The fundamental performance of a bio-electrochemical reactor for the direct treatment of metal pickling wastewater was investigated experimentally. In the reactor, carbon anode and cathode were installed. On the cathode, denitrifying microorganisms were immobilized. Continuous experiments were carried out by feeding a synthetic wastewater containing nitrate and binary heavy metal ions, copper and lead, under different operating conditions. Acetate as well as the electric current was supplied at the minimum amount for stoichiometry of the dissimilatory denitrification reaction. The results indicated that the dissolved copper and lead removal, denitrification and neutralization could be achieved simultaneously in a single bio-electrochemical reactor. The dissolved heavy metals were removed by electrochemical deposition on cathode and by the other phenomena such as the formation of insoluble suspensions and the sorption on suspended bacterial sludge. Denitrification proceeded effectively with the utilization of both added acetate and hydrogen gas generated by electrolysis of water. The pH value increased up to around neutral due to the occurrence of denitrification in the reactor, although the influent pH was less than 3. The removal efficiencies of heavy metals and nitrate increased with increasing the current density. The applied electric current was indispensable for sustaining the stable treatment in the reactor.
To explain the huge difference in the second harmonic generation (SHG) response of two novel interpenetrated metal−organic frameworks (MOFs) that consist of Zn 2+ ions coordinated to the trans-2-(4-pyridyl)-4-vinylbenzoate (pvb) ligand, eightfold interpenetrated Zn(pvb) 2 (M1) and sevenfold interpenetrated [Zn(pvb) 2 ]•DMF (M2), first-principles calculations were performed to study the geometries, band structures, and various linear and second-order nonlinear optical properties of M1 and M2 and two other hypothetical Zn-MOFs. Our results indicate that the structural transformation from M2 to M1 by the loss of the DMF guest is energetically favorable, and the M1 compound with the most tightly packed structure has the largest dielectric constant. For MOFs with the same order of interpenetration, the presence of the DMF guest has a small effect on the optical anisotropy of the system. Due to the different coordination environments of two kinds of Zn atoms, eightfold interpenetrated M1 shows more significant optical anisotropy than M2, and correspondingly, the range of phase matchability of M1 (>863 nm) is wider than that of M2 (>1126 nm). This means that at an experimental wavelength of 950 nm, M1 has a favorable phase-matching feature and displays strong SHG response, while the phase-mismatched behavior of M2 with sevenfold interpenetration leads to a weak SHG signal. Therefore, the difference in the interpenetrated structure induced by the guest DMF solvent is the main reason for the giant deviation in SHG intensity between M1 and M2 compounds. The present work provides new insights into how the phase-matching ability can be tuned by switching of the degree of interpenetration to enhance SHG response of MOFs.
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