and 18 nm in diameter), which are uniformly distributed inside the flakes. These materials are also implemented for sodium (Na) ion battery (NIB) anode as a proof of concept. The electrode employing the mesoporous Cu2 Se exhibits superior and more stable specific capacity as a NIB anode compared to the non-porous samples. The electrode also exhibits excellent rate tolerance at each current density, from 100 to 1000 mA g-1 . It is suggested that the mesoporous structure is advantageous for the insertion of Na ions inside the flakes. Electrochemical analysis indicates that the mesoporous electrode possesses more prominent diffusion-controlled kinetics during the sodiation-desodiation process, which contributes to the improvement of Na-ion storage performance.

Shaping and Edge Engineering of Few-Layered Freestanding Graphene Sheets in a Transmission Electron Microscope.

Full exploitation of graphene's superior properties requires the ability to precisely control its morphology and edge structures. We present such a structure-tailoring approach via controlled atom removal from graphene edges. With the use of a graphitic-carbon-capped tungsten nanoelectrode as a noncontact "milling" tool in a transmission electron microscope, graphene edge atoms approached by the tool tip are locally evaporated, thus allowing a freestanding graphene sheet to be tailored with high precision and flexibility. A threshold for the tip voltage of 3.6 ± 0.4 V, independent of polarity, is found to be the determining factor that triggers the controlled etching process. The dominant mechanisms involve weakening of carbon-carbon bonds through the interband excitation induced by tunneling electrons, assisted with a resistive-heating effect enhanced by high electric field, as elaborated by first-principles calculations. In addition to the precise shape and size control, this tip-based method enables fabrication of graphene edges with specific chiralities, such as "armchair" or "zigzag" types. The as-obtained edges can be further "polished" to become entirely atomically smooth via edge evaporation/reconstruction induced by in situ TEM Joule annealing. We finally demonstrate the potential of this technique for practical uses through creating a graphene-based point electron source, whose field emission characteristics can effectively be tuned via modifying its geometry.

Young's Modulus and Tensile Strength of Ti3C2 MXene Nanosheets As Revealed by In Situ TEM Probing, AFM Nanomechanical Mapping, and Theoretical Calculations.

Two-dimensional transition metal carbides, that is, MXenes and especially Ti3C2, attract attention due to their excellent combination of properties. Ti3C2 nanosheets could be the material of choice for future flexible electronics, energy storage, and electromechanical nanodevices. There has been limited information available on the mechanical properties of Ti3C2, which is essential for their utilization. We have fabricated Ti3C2 nanosheets and studied their mechanical properties using direct in situ tensile tests inside a transmission electron microscope, quantitative nanomechanical mapping, and theoretical calculations employing machine-learning derived potentials. Young's modulus in the direction perpendicular to the Ti3C2 basal plane was found to be 80-100 GPa. The tensile strength of Ti3C2 nanosheets reached up to 670 MPa for ∼40 nm thin nanoflakes, while a strong dependence of tensile strength on nanosheet thickness was demonstrated. Theoretical calculations allowed us to study mechanical characteristics of Ti3C2 as a function of nanosheet geometrical parameters and structural defect concentration.

True Meaning of Pseudocapacitors and Their Performance Metrics: Asymmetric versus Hybrid Supercapacitors.

The development of pseudocapacitive materials for energy-oriented applications has stimulated considerable interest in recent years due to their high energy-storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery-like to the pseudocapacitive-like behavior. As a result, it becomes challenging to distinguish "pseudocapacitive" and "battery" materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery-type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid-state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state-of-the-art progress in the engineering of active materials is summarized, which will guide for the development of real-pseudocapacitive energy storage systems.

Intrinsic and Defect-Related Elastic Moduli of Boron Nitride Nanotubes As Revealed by in Situ Transmission Electron Microscopy.

