Advanced Strategies to Improve Performances of Molybdenum-Based Gas Sensors

Molybdenum-based materials have been intensively investigated for high-performance gas sensor applications.Particularly,molybdenum oxides and dichalcogenides nanostructures have been widely examined due to their tunable structural and physicochemical properties that meet sensor requirements.These materials have good durability,are naturally abundant,low cost,and have facile preparation,allowing scalable fabrication to fulfill the growing demand of susceptible sensor devices.Significant advances have been made in recent decades to design and fabricate various molybdenum oxides-and dichalcogenides-based sensing materials,though it is still challenging to achieve high performances.Therefore,many experimental and theoretical investigations have been devoted to exploring suitable approaches which can significantly enhance their gas sensing properties.This review comprehensively examines recent advanced strategies to improve the nanostructured molybdenum-based material performance for detecting harmful pollutants,dangerous gases,or even exhaled breath monitoring.The summary and future challenges to advance their gas sensing performances will also be presented.

Charge Storage Properties of Aqueous Halide Supercapatteries with Activated Carbon and Graphene Nanoplatelets as Active Electrode Materials

Device level performance of aqueous halide supercapatteries fabricated with equal electrode mass of activated carbon or graphene nanoplatelets has been characterized.It was revealed that the surface oxygen groups in the graphitic structures of the nanoplatelets contributed toward a more enhanced charge storage capacity in bromide containing redox electrolytes.Moreover,the rate performance of the devices could be linked to the effect of the pore size of the carbons on the dynamics of the inactive alkali metal counterion of the redox halide salt.Additionally,the charge storage performance of aqueous halide supercapatteries with graphene nanoplatelets as the electrode material may be attributed to the combined effect of the porous structure on the dynamics of the non-active cations and a possible interaction of the Br^(-)/(Br_(2)+Br^(-)_(3))redox triple with the surface oxygen groups within the graphitic layer of the nanoplatelets.Generally,it has been shown that the surface groups and microstructure of electrode materials must be critically correlated with the redox electrolytes in the ongoing efforts to commercialize these devices.

Synthesis and applications of MOF-derived porous nanostructures

Metal organic frameworks(MOFs) represent a class of porous material which is formed by strong bonds between metal ions and organic linkers. By careful selection of constituents, MOFs can exhibit very high surface area, large pore volume, and excellent chemical stability.Research on synthesis, structures and properties of various MOFs has shown that they are promising materials for many applications, such as energy storage, gas storage, heterogeneous catalysis and sensing. Apart from direct use, MOFs have also been used as support substrates for nanomaterials or as sacrificial templates/precursors for preparation of various functional nanostructures. In this review, we aim to present the most recent development of MOFs as precursors for the preparation of various nanostructures and their potential applications in energy-related devices and processes. Specifically, this present survey intends to push the boundaries and covers the literatures from the year 2013 to early 2017,on supercapacitors, lithium ion batteries, electrocatalysts, photocatalyst, gas sensing, water treatment, solar cells, and carbon dioxide capture.Finally, an outlook in terms of future challenges and potential prospects towards industrial applications are also discussed.

Optical Investigation of Sm^(3+) Doped Zinc-Lead-Phosphate Glass

Samarium doped lead-zinc-phosphate glasses having composition(60-x)P_(2)O_(5)-20PbO-20ZnO-xSm_(2)O_(3) where x=0,0.5,1.0,3.0mol%were prepared by using the melt quenching technique.The Archimedes method was used to measure their densities,which are used to calculate the molar volumes.The values of densities lie in the range 3.698–4.090 gm/cm^(3) whereas those of molar volume lie in the range of 37.24–40.00 cm^(-3).UV-vis-NIR absorption spectroscopy in the wavelength range 200–2000 nm was carried out.Absorption spectra consist of seven absorption peaks corresponding to the transitions from the 6H5/2 ground state to various excited energy levels.The energy band gap measured from the optical absorbance is found to be in the range of 3.88–4.43 eV and 3.68–4.33 eV for direct and indirect transitions,respectively.In addition,the photoluminescence spectrum shows four prominent emission bands centered at 560,597,642 and 700 nm corresponding to the 4G5/2–6HJ(J=5/2,7/2,9/2,11/2)transitions respectively and the intensity of all the bands are enhanced as the concentration of Sm3+ions increases.

