Polyphenol-mediated defect patching of graphene oxide membranes for sulfonamide contaminants removal and fouling control.

Graphene oxide (GO)-based laminar membranes are promising candidates for next-generation nanofiltration membranes because of their theoretically frictionless nanochannels. However, nonuniform stacking during the filtration process and the inherent swelling of GO nanosheets generate horizontal and vertical defects, leading to a low selectivity and susceptibility to pore blockage. Herein, both types of defects are simultaneously patching by utilizing tannic acid and FeⅢ. Tannic acid first partially reduced the upper GO framework, and then coordinated with FeⅢ to form a metal-polyphenol network covering horizontal defects. Due to the enhanced steric hindrance, the resulting membrane exhibited a two-fold increase in sulfonamide contaminants exclusion compared to the pristine GO membrane. A non-significant reduction in permeance was observed. In terms of fouling control, shielding defects significantly alleviated the irreversible pore blockage of the membrane. Additionally, the hydrophilic metal-polyphenol network weakened the adhesion force between the membrane and foulants, thereby improving the reversibility of fouling in the cleaning stage. This work opens up a new way to develop GO-based membranes with enhanced separation performance and antifouling ability.

Positively charged membranes for dye/salt separation based on a crossover combination of Mannich reaction and prebiotic chemistry.

With the advent of increasingly loose nanofiltration membranes for dye desalination, synthesis methods based on interfacial polymerization and bio-inspired materials such as polydopamine (pDA) have been investigated. However, the long polymerization time of pDA greatly limits the synthesis and application of fast dye/salt separation membranes. In this work, prebiotic chemistry-inspired aminomalononitrile (AMN) was used as a binder to co-deposit the Mannich reaction of tetrakis(hydroxymethyl)phosphonium chloride (THPC) and polyethyleneimine (PEI) to form the positively charged selective layer rapidly. The optimum membrane had a water permeance of 30.7 LMH bar-1 and a rejection of positively charged Victoria blue B (VBB, 200 ppm) and Na2SO4 (1 g/L) of 99.5 % and 9.9 %, respectively. Moreover, the results of a practical application test showed that it had excellent separation performance towards various positively charged dyes and salts. In addition, the actual application test results show that the membrane has good long-term stability during application. In terms of antifouling and antibacterial, the membrane has excellent antibacterial and antifouling properties., Further antibacterial tests were carried out, and the inactivation effect of the membrane on E. coli was also confirmed. The preparation method proposed in this work provides technical support for developing new dye/salt separation membranes.

Mechanistic Insights of a Thermoresponsive Interface for Fouling Control of Thin-Film Composite Nanofiltration Membranes.

In spite of extensive research, fouling is still the main challenge for nanofiltration membranes, generating an extra transport resistance and requiring a larger operational pressure in practical applications. We fabricated a highly antifouling nanofiltration membrane by grafting poly(N-isopropylacrylamide) (PNIPAM) chains on a bromine-containing polyamide layer. The resulting membrane was found to have a double permeance compared to the pristine membrane, while the rejection of multivalent ions remained the same. In addition, PNIPAM chains yielded a better deposition resistance and adhesion resistance, thereby mitigating the increase of fouling and promoting the recovery of flux during the filtration and traditional cleaning stages, respectively. Moreover, PNIPAM chains shrank when the water temperature was above the lower critical solution temperature (LCST), indicating the formation of a buffer layer between the membrane and pollutants. The buffer layer would eliminate the membrane-foulant interaction energy, thus further enhancing the detachment of pollutants. This simple and efficient cleaning method could act as an enhanced cleaning procedure to remove irreversible fouling. This provides new insights into the fabrication of enhanced antifouling membranes using smart responsive polymer chains.

Fast start-up of PN/A process in a single-stage packed bed and mechanism of nitrogen removal.

The single-stage partial nitritation-anammox (PN/A) process is severely limited by a long start-up time and unstable removal efficiency. In this study, PN/A was developed in 67 days in a novel packed bed equipped with porous bio-carriers by gradually increasing the influent nitrogen loading rate (0.15-0.73 kg-N m-3·d-1) and controlling the dissolved oxygen (< 1.2 mg L-1). An average ammonium nitrogen removal efficiency (ARE) and total nitrogen removal efficiency (TNR) of 87.01 and 72.41%, respectively, were obtained. This represents a reliable alternative method of achieving rapid PN/A start-up. The results of 16S rRNA sequencing showed that Proteobacteria and Planctomycetes, with which ammonia-oxidizing bacteria and anammox bacteria were affiliated, accounted for 38.8%, representing the dominant phylum in the system after acclimation. The abundance of Nitrosomonas and Candidatus Brocadia increased by 16 and 1.79%, respectively. The results of metagenomics and metatranscriptomics revealed that the nitrite oxidation process was blocked by the transcriptional suppression of nitrite oxidoreductase and the entire nitrogen metabolism process was dominated by the partial nitritation and anammox process. Moreover, a high abundance of heterotrophic bacteria with potential for nitrogen removal was detected. In the nitrogen cycle, a widespread nitrite-accumulated denitrification helps to form a nitrite loop, which promotes the efficiency of total nitrogen removal. This is crucial for further improving the nitrogen removal mechanism in the PN/A system.

Effect of inorganic salt ions on the adsorption of quinoline using coal powder.

In this study, coal powder was used as the adsorbent for quinoline. The effect of inorganic salt ions on the adsorption was explored, and the results suggest that the addition of inorganic salt ions can enhance both the removal rate and the amount of quinoline adsorbed. The removal rate and adsorbed amount of quinoline were 83.87% and 1.26 mg/g without inorganic salt ions. Under the same adsorption conditions, the removal rate and adsorbed amount of quinoline could reach 90.21% and 1.35 mg/g when Na+ was present in the solution, and 94.47% and 1.42 mg/g with the presence of Ca2+. In addition, the adsorption of quinoline using coal fitted the Freundlich isothermal adsorption model. Changes in the Gibbs free energy, entropy and heat of adsorption were all negative, indicating that the adsorption was spontaneous and exothermic. The changes in the absolute value of Gibbs free energy under both Na+ and Ca2+ were higher than that in the blank(without inorganic salt ions). The pseudo-second-order kinetic model was found to fit the adsorption kinetic data well, and the activation energy of adsorption under Na+ and Ca2+ were lower than that in the blank. These indicate that the addition of inorganic salt ions was beneficial to the adsorption process.