The sulfidation behavior of zinc during microwave hydrothermal sulfidation of heavy metal-containing sludge.

The heavy metals present in the sludge can undergo a reaction with sulfur, leading to their conversion into metal sulfides through hydrothermal sulfidation. Sulfur ions, possessing a strong sulfidation capability, can operate within a wider pH range at elevated temperatures. The high temperature environment promotes the sulfidation process of zinc within heavy metal-laden sludge. Increasing the temperature of microwave hydrothermal sulfidation and extending the sulfidation duration for heavy metal-containing sludge can enhance the growth of crystal size in the artificially synthesized zinc sulfide. Zinc sulfide predominantly takes the form of ZnS, which facilitates the subsequent flotation recovery of zinc.

The σ+π dual aromaticity of typical bi-tetrazole ring molecule TKX-50.

Two complexes of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) were employed to evaluate the aromaticity of their tetrazole rings via deep analysis such as the electronic structure, the ZZ component of the natural chemical shielding tensor (NICSZZ) and component orbitals, localized orbital locator purely contributed by σ-orbitals (LOL-σ) and localized orbital locator purely contributed by π-orbitals (LOL-π), the anisotropy of the induced current density (AICD) and the ZZ component of iso-chemical shielding surface (ICSSZZ) of these tetrazole rings thereof. The conclusion shows: that all tetrazole rings and bi-tetrazole rings in complexes have strong σ and a comparable strength π double aromaticity; all these magnetic shields almost symmetrically increase from the central axis to the tetrazole ring atoms; tetrazole rings in complex II show a little stronger dual aromaticity than that in complex I mainly due to the different orientation of the fragment 2 encompassing two hydroxylamine groups resulting in different effects on the contributions of σ orbitals and π orbitals to total aromaticity of tetrazole rings thereof; the difference in aromaticity is fundamentally caused by the atoms O with stronger electron-withdrawing than atom N in fragment 2 interact with bi-tetrazole ring through O in complex I but through N in complex II.

Theoretical study on intra-molecule interactions in TKX-50.

To fully and deeply understand the weak interactions in the gaseous structure of the TKX-50 molecule, two conformations I and II of the TKX-50 molecule confirmed in a crystal cell were optimized at the B3LYP/6-311g(d,p) level in the gas state, and the single point energy of the optimized structure was calculated at the M06-2X/ma-TZVPP level. Analyzing methods for weak interactions such as the interaction region indicator (IRI), topological basin analysis, and the extended transition state-natural orbitals for chemical valence (ETS-NOCV) theory with the help of Multiwfn code were employed to reveal the corresponding intramolecular weak interactions. The results showed that there were 5 kinds of intramolecular weak interaction in both conformations. They are two types of H bond, two types of intra-ring weak interaction, and one type of O-N bond within the molecular fragment containing the bis-tetrazole ring. The combined effect of all these weak interactions holds the bis-tetrazole ring of TKX-50 retaining an almost coplanar configuration. Meanwhile, the strength of these weak interactions is significantly different in conformation I and conformation II. The most obvious difference is that conformation II has a significant H transfer between intramolecular fragments due to the mirror rotation of almost 180° of cations (NH3OH)+ perpendicular to the N-O bond axis thereof as compared to the reference conformation I. This conformational difference not only makes the weak interaction between the two conformations very different but also forms a quasi-covalent bond in conformation II with much larger bonding energy than other H bonds, thus resulting in conformation II having lower electron energy and more stable geometry. In addition, the order of breaking various H bonds in the combustion decomposition process of TKX-50 is deduced by comparing various H bonds.

Microwave irradiation coupled with zero-valent iron that enhances the composite geopolymerization of chromite ore processing residue and its mechanisms.

In this work, microwave (MW) irradiation was employed to enhance the zero-valent iron (ZVI)-dominated de-contamination of chromite ore processing residue (COPR). A coupling system and the traditional two-step procedure were both conducted to evaluate the effects of MW irradiation on the reduction and the incorporation of COPR into the composite materials-based geopolymers. The factors including the ratios of liquid to solid, the mass ratios of ZVI to COPR, and the acid dosage had some obvious influence on the reduction of COPR in the MW system. The compressive strengths of 31.54 and 41.56 MPa were determined from the two-step procedure and the coupling system at the COPR dosage of 10% (mass ratio), respectively. The employment of MW irradiation not only strengthened the formation of the geopolymer matrices but also improved the chemical stabilization of Cr species in the solidified blocks. The coupled process was more conducive to incorporating the treated COPR into the geopolymer-based crystalline microstructures compared with the subsequent usage of ZVI reduction and MW irradiation.

A green rust-coated expanded perlite particle electrode-based adsorption coupling with the three-dimensional electrokinetics that enhances hexavalent chromium removal.

A green rust-coated expanded perlite (GR-coated Exp-p) microelectrode was synthesized and incorporated into a column-mode three-dimensional electrokinetic (3D-EK) platform to effectively pursue a continuous Cr(VI) removal from the aqueous solution. Brucite-like layers of GR were decorated onto the Exp-p material. The molar ratio of Fe(II) to Fe(III) played a most vital role among the three synthesis factors in influencing the performance of the particle electrode. For the equilibrium adsorption experiments, the target maximum adsorption capacity of 122 mg/g was predicted by a target optimizer and desirability function at the conditions following the pH of 4.7, the initial concentration of 172.4 mg/L, the dosage of 0.28 g/L, and the temperature of 28.96 °C, respectively. SO42-, Cl-, and NO3- fiercely competed with Cr(VI) anions in the acidic conditions for the locally positive sites. A low concentration and a slow flow were favored in the column-mode 3D-EK platform. The pseudo-first-order and Langmuir models were suitable for describing the kinetics and isotherms of the adsorption process, respectively. Cr(VI) anions were electrostatically attracted to the silanol groups and GR surface of the adsorbent, subsequently reduced in both heterogeneity and homogeneity, and finally immobilized by coordinating with silanediol groups and silanetriol groups.

Hydroxyapatite nanoparticle functionalized activated carbon particle electrode that removes strontium from spiked soils in a unipolar three-dimensional electrokinetic system.

Biohazard performance of Sr radionuclide can be significantly magnified by its release from the contaminated sedimentation. In this study, hydroxyapatite nanoparticle-functionalized activated carbon electrode (AC-HAP) was synthesized and stacked to the cathode compartment of the electrokinetic (EK) system to develop a unipolar three-dimensional (3D) electrochemical process for Sr2+ removal from spiked soils. Sr2+ adsorption by AC-HAP can be fitted by the pseudo-first-order and pseudo-second-order kinetic models and the Langmuir, Freundlich, and Temkin isotherm models. The largest monolayer adsorption capacity of AC-HAP of 69.49 mg g-1 was evaluated in the pH range of 10-12 and at 40 °C. 3D EK further intensified the adsorption process of AC-HAP and the corresponding Sr2+ removal from aqueous environments. Voltage gradients and proposing time had a significant effect on the migration and transmission of Sr2+ in the electrolyzer. The influence of competitive ions on Sr2+ removal in the stock solutions followed Al3+ < Mg2+ < K+ < Na+ < Ca2+ while followed Al3+ < Na+ < K+ < Mg2+ < Ca2+ in 3D EK. The first three cycles for AC-HAP had taken roughly 50% of the reusability percentage. Sr2+ removal from spiked samples in 3D EK was achieved by acid dissolution, electromigration, and selective uptake on particle electrode.