The Oleic Acid Composition Effect on the Carboxymethyl Cellulose Based Biopolymer Electrolyte

Biopolymer electrolyte based on carboxymethyl cellulose has been prepared by doping with different concentration of oleic acid via solution casting technique. Fourier Transform Infrared spectroscopy was used to study the complexation between the salt and polymer. New peak was observed at 1710, 2850, 2920 cm-1. X-ray diffraction study reveals the amorphous nature of the biopolymer electrolyte. Impedance study shows the highest ionic conductivity, σ, was found to be 2.11 × 10-5 S·cm-1 at room temperature (303 K) for sample containing 20 wt.% of oleic acid and the biopolymer electrolyte obeys Arrhenius behaviour.

Phase modification and dielectric properties of a cullet–paper ash–kaolin clay-based ceramic

Novel ceramics from waste material made of(x) paper ash–(80-x) cullet–20 kaolin clay(10 wt% ≤ x ≤ 30 wt%) were successfully synthesized using a conventional solid-state reaction technique. Energy-dispersive X-ray analysis confirmed the presence of Si, Ca, Al, and Fe in the waste material for preparing these ceramics. The influence of the cullet content on the phase structures and the dielectric properties of these ceramics were systematically investigated. The impedance spectra were verified in the range from 1 Hz to 10 MHz at room temperature. The phase of the ceramics was found to primarily consist of wollastonite(CaSiO_3), along with minor phases of γ-dicalcium silicate(Ca_2SiO_4) and quartz(SiO_2). The sample with a cullet content of 55 wt% possessed the optimum wollastonite structure and exhibited good dielectric properties. An increase of the cullet content beyond 55 wt% resulted in a structural change from wollastonite to dicalcium silicate, a decrease in dielectric constant, and an increase in dielectric loss. All experimental results suggested that these novel ceramics from waste are applicable for electronic devices.

Tailoring the degradation rate of magnesium through biomedical nano-porous titanate coatings

A novel approach was developed to reduce the corrosion rate of magnesium(Mg)metal,utilising titanate coatings.Magnetron sputtering was used to deposit ca.500 nm titanium(Ti)coatings onto pure Mg discs,followed by hydrothermal conversion and ion exchange reactions to produce sodium and calcium titanate coatings.SEM confirmed the characteristic nanoporous structure of sodium and calcium titanate,with thicknesses ranging from ca.0.8 to 1.4μm.XPS analysis confirmed the presence of Ti^(4+)-O,Na-O,and Ca-O bonding,whilst Raman spectroscopy demonstrated characteristic vibrational modes(such as TiO 6 octahedral vibrations)of the sodium and calcium titanate perovskite structure.Furthermore,corrosion studies through potentiodynamic polarisation measurements demonstrated the NB/NH CaTC samples to be superior in reducing Mg degradation,compared to other samples tested,through an increase in E_(corr)from-1.49 to-1.33 V,and the reduction in corrosion current density,i corr,from 0.31 to 0.06 mA/cm^(2)for Mg and NB/NH CaTC samples,respectively.There was a clear trend noted for the NB/NH samples,which showed an increase in E corr to more positive values in the following order:Mg<Ti coated<NaTC<CaTC.These nanoporous titanate coatings have potential to be applied onto degradable plates for bone fracture fixation,or other orthopaedic applications.

Germanium nanoislands grown by radio frequency magnetron sputtering: Annealing time dependent surface morphology and photoluminescence

Structural and optical properties of ～ 20 nm Ge nanoislands grown on Si（100） by radio frequency （rI） magnetron sputtering under varying annealing conditions are reported. Rapid thermal annealing at a temperature of 600 ℃ for 30 s, 90 s, and 120 s are performed to examine the influence of annealing time on the surface morphology and photoluminescence properties. X-ray diffraction spectra reveal prominent Ge and GeO2 peaks highly sensitive to the annealing time. Atomic force microscope micrographs of the as-grown sample show pyramidal nanoislands with relatively high-density （～ 10^11 cm^-2）. The nanoislands become dome-shaped upon annealing through a coarsening process mediated by Oswald ripening. The room temperature photoluminescence peaks for both as-grown （～ 3.29 eV） and annealed （～ 3.19 eV） samples consist of high intensity and broad emission, attributed to the effect of quantum confinement. The red shift （～ 0.10 eV） of the emission peak is attributed to the change in the size of the Ge nanoislands caused by annealing. Our easy fabrication method may contribute to the development of Ge nanostructure-based optoelectronics.

