MgO Shell Research Articles

Sulfur-resistant mechanism of MnOx@CeO2@MgO core-shell catalyst in simultaneous removal of NOx and chlorobenzene

Herein, Mn-Ce based catalysts with different structures were rationally designed to explore their sulfur-resistant mechanism for simultaneous removal of NOx and chlorobenzene (CB) from waste incineration at low temperature. In the presence of SO2, MnOx@CeO2@MgO exhibits the highest sulfur resistance among prepared catalysts. Both NOx and CB conversion over MnOx@CeO2@MgO can reach up to 80% at 300 °C. However, the significant deactivation is observed for MnCeMgOx within all temperature ranges. For the selectivity of products, MnOx@CeO2@MgO displays the excellent N2 selectivity (93%) and good CO2 selectivity (80%) at 300 °C. Compared with NO reduction, SO2 has a greater impact on CB destruction due to the consumption of reactive oxygen species during SO2 oxidation. The reduction of active oxygen is proposed to be the reason for the significant inhibition of CB oxidation. The addition of MgO shell increases the proportion of lattice oxygen, which is beneficial to improving the sulfur resistance of MnOx@CeO2@MgO catalyst. In addition, SO2 can react with MgO preferentially to protect the active sites and improve the sulfur resistance. This work indicates that MnOx@CeO2@MgO core-shell catalyst with good sulfur tolerance and stability is expected to be applied in the potential application.

Synergistically enhanced dielectric properties and thermal conductivity in percolating flaky copper/poly(vinylidene fluoride) nanocomposites via engineering magnesium oxide as a buffer interlayer

AbstractHigh dielectric constant (ε), thermal conductivity (TC), and breakdown strength (Eb) along with low loss flexible polymeric nanocomposites display multifunctional applications. In this work, to synergistically bolster the TC and Eb while restraining dielectric loss and leakage current in the percolating flaky copper (f‐Cu)/poly(vinylidene fluoride) (PVDF), presenting a giant ε, the core@shell structured f‐Cu@MgO (magnesium oxide) nanosheets were first created via a chemical precipitation method, then incorporated into host PVDF to explore the MgO shell’ impact on the TC and dielectric properties of the resulting nanocomposites. The introduced MgO interlayer strengthens the interfacial interactions and significantly mitigates the interfacial mismatch in both ε and conductivity between the f‐Cu and PVDF, resulting in elevated TC and Eb of the f‐Cu@MgO/PVDF in comparison to pristine f‐Cu/PVDF. Furthermore, the insulating MgO interlayer introduces deep traps and inhibits the long‐distance migration of electrons, leading to remarkably suppressed dielectric loss. More importantly, the TC and dielectric properties of nanocomposites can be optimized by tuning the MgO thickness. The fitting results via the Havriliak‐Negami equation theoretically support the MgO shell's suppression effect on charge migration and reveal the underlying polarization mechanism in the nanocomposites. The developed nanocomposites with currently high ε, Eb and TC but low loss, present promising applications in electrical power systems.

Synergistically depressed dielectric loss and elevated breakdown strength in core@double-shell structured Cu@CuO@MgO/PVDF nanocomposites

To synergistically bolster breakdown strength (Eb) and restrain dielectric loss in the copper (Cu)/poly(vinylidene fluoride, PVDF) presenting a giant dielectric constant (ε), we explore the PVDF nanocomposites with a serial of core@double-shell Cu@CuO (copper oxide)@MgO (magnesium oxide) nanofillers with various MgO shell thicknesses. The double-shell CuO@MgO not only improves the interface compatibility between filler and matrix but also increases the energy barrier height for charge migration across the nanocomposites and facilitates the formation of charge traps, thus impeding long-distance carrier transport and resulting in restrained dielectric loss. Further, the MgO shell with appropriate ε and wide bandgap effectively alleviates the strong dielectric mismatch between neat Cu and PVDF, which significantly lessens the local electric field distortion thereby resulting in elevated Eb. Moreover, the overall dielectric performances of the Cu@CuO@MgO/PVDF can be modulated via altering the MgO shell thickness. This core@double-shell strategy offers a new paradigm for the design and preparation of percolating nanocomposites with desirable integrated dielectric performances.

