No abstract

Aqueous zinc ion batteries (AZIBs) are receiving increasing attention for large-scale energy storage systems owing to their appealing features with intrinsic safety, low cost, and scalability. Unfortunately, the water-induced parasitic reactions and dendrite growth on the Zn anode severely impede the further development of AZIBs. Herein, a thiourea additive is introduced into ZnSO 4 electrolyte to construct unique metal-molecule interface for simultaneously regulating the Zn anode interface chemistry and the bulk electrolyte environment. Experimental results and theoretical calculations reveal that the formed metal-molecule interface can not only serve as a corrosion inhibitor for alleviating the water-induced side reactions, but also act as a Zn 2+ ion regulator for promoting the homogenous Zn deposition, thus achieving a corrosion-free and dendrite-free Zn anode. Consequently, the Zn|Zn symmetric cell exhibits an extended lifespan of 1200 h at 1 mA cm -2 , 1mAh cm -2 , and a high cumulative capacity of 3000 mAh cm -2 at 10 mA cm -2 . When paired with V 2 O 5 cathode, the Zn|V 2 O 5 full cell delivers a high capacity retention of 76.0% after 1000 cycles at 1 A g -1 . This study paves a new way to modulate Zn electrode interface chemistry by the novel design of metal-molecule interface for advanced rechargeable Zn metal batteries and beyond.

Contamination of water and soils with arsenic, especially inorganic arsenic, has been one of the most important topics in the fields of environmental science and technology. The interactions between iron and arsenic play a very significant role in the environmental behavior and effect of arsenic species. However, the mechanism of As(III) oxidation in the presence of iron has remained unclear because of the complicated speciation of iron and arsenic. Photooxidation of As(III) on nascent colloidal ferric hydroxide (CFH) in aqueous solutions at pH 6 was studied to reveal the transformation mechanism of arsenic species. Experiments were done by irradiation using light-emitting diodes with a central wavelength of 394 nm. Results show that photooxidation of As(III) and photoreduction of Fe(III) occurred simultaneously under oxic or anoxic conditions. Photooxidation of As(III) in the presence of nascent CFH occurred through electron transfer from As(III) to Fe(III) induced by absorption of radiation into a ligand-to-metal charge-transfer (LMCT) band. The estimated quantum yield of photooxidation of As(III) at 394 nm was (1.023 ± 0.065) × 10(-2). Sunlight-induced photooxidation of As(III) also occurred, implying that photolysis of the CFH-As(III) surface complex could be an important process in environments wherein nascent CFH exists.

Disinfection is an indispensable process in wastewater treatment plants. New bacterial inactivation technologies are of increasing interest and persistent demand. A category of simple and efficient bactericidal systems have been established in this study, that is, the combination of divalent transition metal (Mn(II), Co(II), Fe(II), or Cu(II)) and sulfite. In these systems, metal catalyzed auto-oxidation of sulfite was manifested to generate reactive intermediary SO that played the major role in Escherichia coli inactivation at pH 5-8.5. Increasing concentrations of metal ion or sulfite, and lower pH, led to higher bacterial deaths. Bacterial inactivation by Me(II)/sulfite systems was demonstrated to be a surface-bound oxidative damage process through destructing vital cellular components, such as NADH and proteins. Additionally, the developed Me(II)/sulfite systems also potently killed other microbial pathogens, that is, Pseudomonas aeruginosa, Bacillus subtilis, and Cu(II)-antibiotic-resistant E. coli. The efficacy of Me(II)/sulfite in treating real water samples was further tested with two sewages from a wastewater treatment plant and a natural lake water body, and Cu(II)/sulfite and Co(II)/sulfite rapidly inactivated viable bacteria regardless of bacteria species and cell density, therefore holding great promises for wastewater disinfection.

The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demonstrates this important possibility for the case of two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) bound at goethite (α-FeOOH) used as a model mineral surface. Our multidisciplinary study, which makes use of batch sorption experiments, vibration spectroscopy and periodic density functional theory calculations, reveals enhanced binding of the otherwise weakly bound NFA caused by unforeseen intermolecular interactions with mineral-bound NA. This enhancement is ascribed to the formation of a NFA-NA dimer whose energetically favored formation (-0.5 eV compared to free molecules) is predominantly driven by van der Waals interactions. A parallel set of efforts also showed that no cobinding occurred with sulfamethoxazole (SMX) because of the lack of molecular interactions with coexisting contaminants. As such, this article raises the importance of recognizing drug cobinding, and lack of cobinding, for predicting and developing policies on the fate of complex mixtures of antibiotics and anti-inflammatory agents in nature.