Dielectric Function of Silicon Nanoclusters: Role of Hydrogen

Electronic and optical properties of small silicon quantum dots having 3 to 44 atoms per dot with and without surface passivation are investigated by computer simulation using the pseudo-potential approach.An empirical pseudo-potential Hamiltonian,a plane-wave basis expansion and a basic tetrahedral structure with undistorted local bonding configurations are used.The structures of the quantum dots are relaxed and optimized before and after hydrogen passivation.It is found that the gap increases more for a hydrogenated surface than the unpassivated one.Thus,both quantum confinement and surface passivation determine the optical and electronic properties of Si quantum dots.Visible luminescence is probably due to the radiative recombination of electrons and holes in the quantum-confined nanostructures.The effect of passivation of the surface dangling bonds by hydrogen atoms and the role of surface states on the gap energy is also examined.The results for the density of states,the dielectric function,the frequency dependent optical absorption cross section,the extinction coefficient and the static dielectric constants of the size are presented.The importance of the confinement and the role of surface passivation on the optical effects are discussed.

Effects of annealing temperature on shape transformation and optical properties of germanium quantum dots

The influences of thermal annealing on the structural and optical features of radio frequency（rf） magnetron sputtered self-assembled Ge quantum dots（QDs） on Si（100） are investigated.Preferentially oriented structures of Ge along the（220） and（111） directions together with peak shift and reduced strain（4.9%to 2.7%） due to post-annealing at 650 ℃ are discerned from x-ray differaction（XRD） measurement.Atomic force microscopy（AFM） images for both pre-annealed and post-annealed（650 ℃） samples reveal pyramidal-shaped QDs（density - 0.26×10^11 cm^-2） and dome-shape morphologies with relatively high density - 0.92×10^11 cm^-2,respectively.This shape transformation is attributed to the mechanism of inter-diffusion of Si in Ge interfacial intermixing and strain non-uniformity.The annealing temperature assisted QDs structural evolution is explained using the theory of nucleation and growth kinetics where free energy minimization plays a pivotal role.The observed red-shift - 0.05 eV in addition to the narrowing of the photoluminescence peaks results from thermal annealing,and is related to the effect of quantum confinement.Furthermore,the appearance of a blue-violet emission peak is ascribed to the recombination of the localized electrons in the Ge-QDs/SiO2 or GeOx and holes in the ground state of Ge dots.Raman spectra of both samples exhibit an intense Ge-Ge optical phonon mode which shifts towards higher frequency compared with those of the bulk counterpart.An experimental Raman profile is fitted to the models of phonon confinement and size distribution combined with phonon confinement to estimate the mean dot sizes.A correlation between thermal annealing and modifications of the structural and optical behavior of Ge QDs is established.Tunable growth of Ge QDs with superior properties suitable for optoelectronic applications is demonstrated.

Plasmon-Enhanced Upconversion Fluorescence in Er^(3+):Ag Phosphate Glass:the Effect of Heat Treatment

The melt quenching method is used to prepare erbium-doped silver nanoparticle(NP)embedded phosphate glass.The effect of annealing on the glass on the formation of silver NPs produced by the reduction of silver(Ag^(+)→Ag^(o))is studied.The glass samples are characterized by x-ray diffraction,UV-vis-NIR absorption,photoluminescence spectroscopy and transmission electron microscopy(TEM)imaging.The absorption spectra reveal not only the peaks due to Er^(3+)ions,but also the surface plasmon resonance band of silver NPs located around~442 nm.The TEM imaging shows the homogeneous distribution of silver NPs of almost spherical shape with an average diameter of~5 nm.Upconversion luminescence spectra show two major emissions at 550 and 638 nm,originating from the 4S_(3/2)and 4F_(9/2)energy levels of the Er^(3+)ions,respectively.The enhancement in the luminescence intensity of both the green and red bands is found to be due to the effective local field of the silver NPs as well as the energy transfer from the nanoclusters,comprised of centers with silver ions bound to silver atoms in dimers or trimers to Er^(3+)ions,whereas quenching occurred due to the energy transfer from erbium ions to silver NPs(Er^(^(3^(+)))→Ag^(o)).