Stability of Plasmonic Mg-MgO Core-Shell Nanoparticles in Gas-Phase Oxidative Environments.

Magnesium is a recent addition to the plasmonic toolbox: nanomaterials that efficiently utilize photons' energy due to their ability to sustain localized surface plasmon resonances. Magnesium nanoparticles protected by a native oxide shell can efficiently absorb light across the solar spectrum, making them a promising photocatalytic material. However, their inherent reactivity toward oxidation may limit the number of reactions in which Mg-MgO can be used. Here, we investigate the stability of plasmonic Mg-MgO core-shell nanoplates under oxidative conditions. We demonstrate that the MgO shell stabilizes the metallic Mg core against oxidation in air at up to 400 °C. Furthermore, we show that the reactivity of Mg-MgO nanoplates with water vapor (3.5 vol % in N2) decreases with temperature, with no oxidation of the Mg core detected from 200 to 400 °C. This work unravels the potential of Mg-MgO nanoparticles for a broad range of catalytic transformations occurring in oxidative environments.

Mechanochemical synthesis, purification, and optimization studies of Cr boride@MgO particles

Chromium boride, an advanced ceramic material, is commonly produced by powder metallurgy methods using elemental boron and chromium powder, borothermic reactions, or boron carbide reduction of Cr2O3. In this study, a mechanochemical method for the production of chromium boride was developed, subsequent purification was performed, and the whole process was optimized. The amounts of Cr2O3, B2O3, and Mg in the initial powder blends were determined by computational thermodynamic methods based on their equilibrium compositions. Firstly, stoichiometric starting-powder blends were milled at different durations (1, 2, 3, 4, 5, and 8 h). The optimum purification route was determined using acid leaching experiments carried out with different acids, at different temperatures, and concentrations. Secondly, powders prepared in excess amounts were synthesized at the optimum duration (5 h) and leaching condition (0.1 M HCl, 25 °C). For the 100 wt % excess B2O3, 25 wt % excess Mg and 0.8 moles of Cr2O3 composition, annealing was conducted at 1100 °C. Characterization studies, X-ray diffractometry (XRD), scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), and atomic absorption spectroscopy (AAS) were conducted on the milled and leached powders. After annealing, CrB, CrB2, Cr3B4 and MgO phases were obtained in the XRD patterns. The particle sizes of the resulting materials were also analyzed, and it was found to be nearly 3.11 μm after annealing. Finally, the TEM analysis revealed that the MgO peak evident in the XRD patterns was MgO shell covering the Cr boride particles having submicron sizes; hence, a pure Cr boride@MgO core-shell structure was obtained.

Improving Performance of InP-Based Quantum Dot Light-Emitting Diodes by Controlling Defect States of the ZnO Electron Transport Layer

ZnO nanoparticles (NPs) are currently the benchmark of electron transport materials for preparing indium phosphide (InP)-based environmentally friendly quantum dot light-emitting diodes (QLEDs). However, the defect-dependent exciton quenching and charge injection limiting behavior at the ZnO/quantum dot (QD) interface seriously restrict the improvement in device performance. Herein, we report a strategy based on Li doping and MgO shell coating to regulate the defect state of ZnO to improve the performance of InP-based QLEDs. It is found that Li doping passivates the intrinsic defect states of ZnO NPs and improves the electron mobility and reduces the spontaneous charge transfer at the ZnO/QD interface and the current leakage of QLEDs. The MgO shell passivates the surface oxygen defects of ZnO NPs, thus reducing the exciton quenching and non-radiative recombination centers at the ZnO/QD interface, resulting in enhanced QLED performance. As a result, the optimized QLED prepared by Li-doped and MgO shell-coated ZnO NPs shows an external quantum efficiency of 9.7% and a brightness of 22,200 cd m–2 at 4.2 V, which are, respectively, 2.6 and 7 times higher than those of a QLED based on pure ZnO. This work shows that controlling the defect states of the ZnO electron transport layer by ion doping and shell coating provides an effective way to obtain high-performance environment-friendly QLEDs.

