Continuous and Scalable Synthesis of Prussian Blue Analogues with Tunable Structure and Composition in Surfactant-Free Microreactor for Stable Zinc-Ion Storage.

We represent a segmented flow surfactant-free microfluidic strategy for continuous synthesis of Prussian blue analogues (PBAs) with high dispersity and high crystallization. Representative zinc hexacyanoferrate (ZnHCF) nanocubes were successfully synthesized in a microfluidic reactor within a few minutes via the cooperation method and possessed lower contents of crystal water and Fe(CN)6 3- vacancies than that of synthesis in bulk solution. The nucleation and particle growth process can be precisely controlled by the exploration of different flow rates and reaction temperatures during the formation of ZnHCF nanocubes in segmented flow microfluidic reactors. High crystallinity, low crystal water and vacancies in the ZnHCF structure were presented at relatively high temperatures for the crystal growth process. High-quality ZnHCF with a low content of crystal water showed excellent electrochemical activity and stability towards zinc-ion storage. The continuous and scalable synthesis approach can be extended to the fabrication of other PBAs such as NiHCF, CoHCF, MnHCF, and CuHCF with high dispersity without using any surfactants. The controllable construction of PBAs with tunable properties in microfluidic reactors provides a promising direction to minimize the gap between commercial reality and laboratory research.

Unleashing the high energy potential of zinc-iodide batteries: high-loaded thick electrodes designed with zinc iodide as the cathode.

The realization of high energy is of great importance to unlock the practical potential of zinc-iodine batteries. However, significant challenges, such as low iodine loading (mostly less than 50 wt%), restricted iodine reutilization, and severe structural pulverization during cycling, compromise its intrinsic features. This study introduces an optimized, fully zincified zinc iodide loaded onto a hierarchical carbon scaffold with high active component loading and content (82 wt%) to prepare a thick cathode for enabling high-energy Zn-I2 batteries. The synergistic interactions between nitrogen heteroatoms and cobalt nanocrystals within the porous matrix not only provide forceful chemisorption to lock polyiodide intermediates but also invoke the electrocatalytic effects to manipulate efficient iodine conversion. The ZnI2 cathode could effectively alleviate continuous volumetric expansion and maximize the utilization of active species. The electrochemical examinations confirm the thickness-independent battery performance of assembled Zn-I2 cells due to the ensemble effect of composite electrodes. Accordingly, with a thickness of 300 µm and ZnI2 loading of up to 20.5 mg cm-2, the cathode delivers a specific capacity of 92 mA h gcathode-1 after 2000 cycles at 1C. Moreover, the Zn-I2 pouch cell with ZnI2 cathode has an energy density of 145 W h kgcathode-1 as well as a stable long cycle life.

Bidirectional Confined Redox Catalysis Manipulated Quasi-Solid Iodine Conversion for Shuttle-Free Solid-State Zn-I2 Battery.

Electrochemically reversible conversion of I2/I- redox couple in a controllable iodine speciation manner is the eternal target for practical metal-iodine batteries. This contribution demonstrates an advanced polyiodide-free Zn-I2 battery achieved by the bidirectional confined redox catalysis-directed quasi-solid iodine conversion. A core-shell structured iodine cathode is fabricated by integrating multiporous Prussian blue nanocubes as a catalytic mediator, and the polypyrrole sheath afforded a confinement environment that favored the iodine redox. The zincate Znx+1FeIII/II[Fe(CN)6]y has substantially faster zinc-ion intercalation kinetics and overlapping kinetic voltage profiles compared with the I2/ZnI2 redox, and behave as a redox mediator that catalyze reduction of polyiodides via chemical redox reactions during battery discharging and an exemplary reaction is Zn(I3)2+2Znx+1FeII[Fe(CN)6]y=3ZnI2+2ZnxFeIII[Fe(CN)6]y,ΔG=-19.3 kJ mol-1). During the following recharging process, the electrodeposited ZnI2 can be facially activated by iron redox hotspots, and the ZnxFe[FeIII/II(CN)6]y served as a cation-transfer mediator and spontaneously catalyze polyiodides oxidation (Zn(I3)2+2ZnxFe[FeIII(CN)6]y=3I2+2Znx+1Fe[FeII(CN)6]y,ΔG = -7.72 kJ mol-1), manipulating the reversible one-step conversion of ZnI2 back to I2. Accordingly, a flexible solid-state battery employing the designed cathode can deliver an energy density of 215 Wh kgiodine -1.