Boron nitride nanotubes (BNNTs) are promising for mechanical applications owing to the high modulus, high strength, and inert chemical nature. However, up to now, precise evaluation of their elastic properties and their relation to defects have not been experimentally established. Herein, the intrinsic elastic modulus of BNNTs and its dependence on intrinsic and deliberately irradiation-induced extrinsic defects have been studied via an electric-field-induced high-order resonance technique inside a high-resolution transmission electron microscope (HRTEM). Resonances up to fourth order for normal modes and third order for parametric modes have been initiated in the cantilevered tubes, and the recorded frequencies are well consistent with the theoretical calculations with a discrepancy of ∼1%. The elastic moduli of the BNNTs measured from high-order resonance is about 906.2 GPa on average, with a standard deviation of 9.3%, which is found to be closely related to the intrinsic defect as cavities in the nanotube walls. Furthermore, electron irradiation in HRTEM has been used to study the effects of defects to elastic moduli and to evaluate the radiation resistance of the BNNTs. Along with an increase in the irradiation dose, the outer diameter has linearly reduced due to the knock-on effects. A defective shell with nearly constant thickness has been formed on the outer surface, and as a result, the elastic modulus decreases gradually to ∼662.9 GPa, which is still 3 times that of steel. Excellent intrinsic elastic properties and decent radiation-resistance prove that BNNTs could be a material of choice for applications in extreme environments, such as those existing in space.

Crystallography-Derived Young's Modulus and Tensile Strength of AlN Nanowires as Revealed by in Situ Transmission Electron Microscopy.

Aluminum nitride (AlN) has a unique combination of properties, such as high chemical and thermal stability, nontoxicity, high melting point, large energy band gap, high thermal conductivity, and intensive light emission. This combination makes AlN nanowires (NWs) a prospective material for optoelectronic and field-emission nanodevices. However, there has been very limited information on mechanical properties of AlN NWs that is essential for their reliable utilization in modern technologies. Herein, we thoroughly study mechanical properties of individual AlN NWs using direct,  in situ bending and tensile tests inside a high-resolution TEM. Overall, 22 individual NWs have been tested, and a strong dependence of their Young's moduli and ultimate tensile strengths (UTS) on their growth axis crystallographic orientation is documented. The Young's modulus of NWs grown along the [101̅1] orientation is found to be in a range 160-260 GPa, whereas for those grown along the [0002] orientation it falls within a range 350-440 GPa. In situ TEM tensile tests demonstrate the UTS values up to 8.2 GPa for the [0002]-oriented NWs, which is more than 20 times larger than that of a bulk AlN compound. Such properties make AlN nanowires a highly promising material for the reinforcing applications in metal matrix and other composites. Finally, experimental results were compared and verified under a density functional theory simulation, which shows the pronounced effect of growth axis on the AlN NW mechanical behavior. The modeling reveals that with an increasing NW width the Young's modulus tends to approach the elastic constants of a bulk material.

Engineering Platinum-Oxygen Dual Catalytic Sites via Charge Transfer towards Highly Efficient Hydrogen Evolution.

A dual-site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual-site interfaces in single-atom system to maximize the effect. Herein, we report a cation-deficient electrostatic anchorage route to fabricate an atomically dispersed platinum-titania catalyst (Pt1 O1 /Ti1-x O2 ), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt1 O1 /Ti1-x O2 experiences a Pt-O dual-site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer-Tafel process. There is almost no decay in the activity of Pt1 O1 /Ti1-x O2 over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).

Mechanical, Electrical, and Crystallographic Property Dynamics of Bent and Strained Ge/Si Core-Shell Nanowires As Revealed by in situ Transmission Electron Microscopy.

Research on electromechanical properties of semiconducting nanowires, including plastic behavior of Si nanowires and superb carrier mobility of Ge and Ge/Si core-shell nanowires, has attracted increasing attention. However, to date, there have been no direct experimental studies on crystallography dynamics and its relation to electrical and mechanical properties of Ge/Si core-shell nanowires. In this Letter, we in parallel investigated the crystallography changes and electrical and mechanical behaviors of Ge/Si core-shell nanowires under their deformation in a transmission electron microscope (TEM). The core-shell Ge/Si nanowires were bent and strained in tension to high limits. The nanowire Young's moduli were measured to be up to ∼191 GPa, and tensile strength was in a range of 3-8 GPa. Using high-resolution imaging, we confirmed that under large bending strains, Si shells had irregularly changed to the polycrystalline/amorphous state, whereas Ge cores kept single crystal status with the local lattice strains on the compressed side. The nanowires revealed cyclically changed electronic properties and had decent mechanical robustness. Electron diffraction patterns obtained from  in situ TEM, paired with theoretical simulations, implied that nonequilibrium phases of polycrystalline/amorphous Si and ß-Sn Ge appearing during the deformations may explain the regarded mechanical robustness and varying conductivities under straining. Finally, atomistic simulations of Ge/Si nanowires showed the pronounced changes in their electronic structure during bending and the appearance of a conductive channel in compressed regions which might also be responsible for the increased conductivity seen in bent nanowires.

