Facile high yield synthesis of MgCo2O4 and investigation of its role as anode material for lithium ion batteries

In this article, we have reported a one-step scalable synthesis of MgCo₂O₄ nanostructures as efficient anode material for Li-ion batteries and investigated the role of post-synthesis calcination temperature (400, 600 and 800 °C) on its physiochemical properties and electrochemical performances. The XRD pattern of the calcinated sample at 400 °C (MC 400) indicates a pure phase of MgCo₂O₄. However, on increasing the calcination temperature to 600 °C (MC 600), an additional phase corresponding to MgO was detected and the corresponding XRD peak intensity further increased on increasing the calcination temperature to 800 °C (MC 800 °C). This was accompanied by a morphological transformation from flake and rod-like nanostructures, to an agglomerated dense flake-like morphology. Electrochemical studies revealed that the calcination temperature plays an important role in determining the electrochemical performance of the MgCo₂O₄ as anode material. In a half cell, the MC 600 showed the best electrochemical performance with high discharge capacity of 980 mA h g⁻¹ (2nd discharge at 60 mA g⁻¹) and a reversible discharge capacity of 886 mA h g⁻¹ at the end of 50 cycles with high coulombic efficiency of 98%. Long term stability was carried out at 0.5C which showed a capacity retention of 358 mA h g⁻¹ at the end of 500 cycles. The superior electrochemical performance of the MC600 can be attributed to the presence of the small amount of MgO, which is believed to provide the anode materials better structural stability during cycling. The claim was further supported by ex-situ TEM analysis of the anode material of a cycled cell (50 cycles).     

Carbon vacancies improved photocatalytic hydrogen generation of g-C3N4 photocatalyst via magnesium vapor etching

Vacancies engineering was widely reported as the promising strategy for the improvement of the photocatalytic performance of semiconductor photocatalysts. In current work, carbon vacancies are constructed successfully in graphitic carbon nitride (g-C₃N₄) photocatalyst via magnesium vapor etching. Experimental results show that the formed carbon vacancies in g-C₃N₄ photocatalyst can significantly improve the photocatalytic H₂ generation performance. XRD, FTIR, SEM/TEM, XPS and PL characterization data are employed to evidence the construction of carbon vacancies, which are revealed to be the reason for the enhancement of photocatalytic H₂ evolution. This work develops an alternative route to construct carbon vacancies in g-C₃N₄ materials and gives an insight into the influence of vacancies on the photocatalytic performance of photocatalysts.     

Effects of annealing on bandgap and surface plasmon resonance enhancement in Au/SnO2 quantum dots

Au/SnO₂ quantum dots (AuSQDs) were synthesized, and the effects of annealing on their structural and optical properties were examined. Significant changes were observed in the bandgap and surface plasmon resonance (SPR) of the AuSQDs after thermal treatment at different temperatures (400, 500, and 600 °C). The properties of the as-prepared and annealed samples were characterized via X-ray diffraction analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy, and diffuse reflectance spectroscopy. Annealing reduced the bandgap from 3.03 to 2.33 eV and increased the crystallinity while maintaining an average crystallite size below 10 nm. XPS valence band (VB) profiles provided information regarding the VB edge potentials, which helped to determine the conduction band edge potentials. An enhancement in the SPR of the Au nanoparticles was observed for AuSQD-500, which had the smallest bandgap among the samples investigated.     

Effect of carriers on deposition morphologies and catalytic performances of NiCo2O4

In this study, NiCo₂O₄ with different morphologies were fabricated using carriers by homogeneous coprecipitation combined with a sintering method. The phase and microstructure were characterized by XRD, SEM, EDS, TEM and BET, and the catalytic performances were investigated by NaBH₄ hydrolysis experiments. These studies revealed that the deposition morphology of NiCo₂O₄ can be adjusted by using different kinds of carrier templates, and the supported NiCo₂O₄ samples presented the pine-needle-like, network-like, ball-cactus-like and dandelion-like morphologies respectively. The optimal catalytic activity, durability and stability make the network-like NiCo₂O₄ an appropriate catalyst for hydrogen generation of NaBH₄ hydrolysis. It was found that the network-like NiCo₂O₄ is the most reusable and durable catalyst for ten consecutive cycles and 100% hydrogen generation conversion rate without obvious decrease among these morphologies.     

Joining ZTA ceramic by using Dy2O3-Al2O3-SiO2 glass ceramic filler

In this paper, a novel Dy₂O₃-Al₂O₃-SiO₂ (DAS) glass ceramic was designed and prepared for joining zirconia toughened alumina (ZTA) ceramic. The crystallization, thermal expansion behavior and wetting behavior of the DAS glass filler were studied. The effect of cooling rate and joining temperature on the microstructure and flexural strength of joints was investigated. The results show that slow cooling rate (15 °C/min) leads to crystallization of brazing seam, which causes the formation of pores in the joints due to the large density difference between the glass and the crystalline phases. The dissolution of ZrO₂ from ZTA substrate into the filler during joining process improves the mismatch of the coefficient of thermal expansion (CTE) between the brazing seam and substrate. The maximum flexural strength of 535 MPa is obtained when the joining temperature and cooling rate are 1475 °C and 50 °C/min, respectively.     