Comparative study on the toxic effects of secondary nanoplastics from biodegradable and conventional plastics on Streptomyces coelicolor M145.

Because of the excellent properties, plastics have been widely used in the past decades and caused serious environmental issues. As an excellent substitute for conventional plastics, the biodegradable plastics have attracted increasing attention. However, biodegradable plastics may produce more micro/nanoplastics in the short time compared with conventional plastics, and cause more serious ecological risks. In this study, the short-term toxicity of nanoplastics released from biodegradable and conventional plastics on Streptomyces coelicolor M145 was investigated. After 30 days of degradation, the biodegradable microplastics, polylactic acid (PLA) and polyhydroxyalkanoates (PHA) released more secondary nanoplastics than conventional microplastics, polystyrene (PS). After exposure, PLA and PHA nanoplastics showed significant toxicity to M145. The survival rate of M145 cells was 16.1% after treatment with PLA nanoplastics for 7 days (PLA-7). The toxicity of PHA was lower than that of PLA. This might have been due to the agglomeration of PHA nanoplastics in the solution. Compared with the controls, the PS secondary nanoplastics showed no significant toxicity to M145. After the treatment, the production of antibiotics, actinorhodin (ACT) and undecylprodigiosin (RED), significantly increased. The yields of ACT and RED reached their maximum values after treatment with PLA-7, which were 4.2-fold and 2.1-fold higher than those of the controls, respectively. The addition of biodegradable nanoplastics significantly increased the expression of these key pathway-specific regulatory genes, leading to increased antibiotic production. This study provides toxicological insights into the impacts of conventional and biodegradable microplastics on S. coelicolor.

The combined effects of nanoplastics and dibutyl phthalate on Streptomyces coelicolor M145.

The environmental and human health risks posed by nanoplastics have attracted considerable attention; however, research on the combined toxicity of nanoplastics and plasticizers is limited. This study analyzed the combined effects of nanoplastics and dibutyl phthalate (DBP) on Streptomyces coelicolor M145 (herein referred to as M145) and its mechanism. The results demonstrated that when the concentration of both nanoplastics and DBP was 1 mg/L, the co-addition was not toxic to M145. When the DBP concentration increased to 5 mg/L, the combined toxicity of 1 mg/L nanoplastics and 5 mg/L DBP reduced when compared to the 5 mg/L DBP treatment group. Similarly, the combined toxicity of 10 mg/L nanoplastics and 1 mg/L DBP on M145 was also lower than that of only 10 mg/L nanoplastics. The co-addition of 10 mg/L nanoplastics and 5 mg/L DBP resulted in the lowest survival rate (41.3%). The key reason for differences in cytotoxicity were variations in the agglomeration of nanoplastics and the adsorption of DBP on nanoplastics. The combination of 10 mg/L nanoplastics and 5 mg/L DBP maximized the production of antibiotics; actinorhodin and undecylprodigiosin yields were 3.5 and 1.8-fold higher than that of the control, respectively. This indicates that the excessive production of antibiotics may be a protective mechanism for bacteria. This study provides a new perspective for assessing the risk of co-exposure to nanoplastics and organic contaminants on microorganisms in nature.

The toxicity effects of nano/microplastics on an antibiotic producing strain - Streptomyces coelicolor M145.

The toxic effects of nano/microplastics on microorganisms are still unclear. In this study, Streptomyces coelicolor (S. coelicolor) M145 was selected to study the toxicity and mechanism of nano/microplastics (20 nm, 100 nm, 1 µm and 1 mm) at concentration of 0.1, 1 and 10 mg/L on microorganisms. Results showed that the cytotoxicity, reactive oxygen species (ROS) level, permeability, and antibiotic production of M145 cells changed significantly after the addition of nano/microplastics, and the trends were size and concentration dependent. After M145 was exposed to 10 mg/L of 20 nm nanoplastics, its fatality rate was 64.8%, which was the highest among the particle size of 20 nm to 1 mm at a concentration of 0.1-10 mg/L. And the ROS level and cell permeability also reached their highest values, which was about 2.7 folds and 2.2 folds of control, respectively. After this treatment, the maximum yields of actinorhodin and undecylprodigiosin were 6.7 and 5.3 mg/L, respectively. Transcriptome analysis indicated that nanoplastics could inhibit the transport capacity, primary metabolism, and oxidative phosphorylation of M145, and that the inhibition extend was negatively related to the particle size. Moreover, the toxicity of microplastics to M145 was significantly less than that of nanoplastics. This study provides a new perspective for understanding the toxicity of nano/microplastics on microorganisms in nature.