Photocatalysis with Pt-Au-ZnO and Au-ZnO Hybrids: Effect of Charge Accumulation and Discharge Properties of Metal Nanoparticles.

Metal-semiconductor hybrid nanomaterials are becoming increasingly popular for photocatalytic degradation of organic pollutants. Herein, a seed-assisted photodeposition approach is put forward for the site-specific growth of Pt on Au-ZnO particles (Pt-Au-ZnO). A similar approach was also utilized to enlarge the Au nanoparticles at epitaxial Au-ZnO particles (Au@Au-ZnO). An epitaxial connection at the Au-ZnO interface was found to be critical for the site-specific deposition of Pt or Au. Light on-off photocatalysis tests, utilizing a thiazine dye (toluidine blue) as a model organic compound, were conducted and confirmed the superior photodegradation properties of Pt-Au-ZnO hybrids compared to Au-ZnO. In contrast, Au-ZnO type hybrids were more effective toward photoreduction of toluidine blue to leuco-toluidine blue. It was deemed that photoexcited electrons of Au-ZnO (Au, ∼5 nm) possessed high reducing power owing to electron accumulation and negative shift in Fermi level/redox potential; however, exciton recombination due to possible Fermi-level equilibration slowed down the complete degradation of toluidine blue. In the case of Au@Au-ZnO (Au, ∼15 nm), the photodegradation efficiency was enhanced and the photoreduction rate reduced compared to Au-ZnO. Pt-Au-ZnO hybrids showed better photodegradation and mineralization properties compared to both Au-ZnO and Au@Au-ZnO owing to a fast electron discharge (i.e. better electron-hole seperation). However, photoexcited electrons lacked the reducing power for the photoreduction of toluidine blue. The ultimate photodegradation efficiencies of Pt-Au-ZnO, Au@Au-ZnO, and Au-ZnO were 84, 66, and 39%, respectively. In the interest of effective metal-semiconductor type photocatalysts, the present study points out the importance of choosing the right metal, depending on whether a photoreduction and/or photodegradation process is desired.

Torsional Resonators Based on Inorganic Nanotubes.

We study for the first time the resonant torsional behaviors of inorganic nanotubes, specifically tungsten disulfide (WS2) and boron nitride (BN) nanotubes, and compare them to that of carbon nanotubes. We have found WS2 nanotubes to have the highest quality factor (Q) and torsional resonance frequency, followed by BN nanotubes and carbon nanotubes. Dynamic and static torsional spring constants of the various nanotubes were found to be different, especially in the case of WS2, possibly due to a velocity-dependent intershell friction. These results indicate that inorganic nanotubes are promising building blocks for high-Q nanoelectromechanical systems (NEMS).

Pectin-coated boron nitride nanotubes: In vitro cyto-/immune-compatibility on RAW 264.7 macrophages.

BACKGROUND: Boron nitride nanotubes (BNNTs) represent a new opportunity for drug delivery and clinical therapy. The present work has the objective to investigate pectin-coated BNNTs (P-BNNTs) for their biocompatibility on macrophage cultures, since these cells are among the first components of the immune system to interact with administered nanoparticles. METHODS: As first step, the potential toxicity of P-BNNTs is verified in terms of proliferation, oxidative stress induction and apoptosis/necrosis phenomena. Thereafter, the modulation of immune cell response following P-BNNT exposure is evaluated at gene and protein level, in particular focusing on cytokine release. Finally, P-BNNT internalization is assessed through transmission electron microscopy and confocal microscopy. RESULTS: The results proved that P-BNNTs are not toxic for macrophages up to 50 µg/ml after 24 h of incubation. The cytokine expression is not affected by P-BNNT administration both at gene and protein level. Moreover, P-BNNTs are internalized by macrophages without impairments of the cell structures. CONCLUSIONS: Collected data suggest that P-BNNTs cause neither adverse effects nor inflammation processes in macrophages. GENERAL SIGNIFICANCE: These findings represent the first and fundamental step in immune compatibility evaluation of BNNTs, mandatory before any further pre-clinical testing.

