Mechanism of optical limiting in metalloporphyrins under visible continuous radiation.

Here, we present an experimental investigation on the nonlinear optical (NLO) and optical limiting properties of metalloporphyrin compounds (Cu-1-OH, Zn-1-OH, Cu-1-E and Zn-1-E) using spatial self-phase modulation (SSPM) method in the visible range. It is found that all of the samples show a large self-defocusing effect at 532 nm, which is attributed to the thermal nonlinear optical effects with negative nonlinear refractive index coefficient n2 due to the relatively high absorption at 532 nm. In contrast, at 780 nm where absorption is weak for both Zn- and Cu-porphyrins, Zn-porphyrins still exhibit visible self-defocusing while Cu-porphyrins do not show any nonlinear diffraction pattern. Such a phenomenon can be explained by the Kerr effect of Cu-porphyrins at 780 nm. As the thermal nonlinear optical effects (of negative n2) at 780 nm are reduced due to the low absorption, the Kerr effect with positive n2 becomes comparable and the overall nonlinearity is reduced. The Kerr effect of Cu-porphyrins is stronger than that of Zn-porphyrins because of the enhanced π-electron delocalization effect as Cu(II) has a variable number of valence electrons and incompletely filled d atomic orbitals. Finally, the optical limiting performance of Zn-porphyrins is demonstrated as a representative and its dependence on sample position is examined. This work not only enriches the understanding of the physical mechanism of optical limiting in porphyrin materials, but also provides a significant reference to improve the third-order NLO coefficient by adjusting the structure of compounds.

Recovery of Acid and Alkaline from Industrial Saline Wastewater by Bipolar Membrane Electrodialysis under High-Chemical Oxygen Demand Concentration.

Actual high saline wastewater containing concentrated organics and sodium chloride is a bioenergy and renewable resource. This study compared two different bipolar membrane electrodialysis membranes from two companies' stacks to recover HCl and NaOH from sodium chloride solution and actual chemical wastewater. The results demonstrated that the electrolysis rates were around 1.5 kg/m2h, the HCl and NaOH production rates were about 0.9 kg/m2h, energy consumption was in the range of 1.05-1.27 kWh/kg, and the economic benefits were above 1 yuan/h in BMED systems. From analyzing the performance of seven different BMED membrane stacks, the B2 stack was chosen for electrolyzing actual high salt wastewater to observe the effect of chemical oxygen demand on BMED systems, where electrolytic salt performance, HCl-NaOH alkali production rates, and energy consumption show linear dependence on time for 5000 mg/L chemical oxygen demand wastewater. It illustrated chemical oxygen demand can enhance energy consumption and reduce electrolytic salt performance and the acid and alkali production rates, due to improving the membrane area resistance. In this study, the effect of high COD saline wastewater on the performance of a BMED membrane stack was clarified and the mechanism was analyzed for its practical application in treating chemical high salt wastewater.

Excellent removal performance of 4,4'-biphenyldicarboxaldehyde m-phenylenediamine Schiff base magnetic polymer towards phenanthrene and 9-phenanthrol: Experimental, modeling and DFT calculations studies.

Phenanthrene (PTH) and 9-phenanthrol (9-PTH) exhibited severe health threats and ecological hazards, for this reason, exploring a high-efficient removing strategy for PTH and 9-PTH could be considered of great urgency. Herein the 4,4'-biphenyldicarboxaldehyde m-phenylenediamine Schiff base magnetic polymer (magnetic BIPH-PHEN) was successfully fabricated via Schiff base polycondensation reaction and the subsequently one-pot embedded method. The mutual aromatic nucleus of BIPH-PHEN polymer and PTH/9-PTH could form π-π interaction, thus improving the capture ability, the embedded Fe3O4 nanoparticles provided the possibility for rapid separation. The physical and chemical properties of the magnetic BIPH-PHEN were systematically characterized. The removal rate of magnetic BIPH-PHEN towards PTH and 9-PTH was 85.65 % and 98.52 %, respectively (PTH or 9-PTH: 8 mg/L; Adsorbent: 0.2 g/L). The DFT calculations including energy calculations and electrostatic potential distribution analyzed the different bonding modes and proposed the most possible bonding modes in the adsorbent/adsorbate system. Moreover, the LUMO and HOMO orbits combined with energy gaps analysis proved the existence and specific types of the π-π interaction. The monolayer adsorption occurred on the homogeneous magnetic BIPH-PHEN surface, simultaneously the chemisorption was dominant. This work not only proposed new sights on assembling magnetic Schiff base polymer for removing polycyclic aromatic hydrocarbons, but also provided a deeper understanding of intramolecular interactions.

Permeability characteristics and structural evolution of compacted loess under different dry densities and wetting-drying cycles.

