Search Results (957)

Magnesium hydride solids doped with transition metals have received attention recently as prospective hydrogen storage materials for a green energy source and a hydrogen economy. In this study, MgTiH_n (n = 1–20) clusters were investigated for the first time by employing the B3PW91 hybrid density functional theory computational chemistry technique with all electron basis sets to determine precise cluster structures and the maximum hydrogen capacity for this model system. We find that hydrogen atoms bind to the metal cluster core until a MgTiH₁₄ saturation limit is reached, with hydrogen dissociation from this system occurring for MgTiH₁₅ and larger cluster sizes. This MgTiH₁₄ cluster contains a large 16.4% hydrogen by mass. This saturation size limit and hydrogen mass percent is larger than the analogous MgScH_n system previously reported. The clusters relative stabilities and electronic properties are discussed along with a possible novel hydrogen dissociation pathway. MgTiH₁₀ and MgTiH₁₃ clusters are predicted to be especially stable species in this size range. Full article

The fabrication of stable, tailored domain patterns in ferroelectric crystals has wide applications in optical and electronic industries. All-optical ferroelectric poling by pulse laser irradiation has been developed recently. In this work, we studied the creation of the domain structures in MgO-doped lithium tantalate by focused irradiation with a femtosecond near-infrared laser. Cherenkov-type second harmonic generation microscopy was used for domain imaging of the bulk. We have revealed the creation of enveloped domains around the induced microtracks under the action of the depolarization field. The domain growth is due to a pyroelectric field caused by a nonuniform temperature change. The domains in the bulk were revealed to have a three-ray star-shaped cross-section. It was shown that an increase in the field excess above the threshold leads to consequential changes in domain shape from a three-ray star to a triangular and a circular shape. The appearance of comb-like domains as a result of linear scanning was demonstrated. All effects were considered in terms of a kinetic approach, taking into account the domain wall motion by step generation and kink motion driven by excess of the local field over the threshold. The obtained knowledge is useful for the all-optical methods of domain engineering in ferroelectrics. Full article

This study demonstrates that diffusion doping of ZGP single crystals with impurity atoms (Mg, Se, Sn, Pb) leads to a decrease in the specific conductivity of the samples. Consequently, this results in reduced absorption in the terahertz frequency range (150–1000 μm). It has been shown that doping ZGP samples with selenium (Se) and lead (Pb) atoms reduces absorption in the infrared region from 0.3–0.6 cm⁻¹ to 0.06–0.09 cm⁻¹. Doping with tin (Sn) leads to a decrease in absorption only in the wavelength region near 2.1 μm from 0.2 cm⁻¹ to 0.05 cm⁻¹. The proposed mechanism for the decrease in infrared absorption is a reduction in zinc vacancies due to doping with impurity atoms. This research lays the groundwork for a technology that produces ZGP crystals with minimal absorption within the 2–8 μm wavelength range, eliminating the need for fast electron beam irradiation technology. This advancement will facilitate the fabrication of ZGP crystals with arbitrary apertures. Full article

In this study, Fe, N co-doped biochar (Fe@N co-doped BC) was synthesized by the carbonization–pyrolysis method and used as a carbocatalyst to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. In the Fe@N co-doped BC/PMS system, the degradation efficiency of SMX (10.0 mg·L⁻¹) was 90.2% within 40 min under optimal conditions. Radical quenching experiments and electron spin resonance (ESR) analysis suggested that sulfate radicals (SO₄^•−), hydroxyl radicals (^•OH), and singlet oxygen (¹O₂) participated in the degradation process. After the reaction, the proportion of pyrrolic N decreased from 57.9% to 27.1%. Pyrrolic N served as an active site to break the inert carbon network structure and promote the generation of reactive oxygen species (ROS). In addition, pyrrolic N showed a stronger interaction with PMS and significantly reduced the activation energy required for the reaction (∆G = 23.54 kcal/mol). The utilization potentiality of Fe@N co-doped BC was systematically evaluated in terms of its reusability and selectivity to organics. Finally, the intermediates of SMX were also detected. Full article

