Enhanced sludge dewatering using a novel synergistic iron/peroxymonosulfate-polyacrylamide method.

In the sludge dewatering process, a formidable challenge arises due to the robust interactions between extracellular polymeric substances (EPS) and bound water. This study introduces a novel, synergistic conditioning method that combines iron (Fe2+)/peroxymonosulfate (PMS) and polyacrylamide (PAM) to significantly enhance sludge dewatering efficiency. The application of the Fe2+/PMS-PAM conditioning method led to a substantial reduction in specific filtration resistance (SFR) by 82.75% and capillary suction time (CST) by 80.44%, marking a considerable improvement in dewatering performance. Comprehensive analyses revealed that pre-oxidation with Fe2+/PMS in the Fe2+/PMS-PAM process effectively degraded EPS, facilitating the release of bound water. Subsequently, PAM enhanced the flocculation of fine sludge particles resulting from the advanced oxidation processes (AOPs). Furthermore, analysis based on the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory demonstrated shifts in interaction energies, highlighting the breakdown of energy barriers within the sludge and a transition in surface characteristics from hydrophilic (3.79 mJ m-2) to hydrophobic (-61.86 mJ m-2). This shift promoted the spontaneous aggregation of sludge particles. The innovative use of the Flory-Huggins theory provided insights into the sludge filtration mechanism from a chemical potential perspective, linking these changes to SFR. The introduction of Fe2+/PMS-PAM conditioning disrupted the uniformity of the EPS-formed gel layer, significantly reducing the chemical potential difference between the permeate and the water in the gel layer, leading to a lower SFR and enhanced dewatering performance. This thermodynamic approach significantly enhances our understanding of sludge dewatering and conditioning. These findings represent a paradigm shift, offering innovative strategies for sludge treatment and expanding our comprehension of dewatering and conditioning techniques.

Innovative treatment of industrial effluents through combining ferric iron and attapulgite application.

The escalation of industrial activities has escalated the production of pharmaceutical and dyeing effluents, raising significant environmental issues. In this investigation, a hybrid approach of Fenton-like reactions and adsorption was used for deep treatment of these effluents, focusing on effects of variables like hydrogen peroxide concentration, catalyst type, pH, reaction duration, temperature, and adsorbent quantity on treatment effectiveness, and the efficacy of acid-modified attapulgite (AMATP) and ferric iron (Fe(III))-loaded AMATP (Fe(III)-AMATP) was examined. Optimal operational conditions were determined, and the possibility of reusing the catalysts was explored. Employing Fe3O4 as a heterogeneous catalyst and AMATP for adsorption, CODCr was reduced by 78.38-79.14%, total nitrogen by 71.53-77.43%, and phosphorus by 97.74-98.10% in pharmaceutical effluents. Similarly, for dyeing effluents, Fe(III)-AMATP achieved 79.87-80.94% CODCr, 68.59-70.93% total nitrogen, and 79.31-83.33% phosphorus reduction. Regeneration experiments revealed that Fe3O4 maintained 59.48% efficiency over three cycles, and Fe(III)-AMATP maintained 62.47% efficiency over four cycles. This work offers an economical, hybrid approach for effective pharmaceutical and dyeing effluent treatment, with broad application potential.

Erratum: [Corrigendum] Chloroquine potentiates the anticancer effect of sunitinib on renal cell carcinoma by inhibiting autophagy and inducing apoptosis.

[This corrects the article DOI: 10.3892/ol.2017.7635.].

Dihalogenated nitrophenols in drinking water: Prevalence, resistance to household treatment, and cardiotoxic impact on zebrafish embryo.

