Cu-doped K2Ti6O13 (Cu–KTO) nanowires were prepared using a combination of sol–gel and hydrothermal methods to improve the photocatalytic and antibacterial performance of K2Ti6O13 (KTO) nanowires. The Cu–KTO nanowires maintained the monoclinic structure of KTO. The Cu2+ ions could enter into the lattice of KTO by substituting for certain Ti4+ ions and cause the formation of defects and oxygen vacancies. The UV–Visible absorption spectra showed that after Cu doping, the absorption edge of KTO moved to the visible region, indicating that the band gap decreased and the ability to absorb visible light was acquired. The photocatalytic properties of the Cu–KTO nanowires with different doping amounts were assessed by simulating the photodegradation of rhodamine B (RhB) under simulated sunlight irradiation. The 1.0 mol% Cu–KTO nanowires showed the best photocatalytic performance, and 91% of RhB was decomposed by these nanowires (the catalyst dose was only 0.3 g/L) within 5 h. The performance of the Cu–KTO nanowires was much better than that of the KTO nanowires. The Cu–KTO nanowires also showed high antibacterial activity for Escherichia coli (ATCC 25922) of up to 99.9%, which was higher than that of the pure KTO samples. Results proved that Cu doping is an effective means to develop multifunctional KTO nanomaterials. It can be used to degrade organic pollutants and remove harmful bacteria simultaneously in water environments.
1 June 2018 in Chinese Journal of Chemical Physics
Based on the experimental study of the optical properties of K2Ti6O13 doped with Fe or Ag, their electronic structures and optical properties are studied by the first-principles method based on the density functional theory (DFT). The calculated optical properties are consistent with the experiment results. K2Ti6O13 doped with substitutional Fe or Ag has isolated impurity bands mainly stemming from the hybridization by the Fe 3d states or Ag 4d states with Ti 3d states and O 2p states and the band gap becomes narrower, the absorption edge of K2Ti6O13 thus has a clear red shift and the absorption of visible light can be realized after doping. For Fe-doped K2Ti6O13, the impurity bands are in the middle of the band gap, suggesting that they can be used as a bridge for valence band electrons transition to the conduction band. For Ag-doped K2Ti6O13, the impurity bands form a shallow acceptor above the valence band and can reduce the recombination rate of photoexcited carriers. The experimental and calculated results are significant for the development of K2Ti6O13 materials that have absorption under visible light.
Magnesium-based bulk metallic glasses (BMGs) are typical intrinsic brittle lightweight BMG alloys, and their improvement in plasticity has attracted widespread attention in the field of BMGs. We used the electroplating method to modify the surface of Mg59.5Cu22.9Ag11Gd6.6 BMGs and investigated the geometric confinement effect of the Ni coating on the mechanical properties of the BMG. The results show that under the plating conditions of adding 1 g/L nano Al2O3 to the plating solution, adjusting the plating temperature to 50 °C, and plating time to 3 h, a smooth and dense nickel coating with a thickness of about 150 μm can be formed on the surface of the Mg-based BMG. The uniaxial compression tests showed that the average fracture strength of the BMG was increased from 565 MPa to 598 MPa by a 50 μm Ni coating, and the fluctuation range of strength was decreased from 429 MPa to 265 MPa, a reduction of 36%. The Weibull analysis showed that the Weibull modulus m was increased from 4.3 to 4.8 by the coating, and the safety stress was increased from 54 MPa to 235 MPa, indicating that electroplating nickel could improve the reliability of the Mg-based BMG alloy. However, no significant improvement of the compression plasticity was found, which indicated that improving the room temperature plasticity of brittle Mg-based BMG alloys by the geometric confinement of electroplating Ni was limited. The influence of the thickness of the Ni coating on the maximum stress level and stress distribution in the BMG samples was analyzed by ANSYS finite element simulation. It was found that when the thickness of the coating was 30% of the radius of the cylindrical compressed sample, the stress distribution caused by the Ni coating was the most uniform, and the maximum stress level was relatively reduced, which is beneficial for improving the geometric confinement effect. As a result, the Mg-based BMG sample coated with a Ni coating of 150 μm thickness exhibited ~0.3% macroscopic compressive plasticity. This is of great significance for understanding the plastic deformation mechanism of brittle BMGs improved by geometric confinement.