Optical and Optoelectronic Property Analysis of Nanomaterials inside Transmission Electron Microscope.

In situ transmission electron microscopy (TEM) allows one to investigate nanostructures at high spatial resolution in response to external stimuli, such as heat, electrical current, mechanical force and light. This review exclusively focuses on the optical, optoelectronic and photocatalytic studies inside TEM. With the development of TEMs and specialized TEM holders that include in situ illumination and light collection optics, it is possible to perform optical spectroscopies and diverse optoelectronic experiments inside TEM with simultaneous high resolution imaging of nanostructures. Optical TEM holders combining the capability of a scanning tunneling microscopy probe have enabled nanomaterial bending/stretching and electrical measurements in tandem with illumination. Hence, deep insights into the optoelectronic property versus true structure and its dynamics could be established at the nanometer-range precision thus evaluating the suitability of a nanostructure for advanced light driven technologies. This report highlights systems for in situ illumination of TEM samples and recent research work based on the relevant methods, including nanomaterial cathodoluminescence, photoluminescence, photocatalysis, photodeposition, photoconductivity and piezophototronics.

Functionalized hexagonal boron nitride nanomaterials: emerging properties and applications.

Functionalization is an important way to breed new properties and applications for a material. This review presents an overview of the progresses in functionalized hexagonal boron nitride (h-BN) nanomaterials. It begins with an introduction of h-BN structural features, physical and chemical properties, followed by an emphasis on the developments of BN functionalization strategies and its emerging properties/applications, and ends with the research perspectives. Different functionalization methods, including physical and chemical routes, are comprehensively described toward fabrication of various BN derivatives, hetero- and porous structures, etc. Novel properties of functionalized BN materials, such as high water solubility, excellent biocompatibility, tunable surface affinities, good processibility, adjustable band gaps, etc., have guaranteed wide applications in biomedical, electronic, composite, environmental and "green" energy-related fields.

Hybrid two-dimensional materials in rechargeable battery applications and their microscopic mechanisms.

Integration of two-dimensional (2D) nanomaterials and their composites into energy storage devices, especially rechargeable batteries, offers opportunities to timely tackle the challenges of ever growing clean and sustainable energy demands. Therefore, it is crucial to design hybrid 2D electrode materials for high performance rechargeable batteries and to fundamentally understand their storage mechanisms at the atomic or nanoscopic levels. This review firstly describes some of the exciting progress achieved in the economic production of graphenes, 2D transition metal dichalcogenides (TMDCs), and their composites. Then we survey the recent developments in their electrochemical energy storage pathways and present the associated three kinds of storage mechanisms. In addition, we highlight the uncovered structure-performance relationships while utilizing advanced microscopic techniques, such as in situ high resolution transmission electron microscopy (TEM) and spherical aberration-corrected scanning TEM (STEM), both leading to deep unveiling and understanding of the atomic-scale ion storage/release mechanisms and hence providing clear guidance for designing optimized 2D nanostructured electrode materials. Finally, the major challenges and opportunities that researchers have to face in this field are outlined. We hope that this review can deepen the Chemical and Material Science Communities' understanding of this field and thus effectively contribute to the smart design of future-generation 2D nanostructured electrodes and exploitation of their microscopic mechanisms toward novel high-performance rechargeable batteries.

In situ fabrication and investigation of nanostructures and nanodevices with a microscope.

The widespread availability of nanostructures and nanodevices has placed strict requirements on their comprehensive characterization. Herein, in situ techniques are demonstrated to have created a rare opportunity to accurately analyze the intrinsic properties of individual nanostructures and to accomplish the smart design of nanodevices made from these nanostructures. This paper reviews recent developments in in situ fabrication and characterization technologies established within various types of microscopes and the rich information they may provide. The in situ techniques are shown to be important for exploration of many intriguing phenomena at the nanoscale which may then be followed by the smart integration of nanostructures into real functional devices. Successful in situ detection results are presented and discussed, especially in the areas of energy generation, biological imaging and water pumping. Finally, we conclude this article with an examination of the existing challenges and the outlook for this quickly emerging field.