Dihalogenated nitrophenols (2,6-DHNPs), an emerging group of aromatic disinfection byproducts (DBPs) detected in drinking water, have limited available information regarding their persistence and toxicological risks. The present study found that 2,6-DHNPs are resistant to major drinking water treatment processes (sedimentation and filtration) and households methods (boiling, filtration, microwave irradiation, and ultrasonic cleaning). To further assess their health risks, we conducted a series of toxicology studies using zebrafish embryos as the model organism. Our findings reveal that these emerging 2,6-DHNPs showed lethal toxicity 248 times greater than that of the regulated DBP, dichloroacetic acid. Specifically, at sublethal concentrations, exposure to 2,6-DHNPs generated reactive oxygen species (ROS), caused apoptosis, inhibited cardiac looping, and induced cardiac failure in zebrafish. Remarkably, the use of a ROS scavenger, N-acetyl-l-cysteine, considerably mitigated these adverse effects, emphasizing the essential role of ROS in 2,6-DHNP-induced cardiotoxicity. Our findings highlight the cardiotoxic potential of 2,6-DHNPs in drinking water even at low concentrations of 19 µg/L and the beneficial effect of N-acetyl-l-cysteine in alleviating the 2,6-DHNP-induced cardiotoxicity. This study underscores the urgent need for increased scrutiny of these emerging compounds in public health discussions.

Durable Nano-Flower Structured Foam Coupled with Electrically-Driven in Situ Aeration Enable High-Flux Oil/Water Emulsion Separation with Dynamic Antifouling Ability.

The conventional membranes used for separating oil/water emulsions are typically limited by the properties of the membrane materials and the impact of membrane fouling, making continuous long-term usage unachievable. In this study, a filtering electrode with synchronous self-cleaning functionality is devised, exhibiting notable antifouling ability and an extended operational lifespan, suitable for the continuous separation of oil/water emulsions. Compared with the original Ti foam, the in situ growth of NiTi-LDH (Layered double hydroxide) nano-flowers endows the modified Ti foam (NiTi-LDH/TF) with exceptional superhydrophilicity and underwater superoleophobicity. Driven by gravity, a rejection rate of over 99% is achieved for various emulsions containing oil content ranging from 1% to 50%, as well as oil/seawater emulsions. The flux recovery rate exceeds 90% after one hundred cycles and a 4-h filtration period. The enhanced separation performance is realized through the "gas bridge" effect during in situ aeration and electrochemical anodic oxidation. The internal aeration within the membrane pores contributes to the removal of oil foulants. This study underscores the potential of coupling foam metal filtration materials with electrochemical technology, providing a paradigm for the exploration of novel oil/water separation membranes.

An efficient solution based on the synergistic effects of nickel foam in NiFe-LDH nanosheets for oil/water separation.

Efficient oil-water separation has always been a research hotspot in the field of environmental studies. Employing a one-step hydrothermal approach, NiFe-layered double hydroxides (LDH) nanosheets were synthesized on nickel foam substrates. The resulting NiFe-LDH/NF membrane exhibited rejection rates exceeding 99% across six diverse oil-water mixtures, concurrently demonstrating a remarkable ultra-high flux of 1.4 × 106 L·m-2·h-1. This flux value significantly surpasses those documented in existing literature, maintaining stable performance over 1000 manual filtration cycles. These breakthroughs stem from the synergistic interplay among the three-dimensional channels of the nickel foam, the nanosheets, and the hydration layer. By leveraging the pore size of the foam to enhance the functionality of the hydration layer, the conventional trade-off between permeability and selectivity was transformed into a balanced force relationship between the hydration layer and the oil phase. The operational and failure mechanisms of the hydration layer were examined using the prepared NiFe-LDH/NF membrane, validating the correlation between oil phase viscosity and density with hydration layer rupture. Additionally, an extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory was employed to investigate changes in interaction energy, further reinforcing the study's findings. This research contributes novel insights and assistance to the comprehension and application of hydration layers in other membrane studies dedicated to oil-water separation.

Novel combination of iron-carbon composite and Fenton oxidation processes for high-concentration antibiotic wastewater treatment.