The catalytic capabilities of metals in degrading azo dyes have garnered extensive interest; however, selecting highly efficient metals remains a significant challenge. We have developed a Zn-Ca-based metallic glass composite which shows outstanding degradation efficiency for Direct Blue 6. This alloy comprises a Zn2Ca crystalline phase and an amorphous matrix, allowing for the degradation of azo dyes within minutes in a wide temperature range of 0–60 °C. Kinetic calculations reveal an exceptionally low activation energy of 8.99 kJ/mol. The rapid degradation is attributed to the active element Ca and the unique amorphous structure of the matrix, which not only facilitates abundant redox conditions but also minimizes the hydrolysis of the active element. The newly developed metallic glass composite exhibits a notably higher azo dye degradation rate compared to those of general metallic glasses, offering a new avenue for the rapid degradation of azo dyes. This paper holds significant importance for the development of novel azo dye wastewater treatment agents.
The development of novel antibacterial nano-materials with synergistic biological effects has attracted extensive interest of the researchers. In the study, 0.5 mol% Ag and 0.5 mol% Cu co-doped K2Ti6O13 (0.5 Ag-0.5 Cu-KTO) nanomaterial was successfully synthesized using two-step method of sol–gel and hydrothermal synthesis. The crystal structure of 0.5 Ag-0.5 Cu-KTO was the same as that of monoclinic K2Ti6O13. Ag ions and Cu ions were uniformly loaded on K2Ti6O13 by replacing partial Ti ions, so that these antibacterial ions could be slowly released. High specific surface area of 0.5 Ag-0.5 Cu-KTO (337.6 m2 g−1) provided more surface active sites for Ag–Cu doping and adsorption. More negative surface zeta potential (−32.83 mV in phosphate buffer solution and −21.45 mV in physiological saline solution, respectively) would be beneficial to prevent the aggregation of the nanowires in physiological environment. Under the same doping amount, compared to 1.0 mol% Cu doped K2Ti6O13, 0.5 Ag-0.5 Cu-KTO exhibited better antibacterial performance against gram-positive and gram-negative bacteria at only 100 μg ml−1 dose concentration, near to 1.0 mol% Ag doped K2Ti6O13 (1.0 Ag-KTO). And 0.5 Ag-0.5 Cu-KTO showed more excellent biocompatibility than 1.0 Ag-KTO, which was attribute to the introduction of Cu ions effectively decreasing the hemolytic and cytotoxic risks from Ag ions. As expected, the synthesized 0.5 Ag-0.5 Cu-KTO nanowires demonstrated excellent structural stability, high antibacterial activity, good hemocompatibility and cytocompatibility owing to the synergistic effects of Cu and Ag ions. 0.5 Ag-0.5 Cu-KTO nanowires will be a promising antimicrobial candidate for biomedical applications.
Mg-based metallic glass (MG) has attracted extensive attention in the field of wastewater treatment due to its high decolorization rate in degrading azo dyes. However, the azo dye degradation rate of Mg-based MGs is strongly dependent on the particle size. Improving the intrinsic degradation efficiency using large particles is of great interest for future applications. In this work, in-situ metallic glass matrix composites (MGMCs) with high Mg content were successfully prepared by melt spinning. It is found that when the Mg content is 79–82%, the as-spun sample shows typical glassy characteristics. The SEM and XRD tests confirm that the as-spun sample is composed of α-Mg dendrite, multiple Mg-Zn intermetallic particles and an MG matrix. The degradation experiment using Direct Blue 6 and a 500 μm particle sample demonstrate that the Mg82Zn14Ca3Sr1 MGMC sample degrades azo dyes faster than typical Mg-Zn-Ca MG alloy. It can be attributed to the galvanic cell effect on the α-Mg/MG interface, which reduces the waste of active Mg atoms in the MG matrix according to the corrosion protection mechanism by the α-Mg anode sacrifice. This result provides a new perspective and insight into the design of azo dye degradation alloys and the understanding of degradation mechanisms.