Controllable,Wide‐Ranging n‐Doping and p‐Doping of Monolayer Group 6 Transition‐Metal Disulfides and Diselenides

Developing processes to controllably dope transition‐metal dichalcogenides (TMDs) is critical for optical and electrical applications. Here, molecular reductants and oxidants are introduced onto monolayer TMDs, specifically MoS₂, WS₂, MoSe₂, and WSe₂. Doping is achieved by exposing the TMD surface to solutions of pentamethylrhodocene dimer as the reductant (n‐dopant) and “Magic Blue,” [N(C₆H₄‐p‐Br)₃]SbCl₆, as the oxidant (p‐dopant). Current–voltage characteristics of field‐effect transistors show that, regardless of their initial transport behavior, all four TMDs can be used in either p‐ or n‐channel devices when appropriately doped. The extent of doping can be controlled by varying the concentration of dopant solutions and treatment time, and, in some cases, both nondegenerate and degenerate regimes are accessible. For all four TMD materials, the photoluminescence intensity; for all four materials the PL intensity is enhanced with p‐doping but reduced with n‐doping. Raman and X‐ray photoelectron spectroscopy (XPS) also provide insight into the underlying physical mechanism by which the molecular dopants react with the monolayer. Estimates of changes of carrier density from electrical, PL, and XPS results are compared. Overall a simple and effective route to tailor the electrical and optical properties of TMDs is demonstrated.     

Recent advances in metals and metal oxides as catalysts for vanadium redox flow battery:Properties,structures,and perspectives

Vanadium redox flow battery(VRFB)is a kind of battery with wide application prospect.Electrode mate-rial is one of the key components of VRFB,and its stability directly affects the performance of battery.Among all kinds of electrode materials,carbon-based material has the best comprehensive properties.However,carbon-based electrodes still have disadvantages such as poor hydrophilicity and low electro-chemical activity which need to be improved.One of the effective ways to improve the performance of electrode is to modify carbon-based material with metals and metal oxides.The metal catalysts have excellent electrical conductivity and high catalytic activity.The metal oxide catalysts have the advan-tages of low cost,wide variety and strong oxidizing properties.This work introduced the application of metal and metal oxide modified electrodes in VRFB in recent years,classified the catalysts,studied their catalytic performance and mechanism.The metal catalysts were reviewed from precious metals and base metals.The metal oxide catalysts were classified and discussed according to the similar proper-ties of the same group elements.This work compared different modification methods,summarized the research progress of metal and metal oxide modification,and proposes the future development direction of electrodes and catalysts.     

4He Impurities in 3He: Energetics and Dynamics

We have developed the optimized Fermi Hypernetted Chain Theory of a single impurity atom in a Fermi liquid, and have applied the theory to a ⁴He atom in bulk ³He. Previous applications of the theory for one component have produced excellent agreement with the experimental equation of state of ⁴He; the resulting equation of state of bulk ³He is about 0.4 K above the experimental one. Within the same theory, we obtain the pressure dependence of the chemical potential of ⁴He in bulk ⁴He, ³He in ³He, as well as the chemical potential of a ⁴He impurity in ³He. The pressure dependence of the impurity chemical potential agrees well with the experimental data, but we have a constant energy offset of about 1.2 K that disallows conclusive statements. This offset is partly explained by the relative inaccuracy of the ³He equation of state. We then calculate the self-energy of a single ⁴He impurity in ³He. Our results for the effective mass m^* ₄ fall within the experimental error of the best available data; they increase from about m^* ₄/m₄1.4 at zero pressure, to m^* ₄/m₄1.6 at p=20 atm. We show that this effective mass enhancement is, to about equal parts, due to hydrodynamic backflow and to the coupling to particle-hole excitations. When the latter are turned off in the collective approximation of the impurity-background correlations one obtains a significantly lower effective mass, m^* ₄/m₄1.2–1.35.     