Corrosion behavior of Inconel 625 deposited metal in molten KCl-MgCl2

In order to investigate the corrosion behavior of Inconel 625 deposited metal in molten KCl and MgCl2, the corrosion behavior of deposited metal immersed in molten salt for 60 h at 700 °C and 900 °C was studied by static corrosion immersion method. X-ray diffraction (XRD) and Geminisem300 were used to systematically study the phase composition, corrosion morphology and element distribution of the deposited metal. The results show that: the corrosion weight loss of the deposited metal showed an increasing trend at both temperatures, but the increasing range was different in different time intervals. The corrosion weight loss of the deposited metal increased slowly in the first 10 h, and increased sharply in the 10 h–60 h. It can be found that 10 h is the cut-off point of corrosion behavior. The corrosion rate is 0.03 mm/year at 700 °C and 0.50 mm/year at 900 °C for 10 h. The corrosion resistance of the deposited metal at 700 °C is better than that at 900 °C, which is due to the formation of dense MgO on the surface of the deposited metal at 700 °C, which hinders the corrosion reaction; at 900 °C, the content of CrCl3 on the surface of the deposited metal increases, resulting in a ‘shell breaking effect’, which destroys the MgO shell and forms NiCr2O4 with spinel structure. Its corrosion resistance is thus weakened.

Effect of Short Attritor-Milling of Magnesium Alloy Powder Prior to Spark Plasma Sintering.

The spark plasma sintering (SPS) technique was employed to prepare compacts from (i) gas-atomized and (ii) attritor-milled AE42 magnesium powder. Short attritor-milling was used mainly to disrupt the MgO shell covering the powder particles and, in turn, to enhance consolidation during sintering. Compacts prepared by SPS from the milled powder featured finer microstructures than compacts consolidated from gas-atomized powder (i.e., without milling), regardless of the sintering temperatures in the range of 400–550 °C. Furthermore, the grain growth associated with the increase in the sintering temperature in these samples was less pronounced than in the samples prepared from gas-atomized particles. Consequently, the mechanical properties were significantly enhanced in the material made of milled powder. Apart from grain refinement, the improvements in mechanical performance were attributed to the synergic effect of the irregular shape of the milled particles and better consolidation due to effectively disrupted MgO shells, thus suppressing the crack formation and propagation during loading. These results suggest that relatively short milling of magnesium alloy powder can be effectively used to achieve superior mechanical properties during consolidation by SPS even at relatively low temperatures.

Pseudo core-shell LaCoO3@MgO perovskite oxides for high performance methane catalytic oxidation

Magnesia modified LaCoO3 was prepared by a facile one-step sol-gel method and used for removal of dilute methane. Compared with the conventional doping technique, the obtained LaCoO3@MgO-x exhibits pseudo core-shell structure and shows superior catalytic activity. The methane conversion exceeds 90% at 532 °C on LaCoO3@MgO-0.1, while only 60% of methane is conversed using the doped perovskite LaCo0.9Mg0.1O3. The high catalytic performance of LaCoO3@MgO-0.1 is mainly attributed to the adjustment of surface acid-base properties by the MgO shell structure. According to density functional theory (DFT) calculation, the methane is more likely to be adsorbed and cracked on LaCoO3@MgO-0.1. The in situ DRIFTS shows that CH3–O–CH3 intermediate specie is formed. The pseudo core-shell structure also enhances the stability and the LaCoO3@MgO-0.1 maintains high activity after working for 100 h. The above results demonstrate that surface modification by magnesia is an effective strategy for improving LaCoO3 catalytic performance.

Encapsulation of Phase-Changing Eutectic Salts in Magnesium Oxide Fibers for High-Temperature Carbon Dioxide Capture: Beyond the Capacity-Stability Tradeoff.

