One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

Far-red-emitting YAl3(BO3)4:Cr3+ phosphors with excellent thermal stability and high luminescent yield for plant growth LEDs

Phosphors-converted LEDs (pc-LEDs) are excellent artificial light sources for indoor plant cultivation, in which the far-red-emitting component (700−780 nm) plays an important role in regulating the photomorphogenesis of plants. Accordingly, highly efficient and thermally stable far-red-emitting phosphors are indispensable for developing high-performance plant cultivation pc-LEDs. Herein, far-red-emitting YAl₃(BO₃)₄:Cr³⁺ (YAB:Cr³⁺) phosphors were synthesized by solid-state reaction, and their photoluminescence characteristics, thermal quenching, quantum yield (QY), and application in pc-LEDs were systematically investigated. The YAB:Cr³⁺ phosphor has an intense broadband absorption to the blue light, simultaneously exhibiting the sharp-line ²E emission and the broadband ⁴ T₂ emission of Cr³⁺ with a QY of ~86.7%. The far-red broadband emissions of YAB:Cr³⁺ centered at ~735 nm show a high resemblance to the active-state (P_FR) absorption of plant phytochrome. Moreover, the YAB:Cr³⁺ phosphor shows the thermally enhanced luminescence at temperatures of 303−393 K and the near-zero thermal quenching up to 423 K. The anomalous thermal enhancement is attributed to the temperature-dependent repopulation between ²E and ⁴ T₂ states. Finally, a pc-LED device was fabricated with the YAB:Cr³⁺ phosphor and blue chip, exhibiting the light out power of ~50.6 mW and energy conversion efficiency of ~17.4% at 100 mA drive current, respectively. The exceptional PL features including suitable excitation/emission wavelengths, suppressed thermal quenching and high QY make YAB:Cr³⁺ phosphors very promising for applications in plant growth pc-LEDs.     

Synthesis and characterization of the novel nanostructured NiC carbide obtained by mechanical alloying

In the present work, a comprehensive study of mechanical alloying of Ni-carbon nanotubes (CNT) and Ni-Graphite equiatomic powder mixtures under the same technological modes has provided to reveal the features of using different types of carbon (CNT or graphite) as a charge component. The as-milled powders were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and magnetometric study. A novel nanoscale fcc NiC monocarbide was synthesized regardless the type of the charge used. According to the XRD study the formation of this phase takes place in two stages. A two-step carbide formation mechanism has been proposed. The associated changes in the nickel lattice, such as changes in the lattice parameter, lattice strain and residual stresses, which led to the formation of NiC monocarbide were also evaluated and discussed. Parameters of the electronic structure of NiC were calculated using the MStudio MindLab 7.0 software package with the experimental data on the crystal structure of the NiC phase obtained as input. Temperature dependencies of magnetic susceptibility of NiC synthesized have been studied up to 950 K. Carbides synthesized were found to be weak ferromagnets at the room temperature and their Curie temperature T_C ranges within 670 – 725 K. The calculated value of the magnetic moment per nickel atom (2.83μ_B) is higher than that of a bulk Ni (1.3μ_B). Likely, the observed increase of μ is caused by the presence of a certain amount of residual single-domain ferromagnetic Ni nanoparticles in the samples synthesized.     

Integrating coral-like morphology into cyano-containing carbon nitride towards efficient photocatalytic H2 evolution and Cr(Ⅵ) reduction

The incomplete polymerization of graphite carbon nitride (g-C₃N₄) due to the kinetic problems resulted in its high recombination rate of photo-generated electron-hole pairs. Hence, cyano-containing carbon nitride with coral-like morphology (CCCN) was prepared by the molten salt method with heptazine-based melem as precursor, which presented excellent separation rate of photo-generated electron-hole pairs. SEM exhibited that CCCN owned coral-like morphology which exposed ample active sites and enhanced the capture ability of visible light while FT-IR and XPS demonstrated that cyano groups appearing in coral-like carbon nitride enhanced the separation rate of photo-induced charge carriers. The synergistic effect of coral-like morphology and cyano groups endowed CCCN-15% with superior performance of both the photocatalytic H₂ evolution (4207 μmol h^?1 g^?1) and Cr (Ⅵ) reduction (k = 0.059 min^?1), approximately 16.8 and 6.0 times that of g-C₃N₄, which was comparable among the similar materials. Density functional theory calculation (DFT) revealed that cyano groups decreased the bandgap and strengthened the activation degree of reaction substrate, which enhanced the thermodynamic driving force and the interaction between catalyst and substrate. This work provided a potential strategy for both the renewable energy generation and environmental restoration.     

Complex study of protective Cr3C2–NiAl coatings deposited by vacuum electro-spark alloying,pulsed cathodic arc evaporation,magnetron sputtering,and hybrid technology

Coatings were obtained by vacuum electro-spark alloying (VESA), pulsed cathodic arc evaporation (PCAE), magnetron sputtering (MS) techniques and VESA-PCAE-MS hybrid technology using Cr₃C₂–NiAl electrodes. The structure of the coatings was analyzed using scanning and transmission electron microscopy, X-ray diffraction and energy-dispersive spectroscopy. Mechanical properties were determined by nanoindentation, while tribological properties were assessed using pin-on-disk tribometer. Corrosion resistance was estimated by voltammetry in 1 N H₂SO₄ and 3.5%NaCl solutions. Oxidation resistance tests were performed at 800°С in air. The VESA coating had the highest thickness, low friction coefficient and high wear resistance. PCAE coating demonstrated the highest hardness (24 GPa) and elastic recovery (59%), oxidation resistance and superior corrosion resistance both in 1 N H₂SO₄ (i_corr = 70 μА/cm²) and 3.5%NaCl (i_corr = 0.74 μА/cm²) solutions. The MS coating had average mechanical properties and low corrosion current density (71 μА/cm²) in 1 N H₂SO₄. Deposition of coatings using VESA-PCAE-MS hybrid technology led to an increase in corrosion and oxidation resistance at least by 1.5 times in comparison with the VESA coating.     