Investigation of red-emission phosphors (Ca,Sr)(Mo,W)O:Eu crystal structure, luminous characteristics and calculation of EuD0 quantum efficiency

By sol-gel method, (Ca_0.54, Sr_0.34)(Mo_0.2, W_0.8)O₄: Eu³⁺_0.08 luminescent materials can be synthesized. X-ray diffraction analysis indicates that it owns tetragonal scheelite structure, belonging to I-center with space group I4₁/a [88], Z = 4. The emission spectra, excitation spectra and fluorescence decay curves are measured, and the partial Judd-Ofelt parameters and, under 395 nm excitation, quantum efficiency of Eu^{3+ 5}D₀ energy level are calculated. The results indicate that Eu^{3+ 5}D₀-⁷F₂ red luminescence can be excited by 395 nm, 465 nm and 535 nm in the hosts, respectively, and its quantum efficiency can be improved in space and it has potential application for white light emitting diodes as the red luminescent materials.     

Protein‐Directed Synthesis of NIR‐Emitting,Tunable HgS Quantum Dots and their Applications in Metal‐Ion Sensing

The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio‐mineralization process has remained unexplored. Herein, a simple, two‐step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV–vis spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X‐ray analysis (EDX), and picosecond‐resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680–800 nm spectral regions, with a quantum yield of 4–5%. The as‐prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein‐capped HgS QDs would provide additional impetus to explore applications for these materials.     

Understanding excitation energy transfer in metalloporphyrin heterodimers with different linkers,bonding structures,and geometries through stimulated X-ray Raman spectroscopy

We present simulations of stimulated X-ray Raman (SXRS) signals from covalently bonded porphyrin heterodimers with different linkers, chemical bonding structures, and geometries. The signals are interpreted in terms of valence electron wavepacket motion. One- and two-color SXRS signals can both mark excitation energy transfer (EET) between the porphyrin monomers. It is shown that the SXRS signals provide a novel window into EET dynamics in multiporphyrin systems, and can be used as a powerful tool to monitor the subtle chemical environment which affects EET.     

Critical assessment: opportunities in developing semi-solid processing: aluminium,magnesium, and high-temperature alloys

Semi-solid metal processing (SSM) is a modern metal forming technology offering net-shape metal components of complex geometry in a one-step operation. The process relies on the thixotropic behaviour of metals with non-dendritic microstructures in a wide semi-solid temperature range. The beneficial effects are currently exploited in aluminium and magnesium alloys. This alternative manufacturing route to casting and forging has generated high expectations regarding high melting alloys, although no conclusive results have been achieved so far. Current studies focus on a deep understanding of the fundamental basics of alloys in the semi-solid range, e.g. rheology, microstructural evolution, and the consequences of forming, e.g. relations between process parameters, microstructure, and properties. This critical assessment aims at defining the important needs for further development of SSM, and assessing current knowledge.     

Potential energy of two structures of Σ = 110 1 1 tilt grain boundary in silicon and germanium with empirical potentials and tight-binding methods

Two atomic structures A and B of the Σ = 110 1 1 grain boundary were observed in silicon and germanium. We have performed a complete study of the stability of these two grain boundaries using some empirical potentials and also the semiempirical, tight-binding (TB) method. The TB method has confirmed the experimental observations at low temperatures. The A structure is more stable in silicon whereas for germanium the B structure is obtained. The empirical potentials, such as those of Keating (1966), Baraff et al. (1980) and of Stillinger and Weber (1985), give the A structure as the most stable for both germanium and silicon. The non-ability of these empirical potentials to make a difference between germanium and silicon and the advantage of TB method are discussed.     