The research presented herein explores the development of a novel iron-carbon composite, designed specifically for the improved treatment of high-concentration antibiotic wastewater. Employing a nitrogen-shielded thermal calcination approach, the investigation utilizes a blend of reductive iron powder, activated carbon, bentonite, copper powder, manganese dioxide, and ferric oxide to formulate an efficient iron-carbon composite. The oxygen exclusion process in iron-carbon particles results in distinctive electrochemical cells formation, markedly enhancing wastewater degradation efficiency. Iron-carbon micro-electrolysis not only boosts the biochemical degradability of concentrated antibiotic wastewater but also mitigates acute biological toxicity. In response to the increased Fe2+ levels found in micro-electrolysis wastewater, this research incorporates Fenton oxidation for advanced treatment of the micro-electrolysis byproducts. Through the synergistic application of iron-carbon micro-electrolysis and Fenton oxidation, this research accomplishes a significant decrease in the initial COD levels of high-concentration antibiotic wastewater, reducing them from 90,000 mg/L to about 30,000 mg/L, thus achieving an impressive removal efficiency of 66.9%. This integrated methodology effectively reduces the pollutant load, and the recycling of Fe2+ in the Fenton process additionally contributes to the reduction in both the volume and cost associated with solid waste treatment. This research underscores the considerable potential of the iron-carbon composite material in efficiently managing high-concentration antibiotic wastewater, thereby making a notable contribution to the field of environmental science.

Emerging disinfection byproducts 3-bromine carbazole induces cardiac developmental toxicity via aryl hydrocarbon receptor activation in zebrafish larvae.

3-bromine carbazole (3-BCZ) represents a group of emerging aromatic disinfection byproducts (DBP) detected in drinking water; however, limited information is available regarding its potential cardiotoxicity. To assess its impacts, zebrafish embryos were exposed to 0, 0.06, 0.14, 0.29, 0.58, 1.44 or 2.88 mg/L of 3-BCZ for 120 h post fertilization (hpf). Our results revealed that ≥1.44 mg/L 3-BCZ exposure induced a higher incidence of heart malformation and an elevated pericardial area in zebrafish larvae; it also decreased the number of cardiac muscle cells and thins the walls of the ventricle and atrium while increasing cardiac output and impeding cardiac looping. Furthermore, 3-BCZ exposure also exhibited significant effects on the transcriptional levels of genes related to both cardiac development (nkx2.5, vmhc, gata4, tbx5, tbx2b, bmp4, bmp10, and bmp2b) and cardiac function (cacna1ab, cacna1da, atp2a1l, atp1b2b, atp1a3b, and tnnc1a). Notably, N-acetyl-L-cysteine, a reactive oxygen species scavenger, may alleviate the failure of cardiac looping induced by 3-BCZ but not the associated cardiac dysfunction or malformation; conversely, the aryl hydrocarbon receptor agonist CH131229 can completely eliminate the cardiotoxicity caused by 3-BCZ. This study provides new evidence for potential risks associated with ingesting 3-BCZ as well as revealing underlying mechanisms responsible for its cardiotoxic effects on zebrafish embryos.

[Mechanism about LMP1 of EB Virus Promoting Plasma Blast Differentiation of DLBCL Cell via mTORC1].

OBJECTIVE: To investigate possible mechanism on protien LMP1 expressed by EBV inducing plasmablast differentiation of DLBCL cell via the mTORC1 pathway. METHODS: The expression levels of LMP1 protein, CD38 and the phosphorylation levels of p70S6K in EBV+ and EBV- DLBCL cell lines were detected by Western blot. Cell lines overexpressing LMP1 gene stablely were constructed and LMP1 gene was silenced by RNAi. The expression of LMP1 gene was verified by RT-qPCR. The expression levels of LMP1 and CD38 and the phosphorylation levels of p70S6K in each group were detected by Western blot. RESULTS: Compared with EBV-DLBCL cells, the expression of LMP1 was detected on EBV +DLBCL cells (P =0.0008), EBV +DLBCL cells had higher phosphorylation levels of p70S6K (P =0.0072) and expression levels of CD38(P =0.0091). Compared with vector group, the cells of LMP1OE group had higher expression levels of LMP1 and CD38 (P =0.0353; P <0.0001), meanwhile molecular p70S6K was phosphorylated much more(P =0.0065); expression of LMP1 mRNA was verified(P <0.0001). Compared with si-NC group, expression level of LMP1 protein(P =0.0129) was not detected and phosphorylated p70S6K disappeared of LMP1KO group (P =0.0228); meanwhile, expression of CD38 decreased,although there was no significant difference (P =0.2377). CONCLUSION: LMP1 promotes DLBCL cells plasmablast differentiation via activating mTORC1 signal pathway.