Permeability characteristics of compacted loess is always an important topic in soil mechanics and geotechnical engineering. This study explored the permeability characteristics of compacted loess under different dry densities and wetting-drying cycles, and found that as the dry density increases, the compacted loess surface became denser, the saturation permeability coefficient and saturation infiltration rate decreased. However, the wetting-drying cycle presented the opposite result. Meanwhile, the evolution of the microstructure was investigated by Scanning Electron Microscope (SEM) and Nuclear Magnetic Resonance (NMR) to explain the change of its permeability characteristics. The size of compacted loess aggregates was quantitatively analyzed by Image-Pro Plus (IPP) software. It showed that the size of compacted loess aggregates for different dry densities were concentrated from 10-100 µm, occupying 65.0%, 58.19%, and 51.64% of the total aggregates area respectively. And the interesting finding was that the area occupied by 10-50 µm aggregates remained basically unchanged with the number of wetting-drying cycles increasing. Therefore, the size of 10-50 µm aggregates represented the transition zone of compacted loess. NMR analyses revealed that with increasing dry density, the volume of macropores in the compacted loess rapidly decreased, the volume of mesopores and small pores increased. Meanwhile, the change in micropores was relatively small. The pore volume of the compacted loess after three wetting-drying cycles increased by 8.56%, 8.61%, and 6.15%, respectively. The proportion of macropores in the total pore volume shows the most drastic change. Variations in aggregate size and connection relationships made it easier to form overhead structures between aggregates, and the increased of macropore volume will form more water channels. Therefore, the change in permeability characteristics of compacted loess is determined by aggregate size, loess surface morphology, and the total pore volume occupied by macropores.

Comparison and quantitative analysis of microstructure parameters between original loess and remoulded loess under different wetting-drying cycles.

The microstructural evolution of loess had a significant impact on the collapsibility of loess during wetting-drying cycles. Based on the analysis of scanning electron microscope (SEM) images by using Image-Pro Plus, the present study quantitatively compared the microstructural parameters of original loess and remoulded loess with different moisture content before and after wetting-drying cycles in size, shape, and arrangement. In size, the average diameter of both original loess particles and remoulded loess particles increased with the increasing of initial moisture content. However, the average diameter of original loess particles was slightly larger than that of remoulded loess particles before wetting-drying cycles. In contrast, the average diameter of both original loess particles and remoulded loess particles were very close to each other after three wetting-drying cycles. In shape, before wetting-drying cycles, the average shape factor of original loess particles was higher than that of remoulded loess particles. After three wetting-drying cycles, the difference in the average shape factor of both two loess samples with 5% initial moisture content is similar to that before wetting-drying cycles. Nevertheless, the average shape factor of both original loess particles and remouled loess particles with 15% initial moisture content were very close to that with 25% initial moisture content. In the arrangement, directional frequency indicated remoulded loess appeared to be more vertically aligned than original before and after three wetting-drying cycles. Furthermore, the directed anisotropy rate of remoulded loess was higher than that of the original loess before and after three wetting-drying cycles. In summary, the size, shape, and arrangement of both original loess particles and remoulded loess particles varied in different degrees before and after three wetting-drying cycles. Combined with the water retention curve of the loess, we analyzed the microstructural evolution mechanism of two loess particles during wetting-drying cycles. It is an excellent significance to study the engineering properties of original loess and remoulded loess.

Spectroscopic investigations on the simulated solar light induced photodegradation of 4-nitrophenol by using three novel copper(II) porphyrin-TiO2 photocatalysts.

Three porphyrins containing different functional groups (-OH, C-O2C2H5, -COOH), 5-(4-hydroxy) phenyl-10,15,20-triphenyl porphyrin (1a), 5-(4-ethylacetatatomethoxy) phenyl-10,15,20-triphenyl porphyrin (1b), 5-(4-carboxylatomethoxy) phenyl-10,15,20-triphenyl porphyrin (1c), were synthesized and characterized spectroscopically. The CuPp(2a, 2b, 2c)-TiO2 photocatalysts were then prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (UV-vis-DRS), Fourier-transform infrared spectroscopy (FT-IR). The photocatalytic activities of the photocatalysts were investigated by carrying out the photodegradation of 4-nitrophenol in aqueous solution under simulated solar irradiation. It was found that the CuPp(2a, 2b, 2c)-TiO2 enhanced the photocatalytic efficiency of bare TiO2 in photodegrading the 4-NP due to the interaction between CuPp(2a, 2b, 2c) and TiO2, resulted in the enhancement of the photogenerated electron-hole separation. The reasons of this enhanced photocatalytic activity were also discussed. Based on the present study, it could be considered as a promising photocatalyst for the further industrial application.