The effect of an erbium alloying on the hot deformation behavior of the crossover Al3Zn3Mg3Cu0.2Zr alloy was investigated in detail. First of all, Er increases the solidus temperature of the alloy. This allows hot deformation at a higher temperature. The precipitates resulting from the Er alloying of the Al3Zn3Mg3Cu0.2Zr alloy were analyzed using transmission electron microscopy. Erbium addition to the alloy produces the formation of more stable and fine L1₂-(Al₃(Zr, Er)) precipitates with a size of 20–60 nm. True stress tends to increase with a decline in the temperature and an increase in the deformation rate. The addition of Er leads to decreases in true stress at the strain rates of 0.01–1 s⁻¹ due to particle-stimulated nucleation softening mechanisms. The effective activation energy of the alloy with the Er addition has a lower value, enabling an easier hot deformation process in the alloy with an elevated volume fraction of the intermetallic particles. The addition of Er increases the strain rate sensitivity, which makes the failure during deformation less probable. The investigated alloys have a significant difference in the dependence of the activation volume on the temperature. The flow instability criterion allows better deformability of Er-doped alloys and enables the alloys to be formed more easily. The evenly distributed particles prevent the formation of shear bands with elevated storage energy and decrease the probability of crack initiation during the initial stages of hot deformation when only one softening mechanism (dynamic recovery) is working. The microstructure analysis proves that dynamic recovery is the main softening mechanism. Full article

Platinum (Pt)-based materials are among the most competitive electrocatalysts for the hydrogen evolution reaction (HER) due to suitable hydrogen adsorption energy. Due to the rarity of Pt, it is desirable to develop cost-effective Pt-based electrocatalysts with low Pt loading. Herein, Pt/PtS electrocatalysts on S-doped carbon nanofilms (PPS/C) have been successfully fabricated through a precursor reduction route with a complex of Pt and 1-dodecanethiol (1-DDT) as the precursor. The PPS/C achieved at 400 °C (PPS/C-400) exhibits excellent HER performances with an ultralow overpotential of 41.3 mV, a low Tafel slope of 43.1 mV dec⁻¹ at a current density of 10 mA cm⁻², and a long-term stability of 10 h, superior to many recently reported Pt-based HER electrocatalysts. More importantly, PPS/C-400 shows a high mass-specific activity of 0.362 A mg_Pt⁻¹ at 30 mV, which is 1.88 times of that of commercial 20% Pt/C (0.193 A mg_Pt⁻¹). The introduction of sulfur leads to the formation of PtS, which not only reduces the content of Pt but also realizes the interface regulation of Pt/PtS, as well as the doping of carbon. Both regulations make the resulting catalyst have abundant active centers and rapid electron transfer/transport, which is conducive to balancing the adsorption and resolution of intermediate products, and finally achieving great mass-specific activity and stability. The research work may provide ideas for designing effective Pt-based multi-interface electrocatalysts. Full article

As a high energy density cathode material, further development of high working voltage spinel LiNi_0.5Mn_1.5O₄ has hindered by its rapid capacity degradation. To address this, a hetero-valent substitution of magnesium for manganese was used to synthesize spinel LiNi0.5Mg_xMn_1.5−xO₄ (x = 0, 0.03, 0.05) via a microwave sol-gel method. XRD and refined results indicate that such strategy leads to the modification of the 16c interstitial sites. The electrical performance demonstrates that a modest substitution (x = 0.03) significantly improves both rate performance (113.1 mAh/g, charge and discharge at 5 C) and cycling stability (85% capacity retention after 500 cycles at 1 C). A higher substitution level (x = 0.05) markedly improves high-rate cycling performance, achieving 96% capacity retention after 500 cycles at 5 C. It offers tailored solutions for various application needs, including capacity-focused and high-current-rate applications. Furthermore, the stable LiNi_0.5Mg_0.05Mn_1.45O₄ sample could also serve as an effective coating layer for other electrode materials to enhance their cycling stability. Full article