Enhanced methane yield in anaerobic digestion of waste activated sludge by combined pretreatment with fungal mash and free nitrous acid.

This study explores a novel approach for enhancing anaerobic digestion of waste activated sludge (WAS) through the combined pretreatment of fungal mash and free nitrous acid (FNA). Aspergillus PAD-2, a fungal strain with superior hydrolase secretion, was isolated from WAS and cultivated in-situ on food waste to produce fungal mash. The solubilization of WAS by fungal mash achieved a high soluble chemical oxygen demand release rate of 548 mg L-1 h-1 within first 3 h. The combined pretreatment of fungal mash and FNA further improved the sludge solubilization by 2-fold and resulted in a doubled methane production rate of 416±11 mL CH4 g-1 volatile solids. The Gompertz model analysis revealed a higher maximum specific methane production rate and shortened lag time by the combined pretreatment. These results demonstrate that the combined fungal mash and FNA pretreatment offers a promising alternative for fast anaerobic digestion of WAS.

Novel thermodynamic mechanisms of co-conditioning with polymeric aluminum chloride and polyacrylamide for improved sludge dewatering: A paradigm shift in the field.

This study investigated the combined effects of polymeric aluminum chloride (PAC) and polyacrylamide (PAM) on sludge dewatering, aiming to unveil underlying mechanisms. Co-conditioning with 15 mg g-1 PAC and 1 mg g-1 PAM achieved optimal dewatering, reducing specific filtration resistance (SFR) of co-conditioned sludge to 4.38 × 1012 m-1kg-1, a mere 48.1% of raw sludge's SFR. Compared with the CST of raw sludge (36.45 s), sludge sample can be significantly reduced to 17.7 s. Characterization tests showed enhanced neutralization and agglomeration in co-conditioned sludge. Theoretical calculations revealed elimination of interaction energy barriers between sludge particles post co-conditioning, converting sludge surface from hydrophilic (3.03 mJ m-2) to hydrophobic (-46.20 mJ m-2), facilitating spontaneous agglomeration. Findings explain improved dewatering performance. Based on Flory-Huggins lattice theory, connection between polymer structure and SFR was established. Raw sludge formation triggered significant change in chemical potential, increasing bound water retention capacity and SFR. In contrast, co-conditioned sludge exhibited thinnest gel layer, reducing SFR and significantly improving dewatering. These findings represent a paradigm shift, shedding new light on fundamental thermodynamic mechanisms of sludge dewatering with different chemical conditioning.

Efficient oily wastewater treatment by a novel electroflotation-membrane separation system consisting a Ni-Cu-P membrane prepared by electroless nickel plating.

Electroflotation-membrane separation system with a conductive membrane has recently emerged as a promising technology for oily wastewater treatment. However, the conductive membrane prepared by electroless plating often suffers the problems of low stability and high activation cost. To solve these problems, this work proposed a new strategy regarding surface metallization of polymeric membrane by surface nickel-catalyzed electroless nickel plating of nickel­copper­phosphorus alloys for the first time. It was found that, addition of copper source remarkably enhanced the membranes' hydrophilicity, corrosion resistance and fouling resistance. The Ni-Cu-P membrane had an underwater oil contact angle of up to 140°, and simultaneously possessed rejection rate > 98 % with rather high flux of 65,663.0 L·m-2·h-1 and excellent cycling stability when separating n-hexane/water mixtures under gravity drive. The permeability is higher than the state-of-the-art membranes for oil/water separation. The Ni-Cu-P membrane as the cathode can be assembled into an electroflotation-membrane separation system, allowing to separate oil-in-water emulsion with 99 % rejection. Meanwhile, the applied electric field significantly improved membrane flux and fouling resistance (flux recovery up to 91 %) when separate kaolin suspensions. Polarization curve and Nyquist curve analysis further confirmed that addition of Cu element obviously enhanced corrosion resistance of the Ni modified membrane. This work provided a novel strategy to make up high-efficiency membranes for oily wastewater treatment.

