Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

Hydrothermal synthesis of α-SnWO4: Application to lithium-ion battery and photocatalytic activity

The high capacity anode material is required to replace the most commonly used anode - graphite to keep up the global demand to achieve the goal. Multi-metal oxide has gained keen attention for its higher theoretical capacity and relatively stable than a single metal oxide. α-SnWO₄ has a theoretical capacity of 850 mAh g^?1 which is greater than graphite (372 mAh g^?1). α-SnWO₄ has been synthesized through low-temperature hydrothermal method using tin chloride and sodium tungstate as a precursor in acidic medium (succinic acid) at 200 °C for 12 h. The obtained product has been characterized using various analytical tools such as XRD, FT-IR, UV-DRS, BET, PL, SEM, and HR-TEM. XRD analysis shows the orthorhombic phase with a crystallite size of ~25 nm α-SnWO₄has been examined as an electrode material for Li-ion battery (LIB) and displays an initial discharge capacity of 985 mAh g^?1. Columbic efficiency close to 100% has been observed for 100 cycles. The stability of the electrode material was studied at different C-rates. Band-gap calculated using UV-DRS (Eg = 1.9 eV) shows that α-SnWO₄ is a good candidate for photocatalytic degradation. Results of the photocatalytic experiment using methylene blue (MB) as a model pollutant in an aqueous medium shows good results. The above applications show that α-SnWO₄ is multifunctional materials for diverse applications.     

Catalytic combustion synthesis of CNTs/MgO composite powders and the influences on the thermal shock resistance of low-carbon Al2O3–C refractories

Using MgC₂O₄, Mg powders as raw materials and Ni(NO₃)₂?6H₂O as a catalyst, CNTs/MgO composite powders were prepared by a catalytic combustion synthesis method. The CNTs/MgO composite powders were characterized by XRD, Raman spectroscopy, FESEM/EDS and HRTEM. The effects of catalyst content on the degree of graphitization and aspect ratio of the CNTs in composite powders were investigated. Moreover, the thermal shock resistance of low-carbon Al₂O₃–C refractories after adding the composite powder was investigated. The results indicated that the CNTs prepared with 1 wt% Ni(NO₃)₂?6H₂O addition had a higher degree of graphitization and aspect ratio. In particular, the aspect ratio could reach approximately 200. The growth mechanism of hollow bamboo-like CNTs in the composite powders was proven to be a V-L-S mechanism. The thermal shock resistance of Al₂O₃–C samples could be improved significantly after adding CNTs/MgO composite powders. In particular, compared with CM0, the residual strength ratio of Al₂O₃–C samples with added 2.5 wt% composite powders could be increased 63.9%.     

From modification to mechanism: Supercritical hydrothermal synthesis of nano-zirconia

Nano-zirconia has been widely applied due to its excellent physical and chemical properties (e.g., high strength, corrosion resistance, oxygen ion conductivity). Existing preparation methods of nano-zirconia tend to require long reaction time, and the sizes of final particles are large with uneven distributions. Sub-/supercritical hydrothermal synthesis of nanoparticles is favored by researchers owing to controllable reaction process, uniform particle size distribution, good reproducibility, short reaction time, high conversion rate and harmlessness to environment. In this paper, the characteristics and mechanisms of dissolution, crystallization and growth of nano-zirconia during sub-/supercritical hydrothermal synthesis are systematically reviewed. The influences of process and material parameters on the size and purity of particles are analyzed. Then, the reaction mechanism and product phase transition mechanism during hydrothermal synthesis of zirconia are summarized to provide a theoretical reference for the oriented preparation. Finally, the improvement and commercialization of sub-/supercritical hydrothermal synthesis technology are evaluated, and the future research topics are proposed.     

Strain mediated enhancement in magnetoelectric properties of sonochemically synthesized piezoelectric and piezomagnetic composites

Materials with magneto-electric (ME) properties are of great importance because of their demand in electronic industries. Three dimensional nano-particles of the ME-composites having the general formula (1-x)CoCr_0.3Fe_1.7O₄(CCFO)+(x)BaTiO₃(BTO) (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) were obtained by comprising the piezoelectric-BTO and piezomagnetic-CCFO phases. The individual phases of CCFO and BTO were synthesized separately by ultrasonic irradiation assisted sonochemical and sol-gel routs. X-ray diffraction patterns (XRD) confirmed the well-crystalline nature of both the phases. BTO and CCFO phases were under tensile strain as confirmed by the variation in lattice constants with varying proportion of BTO and CCFO. An energy-dispersive X-ray spectroscopy spectrum confirmed the phase purity of the samples and stoichiometric concentration of elements. Magnetic properties were investigated by M ? H loop measurements and dielectric properties by using RF impedance analyzer. Dielectric constant increased with the increasing percentage of BTO. The maximum value of ME coefficient (24.7 mV/cm?Oe) is observed for the 60%CCFO+40%BTO sample. The obtained results were discussed in the light of grain size, strain and the basic properties of the individual phases. The prepared materials can be applicable in electronic devices where high magneto-electric coefficient is desirable.     