Eutectic mixture (EM)-promoted MgO sorbents exhibit high CO2 sorption capacities but experience a significant decrease in uptake after multiple sorption-regeneration cycles due to EM movement and redistribution at high temperatures. Encapsulation of a pseudoliquid, phase-changing EM promoter with MgO may thus prevent the loss of active interface by confining the EM within a fixed area inside a MgO shell. In this work, we successfully embedded an EM composed of KNO3 and LiNO3 in a MgO fiber matrix via core-shell electrospinning. The synthesized sorbent achieved relatively high and steady sorption capacities, maintaining a stable uptake of ∼20 wt % after 25 sorption-regeneration cycles. The sorbent was also characterized using various techniques including in situ transmission electron microscopy (TEM) to describe its morphology, from which it was confirmed that the eutectic salt existed in distributed hollow pockets within the MgO fiber matrix and stayed confined within these fixed areas, favorably limiting its movement and redistribution when exposed to high temperatures where it exists in the liquid form. The EM may also be described as a glue that holds the fiber together, while MgO acts as a protective shell that prevents structural changes and rearrangement caused by EM movement, allowing the sorbent to retain its cyclic stability after multiple cycles and demonstrating its potential for industrial use after further improvement. Thus, the microencapsulation of a phase-changing EM material with pure MgO metal oxide was successfully achieved and might be explored for various material applications.

Effect of MgO coverage on the synthesis and thermal treatment of Pt-Sn/C catalysts

To prevent sintering of carbon supported metal nanoparticles during high temperature annealing in reductive conditions, Pt-Sn nanoparticles were coated with MgO. The agglomeration of Pt-Sn particles upon thermal annealing was significantly inhibited with a MgO shell. The presence of the oxide shell gave rise to a more homogeneous microstructure and a better electrochemical stability.

Effect of MgO shell on electron transfer from Cu doped ZnInS quantum dots to FePt nanoparticles

The effect of MgO shell on the electron transfer between luminescent Cu doped ZnInS quantum dots (QDs) and magnetic FePt/MgO core/shell nanoparticles (NPs) was studied by using steady-state and time-resolved photoluminescence (PL) spectroscopy. MgO-coated FePt NPs were synthesized using 4 nm FePt cores as seeds for the growth of MgO shell, having a reduced saturation magnetization Ms compared to the pure FePt NPs. It was found that the shortening in PL lifetime of Cu doped ZnInS QDs induced by FePt NPs demonstrated an electrons transfer process from excited QDs to the adjacent FePt NPs. When FePt NPs were coated with a MgO shell, the low work function of MgO shell resulted in a formation of higher interfacial barriers between Cu doped ZnInS QDs and FePt NPs, significantly suppressing the electron transfer at Cu doped ZnInS QD-FePt NP interface.

Effect of Material Structure on Photoluminescence of ZnO/MgO Core‐Shell Nanowires

AbstractZinc oxide (ZnO) nanowires are widely studied for use in ultraviolet optoelectronic devices, such as nanolasers and sensors. Nanowires (NWs) with an MgO shell exhibit enhanced band‐edge photoluminescence (PL), a result previously attributed to passivation of ZnO defects. However, we find that processing the ZnO NWs under low oxygen partial pressure leads to an MgO‐thickness‐dependent PL enhancement owing to the formation of optical cavity modes. Conversely, processing under higher oxygen partial pressure leads to NWs that support neither mode formation nor band‐edge PL enhancement. High‐resolution electron microscopy and density‐functional calculations implicate the ZnO m‐plane surface morphology as the key determinant of core‐shell structure and cavity‐mode optics. A ZnO surface with atomic steps along the m‐plane in the c‐axis direction stimulates the growth of a smooth MgO shell that supports guided‐wave optical modes and enhanced UV PL. On the other hand, a smoother ZnO surface leads to nucleation of a rough cladding layer which supports neither enhanced UV PL nor optical cavity modes. Finite‐element analysis shows a clear correlation between allowed Fabry‐Perot and whispering gallery modes and enhanced UV‐PL. These results point the way to fabricating ZnO/MgO core‐shell nanowires for more efficient UV nanolasers, scintillators, and sensors.