3D printing titanium dioxide-acrylonitrile-butadiene-styrene (TiO2-ABS) composite membrane for efficient oil/water separation.

The oily water treatment is becoming one of the hottest topics due to that increase of offshore oil transportation and the various accident oil leakages. In this study, a functional TiO2-ABS composite membrane was generated through the three-dimensional (3D) printing strategy for the first time and was conducted to simulated oily water treatment. The TiO2-ABS composite membrane demonstrated a significant promotion in hydrophilicity and oleophobicity which were evidenced by the water contact angle of 14.8° and the underwater oil contact angle of 144.7°, respectively. The optimal modified membrane had both exceedingly high flux (1.8 × 105 L m-2·h-1) and oil rejection rate (99.5%). Moreover, the results of filtration cycles of 10 days and extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory demonstrated that the modified membranes took possession of excellent stability and antifouling property. What was more, the TiO2-ABS composite membrane revealed over 99% rejection to all five types of oil/water systems. The interestingly experimental results indicated that the prepared membrane possessed a broad development trend and application prospect in the field of oily water treatment.

Algae extract delamination of molybdenum disulfide and surface modification with glycidyl methacrylate and polyaniline for the elimination of metal ions from wastewater.

A special type of two-dimensional (2D) material based conducting polymer was constructed by green synthesis and in-situ polymerization techniques. The 2D Molybdenum Disulfide (MoS2) were first synthesized with the combination of, ammonium tetrathiomolybdate dissolved in 20 mL algae extract under stirring. After stirring for about 2 h, and then finally sulfurization was initiated using sulfur powder in 20 mL of sulfuric solution and stirred for 8 h. The resulting black precipitates of MoS2 were collected by centrifugation at 5000 rpm. Moreover, the prepared MoS2 was functionalized with glycidyl methacrylate (GMA) and form the MoS2@PGMA. Further, the MoS2@PGMA is combined with polyaniline (PANI) to form conducting polymer grafted thin film nanosheets named MoS2@PGMA/PANI with a thickness in micrometer size through grafting method. The prepared materials were characterized by SEM, FTIR, XRD, XPS and EDX techniques. To check the performance of materials the adsorption study was performed. Moreover, the adsorption study toward Cu2+ and Cd2+ showed a tremendous results and the maximum adsorption was 307.7 mg/g and 214.7 mg/g respectively. In addition, the pseudo-first and second order models as well as the adsorption isotherm were investigated using the Langmuir and Freundlich model. The results were best fitted with the pseudo-second order and Langmuir models. The regeneration study was also conducted and MoS2@PGMA/PANI nanosheets can be easily recycled and restored after five successful recycling. The established methodology for preparing the 2D materials and conducting polymer based MoS2@PGMA/PANI nanosheets is expected to be applicable for other multiple applications.

Efficient oil-water emulsion treatment via novel composite membranes fabricated by CaCO3-based biomineralization and TA-Ti(IV) coating strategy.