Efficient sunlight and UV photocatalytic degradation of Methyl Orange,Methylene Blue and Rhodamine B,using Citrus×paradisi synthesized SnO2 semiconductor nanoparticles

In this work, tin dioxide (SnO2) Nanoparticles (NPs) were synthesized through green synthesis, using Citrus × paradisi extract as a stabilizing (capping). The extract concentrations used were 1, 2 and 4% in relation to the aqueous solution. The resulting SnO2 NPs were used for the degradation of Methyl Orange (MO), Methylene Blue (MB) and Rhodamine B (RhB), under both solar and UV radiation. The NPs were characterized via Attenuated Total Reflectance Infrared Spectroscopy (ATR-IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM-SAED), the Brunauer-Emmett-Teller (BET) theory, Ultraviolet to Visible spectroscopy (UV–Vis), and Photoluminescence spectroscopy (PL); while the photocatalytic degradation was evaluated using UV-VIS. The results showed that the Citrus × paradisi extract is a good medium for the formation of SnO2 NPs. These NPs presented quasi-spherical morphology, particle sizes of 4–8 nm, with a rutile phase crystalline structure, and with banned gap of 2.69 at 3.28 eV. The NPs had excellent photocatalytic properties under solar radiation, degrading 100% of the OM in 180 min. Furthermore, under UV radiation, 100% degradation of the three dyes was achieved in a short time; 20 min for MO, and 60 min for MB and RhB. Therefore, green synthesis is a feasible medium for the formation of SnO2 NPs with good photocatalytic properties.     

Effect of heat treatment on the synthesis of hydroxyapatite from Indian clam seashell by hydrothermal method

Hydroxyapatite (HA) powder has been successfully synthesized from low-cost Indian clam seashells by using hydrothermal method. The mixture of tri-calcium phosphate [Ca₃(PO₄)₂], heat-treated ball-milled clam seashell, and demineralized water are heat-treated at several temperatures (700 °C, 800 °C, 900 °C, 1000 °C, and 1100 °C) for various time periods (1 h, 2 h, and 3 h) to perform the hydrothermal reactions. The phases and microstructure of the solid-state reaction products are analyzed through X-ray diffraction (XRD) method and field emission scanning electron microscopy (FESEM) respectively. The crystallite size of all the synthesized powders is calculated by using Scherrer's model. Mainly HA phase is obtained in all the different reaction products. However, these HAs are found to be non-stoichiometric in nature. As per the literature, non-stoichiometric HA is a more biologically active material compared to the stoichiometric one. Almost pure HA is formed with any selected reaction temperature applied for 2 h time duration. The crystallinity and Ca/P ratio of the synthesized pure HA are estimated by using standard model and energy-dispersive X-ray spectroscopy (EDS) analysis, respectively. The highest amount of near stoichiometric crystalline HA has been obtained at 900 °C of reaction temperature applied for 2 h time duration. With raising reaction temperature, the grain size of pure HA is found to be increased. Needle/rod shaped nano grains are noticed to form at lower reaction temperature whereas; beyond 1000 ^oC of temperature globular/spherical shaped grains are also observed to form. At 3 h reaction time agglomeration of grains is found to occur in all the synthesized powders.     

Solution-Synthesized Multifunctional Janus Nanotree Microswimmer

Synthetic active matters are perfect model systems for non-equilibrium thermodynamics and of great potential for novel biomedical and environmental applications. However, most applications are limited by the complicated and low-yield preparation, while a scalable synthesis for highly functional microswimmers is highly desired. In this paper, an all-solution synthesis method is developed where the gold-loaded titania-silica nanotree can be produced as a multi-functional self-propulsion microswimmer. By applying light, heat, and electric field, the Janus nanotree demonstrated multi-mode self-propulsion, including photochemical self-electrophoresis by UV and visible light radiation, thermophoresis by near-infrared light radiation, and induced-charge electrophoresis under AC electric field. Due to the scalable synthesis, the Janus nanotree is further demonstrated as a high-efficiency, low-cost, active adsorbent for water decontamination, where the toxic mercury ions can be reclaimed with enhanced efficiency.     

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).     

Hydrogen generation rate enhancement by in situ Fe(0) and nitroarene substrates in Fe3O4@Pd catalyzed ammonia borane hydrolysis and nitroarene reduction tandem reaction

We report the catalytic enhancement of hydrogen generation by 1) in situ Fe (0) formed and 2) nitroarenes substrates during Fe₃O₄@Pd core-shell nanoparticles catalyzed tandem reaction. The active hydrogen species are generated in Pd shell, which either combine to form H₂ gas or take part in relatively faster nitroarene reduction reaction. The rate of hydrogen generation from ammonia borane is dependent on the nitroarene substrate and is higher when 4-nitrophenol is used. This is due to the difference in ammonia borane adsorption on the surface of the catalyst. During recyclability, the H₂ generation rate of 2 wt% Pd loaded samples is higher than other compositions. Such an enhancement has been attributed to the formation of Fe (0) via γ-FeOOH mediated by Pd species, presumably through Pd(OH)₂. The electronic connection between Fe and Pd interface is thus shown to play an important role in the catalytic enhancement of the tandem reaction.