Toward rapid reduction of carbon tetrachloride in water by zero-valent aluminum/persulfate system.

The oxidation performance of the zero-valent aluminum (ZVAl)/persulfate (PS) combined system had been studied by researchers in the past, which relied on the activation of PS by ZVAl to generate potent oxidizing radicals (•OH and SO4•-) to degrade pollutants. However, ZVAl is a strong reductant and its reduction effect cannot be ignored. The reductive performance of the ZVAl/PS combined system is still unknown. Therefore, carbon tetrachloride (CT), an antioxidant organic pollutant, was selected as the target pollutant to test the reductive performance of the ZVAl/PS system in this study. We found a significant synergistic effect between ZVAl and PS, and the ZVAl/PS combined system could rapidly degrade CT in a wide pH range of 3-11 after an induction period. By SEM-EDS, TEM, XPS, and XRD analysis, it was found that PS could promote the corrosion of the oxide film on the ZVAl surface. The quenching experiment proved that PS could accept the electrons released from ZVAl to produce superoxide radical anion (O2•-), which led to the degradation of CT rather than the oxidative process by •OH and SO4•-. The hydrogen evolution experiment indicated that electronic reduction might play a secondary role in CT degradation. In conclusion, our study further explored the reductive performance of the ZVAl/PS combined system and expanded the pathway of CT degradation without any organic solvent addition, which provides a new strategy for the efficient degradation of refractory halogenated organic pollutants.

Citrate ligand-enhanced microscale zero-valent aluminum corrosion for carbon tetrachloride degradation with high electron utilization efficiency.

Carbon tetrachloride (CT) is highly toxic and recalcitrant in groundwater. In recent years, zero-valent aluminum (ZVAl) is highly reductive but limited by its surface passivation film. One of the effective ways to overcome this bottleneck is to add ligands. In this paper, compared with several other ligands, sodium citrate (SC), a natural organic ligand, was introduced to enhance microscale ZVAl (mZVAl) reactivity for the reductive degradation of CT. The results showed that the SC system could effectively reduce but not completely dechlorinate CT and electron utilization efficiency was as high as 94%. However, without ligands, mZVAl is chemically inert for CT degradation. Through SEM-EDS, BET, XRD, and XPS characterizations and H2 evolution experiments, enhanced mZVAl surface corrosion at the solid-liquid interface of mZVAl/SC system was verified. SC participated in the complexation corrosion reaction with surface inert film to form Al[Cit] complex, which made internal Al0 active sites exposed and then promoted mZVAl corrosion. In the five consecutive reuse experiments of mZVAl, CT can be completely degraded, which indicates that mZVAl, with the help of SC, has excellent sustainable utilization efficiency.

A novel ball-milled aluminum-carbon composite for enhanced adsorption and degradation of hexabromocyclododecane.

Hexabromocyclododecane (HBCD) is one of the priority persistent organic pollutants (POPs), yet a cost-effective technology has been lacking for the removal and degradation of HBCD. Zero-valent aluminum (ZVAl) is an excellent electron donor. However, the inert and hydrophilic surface oxide layer impedes the release of the electrons from the core metallic Al, resulting in poor reactivity towards HBCD. In this research, a new type of modified mZVAl particles (AC@mZVAlbm/NaCl) were prepared through ball milling mZVAl in the presence of activated carbon (AC) and NaCl, and tested for adsorption and reductive degradation of HBCD in water. AC@mZVAlbm/NaCl was characterized with a metallic Al core with newly created reactive surface coated with a thin layer of crushed carbon nanoparticles. AC@mZVAlbm/NaCl was able to rapidly (within 1 h) adsorb HBCD (C0 = 2 mg L-1) and thus effectively enriched HBCD on the carbon surface of AC@mZVAlbm/NaCl. The pre-enriched HBCD was subsequently degraded by the electrons from the core Al, and ∼63.44% of the pre-sorbed HBCD was completely debrominated after 62 h of the contact. A notable time lag (∼12 h) from the onset of the adsorption to the debromination was observed, signifying the importance of the solid-phase mass transfer from the initially adsorbed AC particles to the reactive Al-AC interface. Overall, AC@mZVAlbm/NaCl synergizes the adsorptive properties of AC and the high reactivity of metallic Al, and enables a novel two-step adsorption and reductive degradation process for treating HBCD or likely other POPs.

Iron(II) sulfate crystals assisted mechanochemical modification of microscale zero-valent aluminum (mZVAl) for oxidative degradation of phenol in water.

Microscale zero-valent aluminum (mZVAl) is prone to surface passivation due to formation of the surface Al-(hydr)oxide layer, resulting in short reactive life. To overcome this critical drawback, we developed a mechanochemical ball milling approach to modify and activate commercially available mZVAl assisted by the fragile FeSO4·7H2O crystals. SEM-EDS and XPS analyses indicated that the particle surface of the mechanochemically modified mZVAl (Fe-mZVAlbm) was not only fractured with newly formed fresh reactive surfaces, but also attached with a rough layer of Fe-oxides that were uniformly distributed on mZVAl. While pristine mZVAl failed to degrade any phenol, Fe-mZVAlbm was able to rapidly degrade 88.8% within 90 min (initial phenol = 20 mg/L, pH = 2.50, dosage = 3 g/L) under normal oxic conditions, with a pseudo first-order rate constant of 0.040 min-1 and about 70.0% of phenol mineralized in 8 h. Moreover, Fe-mZVAlbm also showed prolonged reactive life, and no significant reactivity drop was evident after six cycles of consecutive runs for phenol degradation. The much enhanced reactivity and reactive longevity of Fe-mZVAlbm are attributed to the critical roles of the surface Fe-oxides, including 1) protecting the newly exposed reactive Al0 from being oxidized by side reactions, 2) serving as an electron mediator facilitating the electron transfer from the core Al0 reservoir to the exterior surface, and 3) acting as an Fe2+ source and a heterogeneous catalyst to enable the Fenton (-like) reactions. This study provides a novel and practical approach for preparing Fe-oxides modified mZVAl with enhanced and long-lasting reactivity.