Na₅V₁₂O₃₂ is an attractive cathode candidate for aqueous zinc-ion batteries (AZIBs) by virtue of its low-cost and high specific capacity (>300 mAh g⁻¹). However, its intrinsically inferior electronic conductivity and structural instability result in an unfavorable rate performance and cyclability. Herein, K-doped Na₅V₁₂O₃₂ (KNVO) was developed to promote its ionic/electronic migration, and thus enhance the Zn²⁺ storage capability. The as-produced KNVO displays a superior capacity of 353.5 mAh g⁻¹ at 0.1 A g⁻¹ and an excellent retentive capacity of 231.8 mAh g⁻¹ after 1000 cycles at 5 A g⁻¹. Even under a high mass of 5.3 mg cm⁻², the KNVO cathode can still maintain a capacity of 220.5 mAh g⁻¹ at 0.1 A g⁻¹ and outstanding cyclability without apparent capacity decay after 2000 cycles. In addition, the Zn²⁺ storage kinetics of the KNVO cathode is investigated through multiple analyses. Full article

Prosthesis loosening due to lack of osteointegration between an implant and surrounding bone tissue is one of the most common causes of implant failure. Further, bacterial contamination and biofilm formation onto implants represent a serious complication after surgery. The enhancement of osteointegration can be achieved by using bioconductive materials that promote biological responses in the body, stimulating bone growth and thus bonding to tissue. Through the incorporation of antibacterial substances in bioconductive, biodegradable calcium phosphate (CaP) coatings, faster osteointegration and bactericidal properties can be achieved. In this study, Cu-doped CaP supraparticles are spray-dried and suspension-sprayed CaP ceramic coatings with antibacterial properties are prepared using high-velocity suspension flame spraying (HVSFS). The objective was to increase the coatings’ porosity and investigate which Cu-doped supraparticles have the strongest antibacterial properties when introduced into the coating layers. Biocompatibility was tested on human Osteosarcoma cells MG63. A porosity of at least 13% was achieved and the supraparticles could be implemented, enhancing it up to 16%. The results showed that the addition of Cu-doped supraparticles did not significantly reduce the number of viable cells compared to the Cu-free sample, demonstrating good biocompatibility. The antimicrobial activity was assessed against the bacterial strains Escherichia coli and Staphylococcus aureus, with Safe Airborne Antibacterial testing showing a significant reduction in both Gram-positive and Gram-negative strains on the Cu-doped coatings. Full article

Direct Methanol Fuel Cell (DMFC) is a powerful system for generating electrical energy for various applications. However, there are several limitations that hinder the commercialization of DMFCs, such as the expense of platinum (Pt) at market price, sluggish methanol oxidation reaction (MOR) due to carbon monoxide (CO) formation, and slow electrooxidation kinetics. This work introduces carbon nanocages (CNCs) that were obtained through the pyrolysis of polypyrrole (Ppy) as the carbon source. The CNCs were characterized using BET, XRD, HRTEM, TEM, SEM, and FTIR techniques. The CNCs derived from the Ppy source, pyrolyzed at 750 °C, exhibited the best morphologies with a high specific surface area of 416 m²g⁻¹, allowing for good metal dispersion. Subsequently, PtRu catalyst was doped onto the CNC-Ppy750 support using chemical reduction and microwave-assisted methods. In electrochemical tests, the PtRu/CNC-Ppy750 electrocatalyst demonstrated improved CO tolerance and higher performance in MOR compared to PtRu-supported commercial carbon black (CB), with values of 427 mA mg⁻¹ and 248 mA mg⁻¹, respectively. The superior MOR performance of PtRu/CNC-Ppy750 was attributed to its high surface area of CNC support, uniform dispersion of PtRu catalyst, and small PtRu nanoparticles on the CNC. In DMFC single-cell tests, the PtRu/CNC-Ppy750 exhibited higher performance, approximately 1.7 times higher than PtRu/CB. In conclusion, the PtRu/CNC-PPy750 represents a promising electrocatalyst candidate for MOR and anodic DMFC applications. Full article