Influence of MgCl2 content on corrosion behavior of GH1140 in molten NaCl-MgCl2 as thermal storage medium

As a thermal energy storage medium (TESM) at moderate-high temperature of concentrating solar power (CSP), the molten NaCl-MgCl2 has sharp corrosive action on a metal container. The influence of MgCl2 content on a metal corrosion behavior is not clear. The corrosion behavior of a Fe based alloy (GH1140) in molten NaCl-MgCl2 (at 1123K) with different content of MgCl2 (wt%：0.0，48.9，61.0，93.6) were studied by the submergence corrosion experience. Results show that: after corrosion for 5h, there is a negative correlation between the weight loss of samples and the content of MgCl2. In the molten salt without MgCl2, the sample was corroded according to the mechanism of “dissolution as anode- oxidizing- peeling off of oxide film”. After adding a little MgCl2 in the molten salt, an unprotected MgO shell was formed on the sample surface. The samples weight decreased and obeyed a line law. The elements of Fe and Cr deplete in the corrosion layer. Corrosion mechanism is “dissolution as anode- oxidizing- reduction- chlorination”. When the content of MgCl2 is very high in the molten salt, partial pressure of Cl2 increases. The corrosion mechanism is similar to what in the molten salt with a little MgCl2, but the chlorination reaction is more severe.

The shell effect on the room temperature photoluminescence from ZnO/MgO core/shell nanowires: exciton–phonon coupling and strain

The room temperature photoluminescence from ZnO/MgO core/shell nanowires (NWs) grown by a simple two-step vapor transport method was studied for various MgO shell widths (w). Two distinct effects induced by the MgO shell were clearly identified. The first one, related to the ZnO/MgO interface formation, is evidenced by strong enhancements of the zero-phonon and first phonon replica of the excitonic emission, which are accompanied by a total suppression of its second phonon replica. This effect can be explained by the reduction of the band bending within the ZnO NW core that follows the removal of atmospheric adsorbates and associated surface traps during the MgO growth process on one hand, and a reduced exciton–phonon coupling as a result of the mechanical stabilization of the outermost ZnO NW monolayers by the MgO shell on the other hand. The second effect is the gradual increase of the excitonic emission and decrease in the defect related emission by up to two and one orders of magnitude, respectively, when w is increased in the ∼3–17 nm range. Uniaxial strain build-up within the ZnO NW core with increasing w, as detected by x-ray diffraction measurements, and photocarrier tunneling escape from the ZnO core through the MgO shell enabled by defect-states are proposed as possible mechanisms involved in this effect. These findings are expected to be of key significance for the efficient design and fabrication of ZnO/MgO NW heterostructures and devices.

Enhanced hydriding kinetics of Mg-10 at% Al composite by forming Al 12 Mg 17 during hydriding combustion synthesis

Abstract Mg-based alloys are widely considered as promising materials for hydrogen storage. However, owing to the high chemical activity of Mg, the surface of Mg powder is always covered with a layer of close packed MgO, which can retard the hydrogenation of Mg. In this paper, 10 at% Al was added to accelerate the hydriding kinetics of Mg through tabletting and grinding treatments. After heating to 420 °C and subsequent holding at 340 °C for 120 min under 1.5 MPa hydrogen pressure, the Mg-10 at% Al composite could absorb 6.34 wt% H2 in the process of hydriding combustion synthesis (HCS) while the same treated pure Mg powder was barely hydrided. Upon heating from room temperature to 420 °C, Al alloyed with Mg to form an Al12Mg17 phase on the surface of Mg particles and the newly formed alloy was oxide-free, which would react with H2 when the temperature decreased to 340 °C. Then hydrogen was able to get into the inner part of the Mg particle from the former Al12Mg17 sites where the MgO shell had been broken in the alloying period to further react with unhydrided Mg.