Structural and Optical Behavior of Germanium Quantum Dots

Controlled growth,synthesis,and characterization of a high density and large-scale Ge nanostructure by an easy fabrication method are key issues for optoelectronic devices.Ge quantum dots(QDs)having a density of~1011 cm^(-2) and a size as small as~8 nm are grown by radio frequency magnetron sputtering on Si(100)substrates under different heat treatments.The annealing temperature dependent structural and optical properties are measured using AFM,XRD,FESEM,EDX,photoluminescence(PL)and Raman spectroscopy.The effect of annealing is found to coarsen the Ge QDs from pyramidal to dome-shaped structures as they grow larger and transform the nanoislands into relatively stable and steady state configurations.Consequently,the annealing allows the intermixing of Si into the Ge QDs and thereby reduces the strain energy that enhances the formation of larger nanoislands.The room temperature PL spectra exhibits two strong peaks at~2.87 eV and~3.21 eV attributed to the interaction between Ge,GeO_(x) and the possibility of the presence of QDs core-shell structure.No reports so far exist on the red shift~0.05 eV of the strongest PL peak that results from the effect of quantum confinement.Furthermore,the Raman spectra for the pre-annealed QDs that consist of three peaks at around~305.25 cm^(-1),409.19 cm^(-1) and 515.25 cm^(-1) are attributed to Ge-Ge,Ge-Si,and Si-Si vibration modes,respectively.The Ge-Ge optical phonon frequency shift(~3.27 cm^(-1))associated with the annealed samples is assigned to the variation of shape,size distribution,and Ge composition in different QDs.The variation in the annealing dependent surface roughness and the number density is found to be in the range of~0.83 to~2.24 nm and~4.41 to~2.14×10^(11)cm^(-2),respectively.

Growth of Ge/Si(100) Nanostructures by Radio-Frequency Magnetron Sputtering: the Role of Annealing Temperature

Surface morphologies of Ge islands deposited on Si(100) substrates are characterized and their optical properties determined.Samples are prepared by rf magnetron sputtering in a high-vacuum chamber and are annealed at 600℃,700℃ and 800℃ for 2 min at nitrogen ambient pressure.Atomic force microscopy,field emission scanning electron microscopy,visible photoluminescence (PL) and energy dispersive x-ray spectroscopy are employed.The results for the annealing temperature-dependent sample morphology and the optical properties are presented.The density,size and roughness are found to be strongly influenced by the annealing temperature.A red shift of ~0.29 eV in the PL peak is observed with increasing annealing temperature.

Nitrogen-Doped Amorphous Carbon Homojunction from Palmyra Sugar as a Renewable Solar Cell

An a-C/a-C:N junction,which used palmyra sugar as the carbon source and ammonium hydroxide(NH4OH)as the dopant source,was successfully deposited on the ITO glass substrate using the nano-spraying method.The current-voltage relationship of the junction was found to be a Schottky-like contact,and therefore the junction shows the characteristic rectifiers.This means the a-C and a-C:N are semiconductors with different types of conduction.Moreover,the samples showed an increase in current and voltage value when exposed to visible light(bright state)compared to the dark condition,thereby,indicating the creation of electron-hole pairs during the exposure.It was also discovered that the relationship between current and voltage for the a-C/a-C:N junction sample formed a curve that satisfies the rule of the photovoltaic effect when exposed to visible light from a light bulb.The exposure of this sample to direct sunlight at AM 1.5 conditions produced a curve that meets the rules for the emergence of the photovoltaic effect with higher characteristics for the current-voltage relationship.Thus,the a-C/a-C:N junction sample is a solar cell successfully fabricated using a sample method and has a maximum efficiency of 0.0013%.

