Structure,dielectric properties of novel Ba(Zr,Ti)O3 based ceramics for energy storage application

(1-x) Ba(Zr_0.2Ti_0.8)O₃-x Na_0.5Bi_0.5TiO₃ (x = 0, 10, 20 30, 40, 50 mol%) (BZTN) ceramics are prepared by the traditional solid phase method. All BZTN ceramics exhibit a pseudo-cubic BZT based perovskite structure. Both the average grain size and the relaxor ferroelectricity of BZTN ceramics gradually increase with increasing NBT content. The W_rec of 3.22 J/cm³ and η of 91.2% is obtained for the BZTN40 ceramic at 241 kV/cm. BZTN40 ceramic also exhibits good temperature stability from room temperature to 150 °C and frequency stability from 1 Hz to 100 Hz. A P_D of 0.621 J/cm³ and a t_0.9 of 82 ns is obtained for the BZTN40 ceramic at 120 kV/cm. BZTN ceramics show application potential in energy storage and pulse power capacitors.     

Enhanced thermoelectric properties of atomic-layer-deposited Hf:Zn16O/18O superlattice films by interface-engineering

This study examines three novel approaches for enhancing the thermoelectric (TE) properties of atomic-layer-deposited (ALD) ZnO thin films: 1) Hf-doping, which preserved the crystallinity of ZnO and provided effective phonon scattering owing to Hf's similar atomic radius to and large mass difference with Zn, leading to high power factor (PF) and low thermal conductivity (κ); 2) controlling the distribution of Hf into an alternating scattered phase/clustered phase superlattice, which balanced the high PF of the scattered phases with the low κ of the clustered phases, while providing significant energy-filtering effect to raise the Seebeck coefficient; 3) introducing ¹⁸O/¹⁶O periodicity into the Hf:ZnO films—by alternately using H₂¹⁶O and H₂¹⁸O as oxidants in the ALD processes, which further suppressed κ without compromising PF. The combination of the three approaches resulted in a maximum improvement in ZT of ~1600% over that of the undoped ZnO.     

Ultrasmall rhodium nanoclusters anchored on nitrogen-doped carbon nanotubes with embedded nickel nanoparticles as magnetically recyclable catalysts for efficient ammonia-borane hydrolysis

Facile yet efficient synthesis of high-performance nanocatalysts for hydrogen evolution from ammonia-borane (AB) hydrolysis is paramount. Here, we reported a novel hybrid nanocatalyst comprised of Rh nanoclusters (1.56 nm in diameters) anchored on nitrogen (N)-doped carbon nanotubes with embedded Ni nanoparticles (Ni@NCNTs), which was fabricated through adsorption of Rh ions on Ni@NCNTs. The achieved hybrid of Rh/Ni@NCNTs displayed excellent catalytic property (Turnover frequency: 959 min⁻¹) toward AB hydrolysis, higher than many prior developed Rh-based catalysts. Note that this hybrid could be reused for at least nine runs with complete AB conversion to hydrogen. Rh nanoclusters with small size exhibiting high atom utilization and the synergetic effect between Ni and Rh are responsible for the excellent catalytic property of Rh/Ni@NCNTs toward AB hydrolysis. This work highlights the importance of utilization of magnetically recyclable Ni@NCNTs as support and synergetic component for efficient hydrolysis of AB.     

Microstructure,mechanical properties and bio-corrosion properties of Mg-HA bionanocomposites fabricated by a novel severe plastic deformation process

This research investigates the alterations in microstructure, mechanical properties, and corrosion behavior of binary magnesium-hydroxyapatite bionanocomposites with 2, 5, and 10 wt%HA. By mixing Mg and HA powders with different percentages of HA contents, a combined method of cyclic extrusion compression (CEC), equal channel angular pressing (ECAP) and conventional extrusion were employed to consolidate the mixture of powders. All composites were examined. The results indicate that the addition of hydroxyapatite to magnesium improves the mechanical properties, but these properties are deteriorated with the hydroxyapatite content of over 5 wt%. The corrosion behavior of the composites was examined by immersion test, mass loss and polarization tests in Hank’s solution. The results indicate that Mg-5HA exhibits the best corrosion resistance and the corrosion rate increases when the HA content rises to more than 5 wt%. In addition, the specimen produced through the proposed method in this work indicates better corrosion resistance in comparison with cast and extruded pure Mg.     