The aim of this study is to further enhance the thermal storage and heat transfer performances of a low-melting-point quinary salt. The eutectic salt was prepared using LiNO₃, NaNO₃, KNO₃, NaNO₂, and KNO₂ as raw materials, followed by the doping of nano-SiO₂ and nano-MgO into the base salt using a microwave-assisted method. The thermal properties of the samples were analyzed using a Synchronous Thermal Analyzer and a Laser Flash Apparatus. The co-doping of two types of nanoparticles was found to significantly enhance the specific heat capacity of the base salt. The maximum specific heat reached 2.36 J/(g·K), showing a 50.4% increase compared to the base salt. The thermal conductivity of molten salts can be affected by nanoparticles. An observed sample demonstrated a thermal diffusivity of 0.286 mm²/s, indicating a 19.2% improvement over the base salt, which may be attributed to enhanced phonon thermal efficiency. In addition, this study revealed that while interfacial thermal resistance can enhance specific heat capacity, it can also lead to a decrease in the thermal conductivity efficiency of materials. This work can offer insights and references for the enhancement of molten salt properties. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

This work reports on the possibility of sustaining a stable operation of polarization-doped InGaN light emitters over a particularly broad temperature range. We obtained efficient emission from InGaN light-emitting diodes between 20 K and 295 K and from laser diodes between 77 K and 295 K under continuous wave operation. The main part of the p-type layers was fabricated from composition-graded AlGaN. To optimize injection efficiency and improve contact resistance, we introduced thin Mg-doped layers of GaN (subcontact) and AlGaN (electron blocking layer in the case of laser diodes). In the case of LEDs, the optical emission efficiency at low temperatures seems to be limited by electron overshooting through the quantum wells. For laser diodes, a limiting factor is the freeze-out of the magnesium-doped electron blocking layer for temperatures below 160 K. The GaN:Mg subcontact layer works satisfyingly even at the lowest operating temperature (20 K). Full article

Photoreduction is recognized as a desirable treatment method for hexavalent chromium (Cr(VI)). However, it has been limited by the intermittent solar flux and limited light absorption. In this work, a novel Z-scheme photocatalyst combining a covalent organic framework (COF) with Eu²⁺, Dy³⁺ co-doped Sr₂MgSi₂O₇ (Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺) is synthesized, which shows the high spectral conversion efficiency and works efficiently in both light irradiation and dark for Cr(VI) reduction. Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺ serves as both an electron transfer station and active sites for COF molecule activation, thus resulting in 100% photoreduction of Cr(VI) (50 mL, 10 mg/L) with high light stability and over 1 h dark activity. Moreover, the XPS and FT-IR analyses reveal the existence of functional groups (Si-OH on Sr₂MgSi₂O₇:Eu²⁺, Dy³⁺, and -NH- on COF_TP-TTA) on the composited catalyst as active sites to adsorb the resultant Cr(III) species, demonstrating a synergistic effect for total Cr removal. This work provides an alternative method for the design of a round-the-clock photocatalyst for Cr(VI) reduction, allowing a versatile solid surface activation for establishing a more energy efficient and robust photocatalysis process for Cr pollution cleaning. Full article

Metoprolol is a cardioselective beta-blocker drug often used to treat hypertension, but it is considered as a hazardous organic persistent contaminant in wastewater. In this study, a 2.5 L solution of metoprolol (50 mg/L) underwent electro-oxidation in a flow-by reactor using boron-doped diamond electrodes in the batch recirculation mode. The study used multi-objective optimization and multi-criterion decision-making to determine the optimal operating parameters. The response surface methodology and a central composite rotatable design were used with three factors (pH₀: 5–8, I: 2.5–4 A, and Q: 0.8–1.7 L/min) to model the chemical oxygen demand’s (COD’s) removal efficiency and the total organic carbon’s (TOC’s) removal efficiency. The experimental responses were modeled by reduced third- and second-order polynomials with determination coefficients (R²) of 0.9816 and 0.9430. The optimal operating parameters were found to be pH₀ 5, an I value of 3.84 A, and a Q value of 0.8 L/min with an electrolysis time of 7.5 h, resulting in a maximum COD removal efficiency of 60.8% and a TOC removal efficiency of 90.1%. The specific energy consumption was calculated as 9.61 kWh/mg of TOC, with a total operating cost of 0.77 USD/L. In conclusion, this study showed that the electrochemical process is efficient and reliable for treating wastewater containing metoprolol. Full article