High-performing and durable MgO/Ni catalysts via atomic layer deposition for CO2 reforming of methane (CRM)

MgO-coated Ni catalysts with two different shell thicknesses were prepared using atomic layer deposition (ALD) and their catalytic activities for the CO2 reforming of CH4 (CRM) were compared with that of bare Ni catalyst. Conversion of CO2 and CH4 in the CRM reaction at 800°C was enhanced with increasing thickness of the ALD-deposited MgO shells. In particular, the catalytic activity of MgO/Ni catalyst prepared using 200 ALD MgO deposition cycles was fairly durable, with negligible deactivation during a 72h CRM reaction. We suggest that the MgO shell, which is highly basic and has high affinity to CO2, likely, accelerated the reverse CO disproportionation, thereby reducing the poisoning of Ni active sites during the CRM reaction. Furthermore, the 200-cycled MgO shell destroyed ensemble of Ni catalysts surface, allowing preservation of Ni active sites with preferential growth of filamentous carbon to layered graphitic ones. We suggest that the preparation of core–shell structures using ALD can be a promising strategy for fabricating highly active and durable catalysts that are operable at relatively high temperatures.

Enhanced Dielectric Properties of Ba0.5Sr0.5TiO3/MgO Composites Prepared by Coprecipitation Derived Core–Shell Powders

Ba0.5Sr0.5TiO3/MgO (BST/MgO) composite ceramics have been prepared in situ by using an oxalate precipitation process. SEM and TEM images show that oleic acid modified BST/MgO nanocomposite exhibits helminth‐like particles consisting of BST core and MgO shell. Results reveal that oleic acid modification is chemisorbed on MgO particles as a carboxylate to form MgO shell, which connects to interparticles. Accordingly, the BST particles are well surrounded naturally by a thin MgO layer in the composite ceramics. As a result, the oleic acid modified BST/MgO composite ceramics shows better dielectric properties, with permittivity of 203, loss tangent of 0.0025 (at 2.4 GHz), and tunability of 10.2%.

Fabrication of Core-Shell Structured TiO<sub>2</sub>/MgO Electrodes for Dye-Sensitized Solar Cells

We demonstrated the construction and performance of dye-sensitized solar cells (DSCs) based on nanoparticles of TiO2 coated with thin shells of MgO by simple solution growth technique. The XRD patterns confirm the presence of both TiO2 and MgO in the core-shell structure. The effect of varied shell thickness on the photovoltaic performance of the core-shell structured electrode is also investigated. We found that MgO shells of all thicknesses perform as barriers that improve open-circuit voltage (Voc) of the DSCs only at the expense of a larger decrease in short-circuit current density (Jsc). The energy conversion efficiency was greatly dependent on the thickness of MgO on TiO2 film, and the highest efficiency of 4.1% was achieved at the optimum MgO shell layer.

Identification and characteristics of ZnO/MgO core-shell nanowires

In this paper, ZnO/MgO core-shell nanowires are synthesized based on a one-step chemical vapor deposition (CVD) method. The scanning electron microscopy (SEM) images of core-shell nanowires indicate that Mg addition has little influence on the morphology of the synthesizing products. High crystalline quality ZnO/MgO core-shell nanowires instead of ZnMgO ternary compounds are identified by X-ray diffraction (XRD) patterns, transmission electron microscopy (TEM) images, selected area electron diffraction (SAED) pattern and photoluminescence (PL) spectra. The experimental results show that the ultraviolet (UV) emission of these samples with MgO shell is 12 times higher than that of the corresponding bare ZnO nanowires, and the suppression of the green emission is only 1/45 of the bare ZnO nanowires. It is also found that PL properties are proportional to Mg ratio. The UV emission enhancement and green emission suppression are due to the passivation of surface defects and the improvement of ZnO crystalline quality. The results are very useful for the development of optical devices based on nanowires.