Entrapment of enzymes and carbon nanotubes in biologically synthesized silica: glucose oxidase-catalyzed direct electron transfer

This work demonstrates a new approach for building bioinorganic interfaces by integrating biologically derived silica with single-walled carbon nanotubes to create a conductive matrix for immobilization of enzymes. Such a strategy not only allows simple integration into biodevices but presents an opportunity to intimately interface an enzyme and manifest direct electron transfer features. Biologically synthesized silica/carbon nanotube/enzyme composites are evaluated electrochemically and characterized by means of X-ray photoelectron spectroscopy. Voltammetry of the composites displayed stable oxidation and reduction peaks at an optimal potential close to that of the FAD/FADH(2) cofactor of immobilized glucose oxidase. The immobilized enzyme is stable for a period of one month and retains catalytic activity for the oxidation of glucose. It is demonstrated that the resulting composite can be successfully integrated into functional bioelectrodes for biosensor and biofuel cell applications.     

On using exponential basis functions for laminates modeled by CLPT,FSDT and TSDT: Further tests and results

In this paper we present some results from the application of a mesh-free method introduced previously (Compos Struct 2011;93:3112–9 and 94:84–91) for bending analysis of laminated composite plates. This method is applicable to a wide range of bending problems without limitation in the stacking sequence of the laminated plates and the boundary conditions. Herein, two specific types of problems, having traction free boundaries, are examined and the issues related to the solution of them are addressed. Also as new benchmark problems, some more results for cross-ply and angle-ply composites are presented.     

A Systematic Approach for Multidimensional,Closed-Form Analytic Modeling: Minority Electron Mobilities in Ga1?xAlxAs Heterostructures

A significant, practical challenge, which arises in developing computationally efficient physical models for use in computer simulations of microelectronic and optoelectronic devices (for example, transistors in digital cellular phones and lasers in optical networks, respectively), is to represent vast amounts of numerical data for transport properties in two or more dimensions in terms of closed form analytic expressions. In this paper, we present a general methodology to achieve the above goal for a class of numerical data in a bounded two-dimensional space. We then apply this methodology to obtain a closed-form analytic expression for the minority electron mobilities at 300 K in p-type Ga_1−xAl_xAs as functions of the acceptor density N_A between 10¹⁶ cm⁻³ and 10²⁰ cm⁻³ and the mole fraction of AlAs x between 0.0 and 0.3. This methodology and its associated principles, strategies, regression analyses, and graphics are expected to be applicable to other problems beyond the specific case of minority mobilities addressed in this paper.     

Theory construction in design research: criteria: approaches, and methods

Design involves solving problems, creating something new, or transforming less desirable situations to preferred situations. To do this, designers must know how things work and why. Understanding how things work and why requires us to analyze and explain. This is the purpose of theory. The article outlines a framework for theory construction in design. This framework will clarify the meaning of theory and theorizing. It will explain the nature and uses of theory as a general concept. It will propose necessary and sufficient conditions for theory construction in design. Finally, it will outline potential areas for future inquiry in design theory.     

Boosting Catalysis of Pd Nanoparticles in MOFs by Pore Wall Engineering: The Roles of Electron Transfer and Adsorption Energy

The chemical environment of metal nanoparticles (NPs) possesses significant influence on their catalytic performance yet is far from being well understood. Herein, tiny Pd NPs are encapsulated into the pore space of metal–organic frameworks (MOFs), UiO-66-X (X = H, OMe, NH₂, 2OH, 2OH(Hf)), affording Pd@UiO-66-X composites. The surface microenvironment of the Pd NPs is readily modulated by pore wall engineering, via the functional group and metal substitution in the MOFs. Consequently, the catalytic activity of Pd@UiO-66-X follows the order of Pd@UiO-66-OH > Pd@UiO-66-2OH(Hf) > Pd@UiO-66-NH₂ > Pd@UiO-66-OMe > Pd@UiO-66-H toward the hydrogenation of benzoic acid. It is found that the activity difference is not only ascribed to the distinct charge transfer between Pd and the MOF, but is also explained by the discriminated substrate adsorption energy of Pd@UiO-66-X (–OH < –2OH(Hf) < –NH₂ < –OMe < –H), based on CO-diffuse reflectance infrared Fourier transform spectra and density-functional theory (DFT) calculations. The Pd@UiO-66-OH, featuring a high Pd electronic state and moderate adsorption energy, displays the highest activity. This work highlights the influence of the surface microenvironment of guest metal NPs, the catalytic activity of which is dominated by electron transfer and the adsorption energy, via the systematic substitution of metal and functional groups in host MOFs.     