Investigation of the versatility of SPES membranes customized with sulfonated molybdenum disulfide nanosheets for DMFC applications

Sulfonated poly(ether sulfone) (SPES) based proton exchange membranes (PEMs) are fabricated using sulfonated molybdenum disulfide (S-MoS₂) nanosheets via facile solution casting method. SPES (DS = 30%) and S-MoS₂ are synthesized and sulfonation is evidently observed in FTIR and XRD analysis. The anchoring of sulfonic acid group on exfoliated molybdenum disulfide (E-MoS₂) and elemental composition of S-MoS₂ are confirmed by XPS spectrum. Physico-chemical characteristics such as ion-exchange capacity (IEC), water uptake, swelling ratio and oxidation stability are found to be increases after the addition of S-MoS₂ into SPES matrix. Increment in S-MoS₂ content in SPES matrix decreases the surface contact angle due to the increase in hydrophilicity. Further, the dispersing ability of S-MoS₂ in SPES matrix is evidently shown by an increase in surface roughness, tensile strength and thermal stability of the SPES/S-MoS₂ nanocomposite membranes. On the whole, SPES/S-MoS₂-1 membrane showed the highest proton conductivity of 5.98 × 10⁻³ Scm⁻¹, selectivity of 19.6 × 10⁴ Scm⁻³s, peak power density of 28.28 mWcm⁻² and lesser methanol permeability of 3.05 × 10⁻⁸ cm²s⁻¹. The strong interfacial interaction between SPES and S-MoS₂ in nanocomposite membranes create strong hydrogen bond network to facilitate the proton conduction pathway via both vehicle and Grotthuss type mechanisms. Overall results suggested that the SPES/S-MoS₂ nanocomposite membranes are superior and appropriate alternative for commercially high-cost Nafion® membranes for use in renewable direct methanol fuel cell (DMFC) devices.     

Semiconductor Fe-doped SrTiO3-δ perovskite electrolyte for low-temperature solid oxide fuel cell (LT-SOFC) operating below 520 °C

High-temperature operation of solid oxide fuel cells causes several degradation and material issues. Lowering the operating temperature results in reduced fuel cell performance primarily due to the limited ionic conductivity of the electrolyte. Here we introduce the Fe-doped SrTiO_3-δ (SFT) pure perovskite material as an electrolyte, which shows good ionic conduction even at lower temperatures, but has low electronic conduction avoiding short-circuiting. Fuel cell fabricated using this electrolyte exhibits a maximum power density of 540 mW/cm² at 520 °C with Ni-NCAL electrodes. It was found that the Fe-doping into the SrTiO_3-δ facilitates the creation of oxygen vacancies enhancing ionic conductivity and transport of oxygen ions. Such high performance can be attributed to band-bending at the interface of electrolyte/electrode, which suppresses electron flow, but enhances ionic flow.     

Fabrication of platinum thin films for ultra-high electrocatalytic hydrogen evolution reaction

While the noble metals (e.g., platinum, (Pt)) remain the benchmark electrocatalyst for the hydrogen evolution reaction (HER), their mass production require a reduced metal loading and faster fabrication protocols. The aim of the present work is to prepare Pt thin films by simple and fast fabrication technique, and to evaluate their performance for HER. The thin films of Pt are grown on two substrates, namely titanium foil (Ti) and nickel foam (NF), using a single step aerosol assisted chemical vapor deposition (AACVD) method. The film deposition time are varied from 20 to 60 min. Microscopic analyses suggest a gradual evolution of the films into percolated and/or porous nanostructures, a feature that remains highly desired to allow the maximum access of active sites. The performance of the as-prepared electrodes is evaluated by monitoring the HER in acidic electrolyte. The Pt film on nickel foam (Pt/NF) exhibits better electrical conductivity and smaller charge transfer resistance, while the film deposited on the Ti foil (Pt/Ti) demonstrates superior catalytic activity per active sites. The as-prepared Pt/Ti and Pt/NF electrodes produce 10 mA cm⁻² at overpotential of 28 mV and 26 mV, respectively, better in performance than commercial Pt/C electrode (~39 mV), set a new bench mark electrocatalyst for the HER.     

Thermal annealing characteristics of solar selective absorber coatings based on nano-multilayered MoOx films

Designing double metal-dielectric (cermet) solar selective absorber coatings (SSACs) often requires complex co-sputtering techniques with multiple targets. This inevitably limits the simple and low-cost industrial fabrication. Here, we develop novel nano-multilayered MoO_x-based SSACs by simple and stable one-step reactive magnetron sputtering process using single molybdenum target. The proposed multilayer SSACs exhibit good solar absorptance of 0.93 and low thermal emittance of 0.06. Owing to the temperature-induced oxygen diffusion and oxidation phenomenon the as-sputtered SSACs have a poor thermal tolerance under air atmosphere, and after annealing at 200 °C for 150 h, the resulting absorptance is diminished from 0.93 to 0.90. However, the optical performance of the annealed SSAC is relatively stable in high-vacuum environment, even after annealing at 450 °C for 200 h, it still displays an ideal spectral selectivity of 0.92/0.07. With above properties, the resulting MoO_x-based SSAC is a promising absorber for enduring thermal harvesting in solar vacuum collectors.     

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.