9,10-Bis(diphenylmethylene)-9,10-dihydroanthracene-based metal-organic assemblies with aggregation-induced emission for multiple sensing

Developing novel emissive supramolecular assemblies with elegant architectures and tunable perfor-mance remains highly desirable yet challenging.Herein,we report the design and synthesis of several 9.10-bis(diphenylmethylene)-9.10-dihydroanthracene-based metal organic assembles with aggregation-induced emission characteristics.Such assemblies feature intriguing thermochromic and mechanochromic properties,ie.,distinguishable fuorescence responses in terms of emission wavelength and intensity un-der variable temperatures and pressures.Moreover,these assemblies can serve as excellent fluorescent sensors for the detection of polysaccharide molecules.Due to the differentiated charge type and den-sity,the assembles display distinct sensing mechanisms toward different polysaccharide molecules.This study provides novel perspectives for the synthesis of buttrfly-like platinum(I)supramolecular coordi-nation complexes with multistimuli-responsiveness for polysaccharide sensing.which will facllitate the development of stimuli-responsive materials.

Spectral investigation of Sm^(3+)/Yb^(3+) co-doped sodium tellurite glass

Sm3＋/yb3＋ co-doped tellurite glasses are prepared by melt-quenching technique. The density of the glasses varies between 4.65 and 4.84 g/cm3. The optical absorption spectra consist of eight bands in the wavelength range of 350-2 000 nm, which correspond to the transitions from ground level 6H5/2 to the various excited states of the Sm3＋ ion. Energy band gaps vary in the range of 2.73 2.91 eV, and the Urbach energy ranges from 0.21 to 0.27. Emission spectra exhibit four peaks originating from the 4G5/2 energy level centered at 576, 613, 657, and 718 nm. Quenches in emission bands may be due to the energy transfer from the Sm3＋ to Yb3＋ ions.

Understanding bottom-up continuous hydrothermal synthesis of nanoparticles using empirical measurement and computational simulation

Continuous hydrothermal synthesis was highlighted in a recent review as an enabling technology for the production of nanoparticles. In recent years, it has been shown to be a suitable reaction medium for the synthesis of a wide range of nanomaterials. Many single and complex nanomaterials such as metals, metal oxides, doped oxides, carbonates, sulfides, hydroxides, phosphates, and metal organic frameworks can be formed using continuous hydrothermal synthesis techniques. This work presents a methodology to characterize continuous hydrothermal flow systems both experimentally and numerically, and to determine the scalability of a counter current supercritical water reactor for the large scale production （〉1,000 T-year-1） of nanomaterials. Experiments were performed using a purpose-built continuous flow rig, featuring an injection loop on a metal salt feed line, which allowed the injection of a chromophoric tracer. At the system outlet, the tracer was detected using UV/Vis absorption, which could be used to measure the residence time distribution within the reactor volume. Computational fluid dynamics （CFD） calculations were also conducted using a modeled geometry to represent the experimental apparatus. The performance of the CFD model was tested against experimental data, verifying that the CFD model accurately predicted the nucleation and growth of the nanomaterials inside the reactor.

Optical behavior of self-assembled high-density Ge nanoislands embedded in SiO_2

The radio frequency magnetron sputtering method is used to prepare well-dispersed pyramidal-shaped Ge nanoislands embedded in amorphous SiO2 sublayers of various thicknesses. The estimated size and number density of Ge nanoislands in SiO2 sublayer thicknesses beyond 30 nm are approximately 15 nm and 1011 cm-2, respectively. Atomic force microscopy （AFM） reveals root mean square （RMS） roughness sensitivity as the SiO2 sublayer thickness varies from 30 to 40 nm. The formation of nanoislands with high aspect ratios is attributed to the higher rate of surface reactions between Ge adatoms and nucleated Ge islands than reactions associated with SiO2 and Ge. The Ge nanoisland polyorientation on SiO2 （50-nm thickness） is revealed by X-ray diffraction （XRD） patterns. Photoluminescence （PL） peaks of 2.9 and 1.65 eV observed at room temperature （RT） are attributed to the radiative recombination of electrons and holes from the Ge nanoislands/SiO2 and Si02/Si interfaces, respectively. The mean island sizes are determined by fitting the experimental Raman profile to two models, namely, the phonon confinement model and the size distribution combined with phonon confinement model. The latter model yields the best fit to the experimental data. We confirm that SiO2 matrix thickness variations play a significant role in the formation of Ge nanoislands mediated via the minimization of interfacial and strain energies. OCIS codes： 250.5230, 170.5660.