Detecting Cysteine in Bioimaging with a Near-Infrared Probe Based on a Novel Fluorescence Quenching Mechanism

Near-infrared (NIR) fluorescent probes are very significant for detecting cysteine in biological systems. Herein, we report a highly selective and sensitive NIR turn-on fluorescent probe (BDP-NIR) based on BODIPY with large Stokes shift (105 nm) for detecting Cys. We clarified the sensing mechanism based on the different thiol-induced S_NAr substitution/rearrangement reaction of the probe with cysteine and homocysteine/glutathione, which leads to the corresponding amino- and thiol-BODIPY dyes with distinct photophysical properties. Moreover, a novel mechanism of fluorescence quenching was demonstrated by density functional theory calculation. The reason for the fluorescence quenching of the probe might be intersystem crossing (from singlet to triplet excited state). Moreover, BDP-NIR had a high linear dynamic range of 0–500 μM, which was promising for detecting cysteine quantificationally. Significantly, BDP-NIR was capable of sensing endogenous cysteine in living cells and in vivo.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Nanocrystalline transition metal oxides and their composites with reduced graphene oxide and carbon nanotubes for photocatalytic applications

Transition metal oxide nanoparticles (CuO, ZnO & Fe₂O₃) and mixed metal oxides CuO. ZnO.Fe₂O₃ were fabricated by facile co-precipitation approach for photocatalytic treatment of organic dyes. The structural features, phase purity, crystallite size and morphology of individual and mixed metal oxides were analysed by X-rays diffraction patterns (XRD) and scanning electron microscopic (SEM) analysis. Electrical behaviour of CuO, ZnO, Fe₂O₃ and mixed metal oxides CuO. ZnO.Fe₂O₃ was explored by current-voltage (I-V) measurements. Functional groups present in the synthesized metal oxides were investigated by Fourier transform infrared spectroscopy (FTIR) which ensures the existence of M-O functional groups in the samples. The optical bandgap analysis was carried out by UV–visible spectroscopic technique which revealed that the blend of three different transition metal oxides reduced the bandgap energy of mixed metal oxides. The reason behind this reduced bandgap energy is formation of new electronic state which arises due to the metal-oxygen interactions. Moreover, the nanocomposites of CuO.ZnO.Fe₂O₃ with reduced graphene oxide (rGO) and carbon nanotubes (CNTs) were prepared to study the effect of the carbonaceous materials on the rate of photodegradation. These carbonaceous nanomaterials have plethora properties which can bring advancement in sector of photocatalytic treatment of wastewater. The photocatalytic experiments were performed using methylene blue (MB) as standard dye for comparative study of metal oxides and their composites with rGO and CNTs. The percentage degradation of methylene blue (MB) by nanocomposite CuO.ZnO.Fe₂O₃/rGO is 87% which is prominent among all samples. This result ascribed the photocatalytic aspects of reduced graphene oxide along with mixed metal oxides.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

The demand for high-performance non-precious-metal electrocatalysts to replace the noble metal-based catalysts for oxygen reduction reaction(ORR)is intensively increasing.Herein,single-atomic copper sites supported on N-doped three-dimensional hierarchically porous carbon catalyst(Cu₁/NC)was prepared by coordination pyrolysis strategy.Remarkably,the Cu₁/NC-900 catalyst not only exhibits excellent ORR performance with a half-wave potential of 0.894 V(vs.RHE)in alkaline media,outperforming those of commercial Pt/C(0.851 V)and Cu nanoparticles anchored on N-doped porous carbon(CuNPs/NC-900),but also demonstrates high stability and methanol tolerance.Moreover,the Cu₁/NC-900 based Zn-air battery exhibits higher power density,rechargeability and cyclic stability than the one based on Pt/C.Both experimental and theoretical investigations demonstrated that the excellent performance of the as-obtained Cu₁/NC-900 could be attributed to the synergistic effect between copper coordinated by three N atoms active sites and the neighbouring carbon defect,resulting in elevated Cu d-band centers of Cu atoms and facilitating intermediate desorption for ORR process.This study may lead towards the development of highly efficient non-noble metal catalysts for applications in electrochemical energy conversion.     

Iron mediated cathodic electrosynthesis of hausmannite nanoparticles

A novel synthetic route has been proposed to prepare hausmannite nanoparticles. The synthetic route comprises an iron mediated constant current cathodic electrodeposition of manganite and heat treatment of the latter to obtain hausmannite. The obtained nanostructures have been characterized using X-ray Diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and Fourier transform Infrared Spectrometry (FTIR). The role of iron in the formation of manganite precursor has been studied by cyclic voltammetry (CV) and differential thermal analysis (DTA). A formation mechanism based on iron mediated formation of Mn³⁺ and subsequent cathodic reduction of the disproportionated products has been proposed accordingly. The prepared nanoparticles exhibited specific capacitance of 143 F g⁻¹ in 0.5 M Na₂SO₄ solution. The retained specific capacity was 87% after 2000 cycles.