Continuous increasing discharge of industrial oily wastewater and frequent occurrence of oil spill accidents have taken heavy tolls on global environment and human health. Organic-inorganic modifications can fabricate superhydrophilic/submerged superoleophobic membranes for efficient oil-water separation/treatment though they still suffer from complex operation, non-environmental friendliness, expensive cost or uneven distribution. Herein, a new strategy regarding tannic acid (TA)-Ti(IV) coating and CaCO3-based biomineralization through simple inkjet printing processes was proposed to modify polyvinylidene fluoride (PVDF) membrane, endowing the membrane with high hydrophilicity (water contact angle (WCA) decreased from 86.01° to 14.94°) and underwater superoleophobicity (underwater contact angle (UOCA) > 155°). The optimized TA-Ti(IV)-CaCO3 modified membrane possessed perfect water permeation to various oil/water emulsions (e.g., 355.7 L·m-2·h-1 for gasoline emulsion) under gravity with superior separation efficiency (>98.8 %), leading the way in oil/water emulsion separation performance of PVDF membranes modified with polyphenolic surfaces to our knowledge. Moreover, the modified membrane displayed rather high flux recovery after eight cycles of filtration while maintaining the original excellent separation efficiency. The modification process proposed in this study is almost independent of the nature of the substrate, and meets the demand for simple, inexpensive, rapid preparation of highly hydrophilic antifouling membranes, showing abroad application prospect for oil-water emulsion separation/treatment.

Plant Polyphenol Pyrogallol and Polyamine-Based Co-Deposition for High-Efficiency Nanofiltration Membrane Preparation towards Inorganic Salt Removal.

The co-deposition between polyphenols and amines has been demonstrated in order to prepare positively charged nanofiltration (NF) membranes for multivalent cation rejection in recent years; however, the low reactivities of the involved polyphenols usually cause a long co-deposition time and unsatisfactory rejection. Herein, a novel plant polyphenol (PG) was co-deposited with tetraethylenepentamine (TEPA) in a much shorter time period to prepare positively charged NF with high multivalent cation rejection membranes. The performance of the co-deposition membranes can be easily controlled by adjusting the mass ratio of PG and TEPA, reaction time, and pH value of the buffer solution. The optimal membrane, prepared under a polyphenol and polyamine mass ratio of 1:1, coating time of 2 h, and pH value of 8.0, shows a decent pure water permeability of 8.43 L m-2 h-1 bar-1 while maintaining a superior 96.24% MgCl2 rejection. More importantly, the universality of this method was corroborated by employing other amines with different molecular weights in the co-deposition. This work provides new insights for the preparation of high-performance positively charged NF membranes.

Mechanistic insights into Ca-alginate gel-associated membrane fouling affected by ethylene diamine tetraacetic acid (EDTA).

While transparent exopolymer particles (TEP) is a major foulant, and ethylene diamine tetraacetic acid (EDTA) is a strong chelating agent frequently used for fouling mitigation in membrane-based water treatment processes, little has been known about TEP-associated membrane fouling affected by EDTA. This work was performed to investigate roles of EDTA addition in TEP (Ca-alginate gel was used as a TEP model) associated fouling. It was interestingly found that, TEP had rather high specific filtration resistance (SFR) of 2.49 × 1015 m-1·kg-1, and SFR of TEP solution firstly decreased and then increased rapidly with EDTA concentration increase (0-1 mM). A series of characterizations suggested that EDTA took roles in SFR of TEP solution by means of changing TEP microstructure. The rather high SFR of TEP layer can be attributed to the big chemical potential gap during filtration described by the extended Flory-Huggins lattice theory. Initial EDTA addition disintegrated TEP structure by EDTA chelating calcium in TEP, inducing reduced SFR. Continuous EDTA addition decreased solution pH, resulting into no effective chelating and accumulation of EDTA on membrane surface, increasing SFR. It was suggested that factors increasing homogeneity of TEP gel will increase SFR, and vice versa. This study revealed the thermodynamic mechanism of TEP fouling behaviors affected by EDTA, and also demonstrated the importance of EDTA dosage and pH adjustment for TEP-associated fouling control.

A novel composite membrane for simultaneous separation and catalytic degradation of oil/water emulsion with high performance.