Cracks,microcracks and fracture in polymer structures: Formation,detection, autonomic repair

Polymers and polymer composites are susceptible to premature failure due to the formation of cracks and microcracks during their service time. Evolution of cracks and microcracks could induce catastrophic material failure. Therefore, the detection/diagnostics and effective repair of cracks and microcracks are vital for ensuring the performance reliability, cost effectiveness and safety for polymer structures. Cracks and microcracks, however, are difficult to detect and often repair processes are complex. Biologically inspired self-healing polymer systems with inherent ability to repair damage have the potential to autonomically repair cracks and microcracks. This article is a review on the latest developments on the topics of cracks and microcracks initiation and propagation in polymer structures and it discusses the current techniques for detection and observation. Furthermore, cracks and microcrack repair through bio-mimetic self-healing techniques is discussed along with surface active protection. A separate section is dedicated to fracture analysis and discusses in details fracture mechanics and formation.     

A mesh-free method using exponential basis functions for laminates modeled by CLPT, FSDT and TSDT – Part II: Implementation and results

In this part of the paper we give the details of the implementation of the method presented in the first part. Also the solutions of several benchmark plate problems with various geometries are presented to validate the results. It has been observed that the method can perform excellently in a wide range of problems defined for the bending analysis of laminated plates based on various plate theories. For further use, some explicit expressions are given for the exponential basis functions suitable for the solution of symmetric cross-ply laminates.     

Advances in triboelectric nanogenerator powered electrowetting-on-dielectric devices: Mechanism,structures, and applications

Electrowetting-on-dielectric (EWOD) phenomenon is widely employed for liquid actuation at the micro scale. Due to its simple structure, low cost, low power consumption and fast response speed, diverse applications are developed and commercialized based on EWOD, such as digital microfluidics, tunable lenses, electronic displays, small-scale propellers etc. However, the liquid actuation with EWOD requires a high-voltage but low-current power source. The accessory equipment (e.g., waveform generator and amplifier) not only attenuates the benefits originated from microscale liquid actuation, but also limits its portability, wearability, and environmental friendliness of the EWOD inspired applications. Triboelectric nanogenerator (TENG) is a promising technology to convert arbitrary mechanical energy to electricity based on triboelectrification and electrostatic induction. The output electric signal shows a high-voltage but low-current property which well matches the demands in EWOD devices. This paper reviews the technical advances in the TENG powered EWOD devices developed in recent years. The mechanisms, structures, and performance of each application are reviewed. The challenges and future perspectives are put forward. The review and discussion in this study open up opportunities for the development of TENG and EWOD based self-powered liquid actuators.     

Functional gradients and heterogeneities in biological materials: Design principles,functions, and bioinspired applications

Living organisms have ingeniously evolved functional gradients and heterogeneities to create high-performance biological materials from a fairly limited choice of elements and compounds during long-term evolution and selection. The translation of such design motifs into synthetic materials offers a spectrum of feasible pathways towards unprecedented properties and functionalities that are favorable for practical uses in a variety of engineering and medical fields. Here, we review the basic design forms and principles of naturally-occurring gradients in biological materials and discuss the functions and benefits that they confer to organisms. These gradients are fundamentally associated with the variations in local chemical compositions/constituents and structural characteristics involved in the arrangement, distribution, dimensions and orientations of the building units. The associated interfaces in biological materials invariably demonstrate localized gradients and a variety of gradients are generally integrated over multiple length-scales within the same material. The bioinspired design and applications of synthetic functionally graded materials that mimic their natural paradigms are revisited and the emerging processing techniques needed to replicate the biological gradients are described. It is expected that in the future bioinspired gradients and heterogeneities will play an increasingly important role in the development of high-performance materials for more challenging applications.