Microstructure and some properties of powder-pack borided Ti–5Mo–5V–8Cr–3Al alloy with special attention to the microstructure at the interface TiB/substrate

The borided layer was prepared on the surface of the Ti–5Mo–5V–8Cr–3Al alloy by powder-pack boriding at 1000°C-10h. SEM, EPMA and TEM were used to investigate the effects of alloying elements (Al, V, Mo and Cr) on the growth of TiB whiskers in the borided Ti–5Mo–5V–8Cr–3Al alloy. Wear properties of borided Ti–5Mo–5V–8Cr–3Al alloy were investigated using dry reciprocating friction tests. SEM results show that the thickness of boride layer in Ti–5Mo–5V–8Cr–3Al alloy is thinner than that in the Cp-Ti. This is attributed to the enrichment of alloying elements especially V in TiB/substrate by TEM, which hinders the diffusion of B atoms, thus resulting in the short and thick TiB whiskers in Ti–5Mo–5V–8Cr–3Al alloy. Borided Ti–5Mo–5V–8Cr–3Al alloy has the better wear resistance than as-received alloy.     

Facile synthesis of Ti3C2 MXene-modified Bi2.15WO6 nanosheets with enhanced reactivity for photocatalytic reduction of Cr(VI)

Through a facile hydrothermal method, we have successfully prepared Ti₃C₂/Bi_2.15WO₆ (TC/BWO) composite, and systematically investigated their reactivity for the photocatalytic reduction of Cr(VI) under visible light. X-ray diffraction and Raman analysis confirm the formation of heterostructure between Bi_2.15WO₆ and Ti₃C₂. The resultant 7TC/BWO composite exhibits enhanced photoactivity toward Cr(VI) reduction. After 120 min irradiation, the conversion of Cr(VI) reaches 92.5% with the quasi-first-order kinetic constant of k = 0.0145 min^?1, which is higher than that of pure BWO (30% and k = 0.0005 min^?1). The electrochemical and photoluminescent characterization confirm that the introduction of Ti₃C₂ is conducive to the separation of carriers, thus significantly improves the photocatalytic performance of TC/BWO. Furthermore, the radical capture experiments verify that the electrons are important for enhancing reduction of Cr(VI) to Cr(III). As a result, this research provides a comprehensive understanding of the reduction of Cr(VI) by TC/BWO composite under visible light.     

Ni–Cr alloys for effectively enhancing hydrogen evolution processes in phosphate-buffered neutral electrolytes

Significant efforts have been made to develop highly active non-noble metal-based, affordable metallic and stable electro-catalysts for hydrogen evolution reaction (HER). Strong acid and bases are now used in HER operations to achieve large-scale, sustained H₂ fuel production. However, few studies have utilized phosphate-buffered neutral electrolytes (PBS) in the field of neutral electrolyte technology. In this work, a certain alloys with a Ni–Cr basis have been produced as favorable components for the HER under neutral conditions. Additionally, the current investigations are emphasizing on the concentration of buffer phosphate species in the HER activity of various materials. By employing polarization and electrochemical impedance spectroscopy (EIS) in neutral solutions, the electro-catalytic activity of new alloys on HER was evaluated. According to the preliminary findings, the examined Ni–Cr-based alloys show superior HER catalytic activity in neutral electrolytes. Additionally, the Ni–Cr alloy matrix with Fe and Mo added enhances HER electrocatalytic efficiency while lowering interfacial charge transfer resistance. Due to its low overpotential of ?297 mV @ 10 mA cm^?2 and Tafel slope of 94 mV dec^?1 in 1.0 M PBS media, the Ni–Cr–Mo–Fe alloy exhibits an efficient HER, suggesting that the Ni–Cr–Mo–Fe electrode will be a potential noble metal-free electro-catalyst for HER. The Ni–Cr–Mo–Fe cathode is a readily available and affordable material for the production of HER in neutral medium.     

New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

The structure,vacancy characteristics,and magnetic properties of GdMn1-xCrxO3 ceramics

To investigate the evolution of the structural and enhanced magnetic properties of GdMnO₃ systems induced by the substitution of Mn with Cr, polycrystalline GdMn_1-xCr_xO₃ samples were synthesized via solid-state reactions. XRD characterization shows that all GdMn_1-xCr_xO₃ compounds with single-phase structures crystallize well and that Cr³⁺ ions entering the lattice sites of GdMnO₃ induce structural distortion. SEM results indicate that the grain size of the synthesized samples (a few microns) decreases as the Cr substitution concentration increases. Positron annihilation lifetime spectroscopy reveals that vacancy-type defects occur in GdMn_1-xCr_xO₃ ceramics and that the vacancy size and concentration clearly change with the Cr content. The temperature and field dependence of the magnetization curves show that Cr substitution significantly influences the magnetic ordering of the gadolinium sublattice, improving the weak ferromagnetic transition temperature and magnetization of GdMn_1-xCr_xO₃. The enhanced magnetization of GdMn_1-xCr_xO₃ is closely related to the vacancy defect concentration.