It is of great significance to develop novel membranes with dual-function of simultaneously separating oil/water emulsion and degrading the contained water-miscible toxic organic components. To meet this requirement, a dual-functional Ni nanoparticles (NPs)@Ag/C-carbon nanotubes (CNTs) composite membrane was fabricated via electroless nickel plating strategy in this study. The as-prepared composite membrane possessed superhydrophilicity with water contact angle of 0° and splendid underwater oleophobic property with oil contact angle of 142°. When the membrane was applied for separation of surfactant stabilized oil-in-water emulsion, high permeate flux (about 97 L m-2·h-1 under gravity), oil rejection (about 98.8%) and antifouling property were achieved. Benefitting from the NiNPs@Ag/C-CNTs layer on membrane surface, the composite membrane exhibited high catalytic degradation activity for water-miscible toxic organic pollutant (4-nitrophenol) with addition of NaBH4 in a flow-through mode. Meanwhile, the NiNPs@Ag/C-CNTs composite membrane possessed excellent durability, which was verified by the good structural integrity even under ultrasonic treatment. The cost-efficiency, high separation and degradation performance of the prepared membrane suggested its great potential for treatment of oily wastewater.

A unified thermodynamic fouling mechanism based on forward osmosis membrane unique properties: An asymmetric structure and reverse solute diffusion.

Fouling mechanism of the forward osmosis membrane, which was peculiarly featured by the asymmetric membrane structure and reverse solute diffusion, was investigated at the molecular level and from the energy perspective. Two noteworthy fouling behaviors were observed in batch fouling tests conducted in AL-FS mode (active layer facing feed solution) and AL-DS mode (active layer facing draw solution) after filtering foulants with identical volume: 1) after filtering 100 mL of foulants, the flux decline rate in AL-DS mode was 1.78 times faster than that in AL-FS mode, but the flux decline behaviors of the two modes were similar in the subsequent filtration stages; 2) although the foulant layer weight of the same mode increased linearly in middle and late stages, the flux loss rate was distinctly different. Thermodynamic analysis indicated that the attractive interaction energy between the foulants and the support layer was about 5 times higher than that between the foulants and the active layer, well interpreting the higher flux decline rate of AL-DS mode in initial stage. Meanwhile, a non-invasive microscope observed that the structure of the fouling layer remarkably changed from loose to dense in the middle stage, and stabilized in the late stage. Furthermore, quantum chemistry calculation proved that the reverse diffusion of NaCl brought alginate molecular chains closer, whereas the distance between them tended to be constant as the continuous increase of NaCl. Based on these findings, the thermodynamic fouling mechanism proposed by combining the structure change process of the fouling layer with Flory-Huggins lattice theory satisfactorily interpreted the noteworthy fouling behaviors caused by reverse NaCl diffusion in middle and late stages. The revealed fouling mechanism unifies the adhesion and filtration behaviors related to the unique properties of FO membrane, deepening understanding of membrane fouling in the dynamic and complex ternary system of the FO process.

Significantly Enhanced Photocatalytic CO2 Reduction by Surface Amorphization of Cocatalysts.

Rational phase engineering of reduction cocatalyst offers a promising route to modulate the photocatalytic activity and selectivity in the conversion of CO2 to chemical feedstocks. However, it remains a great challenge to choose a suitable phase given that high-crystallinity phase is more conducive to the charge transfer and separation, while amorphous phase is more favorable for the adsorption and activation of CO2 molecules. To resolve this dilemma, herein, with Pd as a well-defined model, a surface amorphization strategy has been developed to fabricate crystalline@amorphous semi-core-shell cocatalysts based on the transformation of outer layer atoms of crystalline cocatalysts to disorder phase. According to the theoretical and experimental analysis, in the heterostructured cocatalysts, crystalline core shuttles the photoexcited electrons from light-harvesting semiconductor to amorphous shell due to its strong electronic coupling with both components. Meanwhile, amorphous shell provides efficient active sites for preferential activation and conversion of CO2 and suppression of undesirable proton reduction. Benefiting from the synergistic effects between crystalline core and amorphous shell, the optimized heterophase cocatalyst with suitable thickness of amorphous shell achieves superior CO (22.2 µmol gcat-1 h-1 ) and CH4 (38.1 µmol gcat-1 h-1 ) formation rates with considerable selectivity and high stability in comparison with crystalline and amorphous counterparts.