Synergistic effect on simultaneous treatment of Cr(VI) and chloramphenicol using a non-thermal plasma technology.

Toxic organic and heavy metal contaminants commonly exist in industrial waste stream(s) and treatment is of great challenge. In this study, a dielectric barrier discharge (DBD) non-thermal plasma technology was employed for the simultaneous treatment of two important contaminants, chloramphenicol (CAP) and Cr(VI) in an aqueous solution through redox transformations. More than 70% of CAP and 20% of TOC were degraded in 60 min, while Cr(VI) was completely removed in 10 min. The hydroxyl radicals were the main active species for the degradation. Meanwhile, the consumption of hydroxyl radicals was beneficial to the reduction of Cr(VI). The synergistic effect was investigated between CAP degradation and Cr(VI) reduction. The reduction of Cr(VI) would be enhanced in the presence of CAP with a low concentration and could be inhibited under a high concentration, because part of hydroxyl radicals could be consumed by the low-concentration CAP and the obtained intermediates with a higher kinetic rate. However, CAP with a high concentration could react with such reductive species as eaq- and •H, which could compete with Cr(VI) and inhibit the reduction. In addition, the presence of Cr(VI) enhanced the degradation and mineralization of CAP; the study of obtained intermediates indicated that the presence of Cr(VI) changed the degradation path of CAP as Cr(VI) would react with reductive species, enhance the generation of hydroxyl radicals, and cause more hydroxylation reactions. Moreover, the mechanism for the simultaneous redox transformations of CAP and Cr(VI) was illustrated. This study indicates that the DBD non-thermal plasma technology can be one of better solutions for simultaneous elimination of heavy metal and organic contaminants in aquatic environments.

The "4 + 1" strategy fabrication of iron single-atom catalysts with selective high-valent iron-oxo species generation.

Single-atom catalysts (SACs) with atomic dispersion active sites have exhibited huge potentials in peroxymonosulfate (PMS)-based Fenton-like chemistry in water purification. However, four-N coordination metal (MN4) moieties often suffer from such problems as low selectivity and narrow workable pH. How to construct SACs in a controllable strategy with optimized electronic structures is of great challenge. Herein, an innovative strategy (i.e., the "4 + 1" fabrication) was devised to precisely modulate the first-shell coordinated microenvironment of FeN4 SAC using an additional N (SA-FeN5). This leads to almost 100% selective formation of high-valent iron-oxo [Fe(IV)═O] (steady-state concentration: 2.00 × 10-8 M) in the SA-FeN5/PMS system. In-depth theoretical calculations unveil that FeN5 configuration optimizes the electron distribution of monatomic Fe sites, which thus fosters PMS adsorption and reduces the energy barrier for Fe(IV)═O generation. SA-FeN5 was then attached to polyvinylidene difluoride membrane for a continuous flow device, showing long-term abatement of the microcontaminant. This work furnishes a general strategy for effective PMS activation and selective high-valent metal-oxo species generation by high N-coordination number regulation in SACs, which would provide guidance in the rational design of superior environmental catalysts for water purification.

Development and testing of alginate/C3N4porphyrin bead as a self-initiated Fenton photocatalyst for highly efficient atrazine removal.

Fenton reaction has been widely used for efficient treatment of organic wastewater. However, its applications are limited by such key factors as pH < 3. In this study, we developed, tested, and optimized an alginate/C3N4porphyrin bead (C3N4por-SA) as a recyclable photocatalyst in a photocatalysis-self-Fenton process to overcome these limitations. Porphyrin-modified C3N4 (C3N4por) was used as the H2O2 donator, while Fe(III) nodes served as the Fenton reagent. The as-prepared floating alginate/C3N4por bead utilized the light source as a driving force for the catalysis. Under visible light irradiation for 6 h, the model pollutant atrazine was degraded by 70.96 % by the optimized photocatalyst (named as C3N4por-SA-Fe1Ca5), demonstrating better photocatalytic performance than alginate/C3N4 beads. This improvement was attributed to the higher H2O2 yield from C3N4por. The alginate/C3N4por bead showed better photocatalytic activity even after several consecutive cycles and could easily be recovered for reuse. Furthermore, Fe(III)/Ca(II) bimetallic alginate bead exhibited better photocatalytic activity and a higher content of •OH radicals than the Ca(II) monometallic alginate beads, due to the ability of Fe(III) nodes to serve as a Fenton reagent. The influences of light sources, and commonly existing matters (namely SO42-, Cl-, CO32-, NO3-, and humic acid) were investigated. Moreover, the alginate/C3N4por bead demonstrated good photocatalytic performance in a simulated natural environment without the addition of extra H2O2, with an atrazine removal percentage of up to 96.3 % after 3-h irradiation. These findings indicated the great potential of alginate/C3N4por bead in practical applications.

Carbon capture and utilization by algae with high concentration CO2 or bicarbonate as carbon source.

Algae plays a key role in carbon capture and utilization (CCU) as it can capture and use the atmospheric CO2 for conversion of value-added products. Concentrated CO2 is common in flue gas and provides opportunities for algae cultivation. The drawbacks are mass transfer limitation, poor CO2 dissolution, and challenges to reach optimal levels for algal growth at given flue gas levels. Bicarbonate is flexible to be used as carbon source and owns the potential to enhance the efficiency of biological carbon fixation by algae. The requirements of algae strains are more stringent. To improve the industrial scale-up of CCU, system optimization is of great importance. More novel algal strains that can grow rapidly under harsh environment and provide valuable bio-products should be developed for large-scale production. Algae-driven CCU is promising for achieving carbon-neutrality.