Photo-electrochemical Osmotic System Enables Simultaneous Metal Recovery and Electricity Generation from Wastewater.

Global depletion of natural resources provides an impetus for developing low-cost, environmentally benign technologies for the recovery of valuable resources from wastewater. In this study, we present an autonomous photo-electrochemical osmotic system (PECOS) that can recover a wide range of metals from simulated metal-laden wastewater with sunlight illumination while generating electricity. The PECOS comprises a draw solution chamber with a nickel nanoparticle-functionalized titanium nanowire (Ni-TiNA) photoanode, a feed solution chamber containing synthetic wastewater with an immersed carbon fiber cathode, and a forward osmosis (FO) membrane mounted between the chambers as a separator. Using a Na2-EDTA anolyte as a draw solution at neutral pH, we demonstrate that a sunlit PECOS achieves copper recovery at a rate of 51 g h-1 per m-2 of membrane area from simulated copper-laden wastewater while simultaneously producing a maximum power density of 228 mW m-2. Moreover, because of the osmotic pressure difference generated by the photo-electrochemical reactions, the PECOS reduces the wastewater volume by extracting fresh water through the FO membrane at a water flux of 0.84 L m-2 h-1. We further demonstrate the feasibility of the PECOS in recovering diverse metals from a simulated metal-laden industrial wastewater under sunlight irradiation. Our proof-of-concept PECOS prototype provides a sustainable technological solution that leverages sunlight in an electrochemical osmotic system to recover multiple resources from wastewater.

In Situ Electrochemical Generation of Reactive Chlorine Species for Efficient Ultrafiltration Membrane Self-Cleaning.

Reactive membranes based on hydroxyl radical generation are hindered by the need for chemical dosing and complicated module and material design. Herein, we utilize an electrochemical approach featuring in situ generation of reactive (radical) chlorine species (RCS) through anodization of chloride ions for membrane self-cleaning. A hybridized carbon nanotube (CNT)-functionalized ceramic membrane (h-CNT/CM), possessing high hydrophilicity, permeability, and conductivity, was fabricated. Using carbamazepine (CBZ) as a probe, we confirmed the presence of RCS in the electrified h-CNT/CM. The rapid and complete degradation of CBZ in a single-pass ultrafiltration indicates a high localized RCS concentration within the three-dimensional porous CNT interwoven layer. We further demonstrate that the electrogeneration of RCS is a critical prestep for free chlorine (HClO and ClO-) formation. The self-cleaning efficiency of the membrane after fouling with a model organic foulant (alginate) was assessed using an electrified cross-flow membrane filtration system. The fouled h-CNT/CM exhibits a near complete water flux recovery following a short (1 min) self-cleaning with an applied voltage of 3 or 4 V and feed solutions of 100 or 10 mM sodium chloride, respectively. Considering the superior performance of the RCS-mediated self-cleaning compared to conventional membrane chemical cleaning using sodium hypochlorite, our results exemplify an effective strategy for in situ electrogeneration of RCS to achieve a highly efficient membrane self-cleaning.

Interaction Analysis between Gravity-Driven Ceramic Membrane and Smaller Organic Matter: Implications for Retention and Fouling Mechanism in Ultralow Pressure-Driven Filtration System.

Gravity-driven membranes (GDM) generally achieve high retention performance in filtration of organic matter with a smaller size than the membrane pore, yet the in-depth mechanism remains unclear. Thorough analysis of the retention mechanism is crucial for optimizing GDM properties and improving GDM filtration performance. The performance and interaction mechanism of gravity-driven ceramic membrane (GDCM) filtrating smaller organic matter (SOM) were systematically studied. Rejection rate grew noticeably for like-charged foulant, whereas it only grew slightly for opposite-charged foulant as operation height decreased. Flux declined more seriously at lower operation height, probably due to heavier cake fouling caused by the rejected foulant. Interactions of ceramic membrane-SOM were analyzed through extended Derjaguin-Landau-Verwey-Overbeek theory (XDLVO) and hydrodynamic permeation drag (PD). Among van der Waals (LW), acid-base (AB), and electrostatic (EL) forces in XDLVO, EL played a significant role on GDCM filtrating SOM, and altering membrane electrostatic property could greatly influence SOM filtration. Furthermore, the rising PD force largely weakened the EL dominant zone with operation height increasing, while barely influencing the LW and AB dominant zones. Therefore, the weakened EL-dominant repulsive zone caused less rejection of like-charged foulant with operation height increasing. Fe2O3- and MnO2-modified membranes further validated the comprehensive influence of LW, AB, EL, and PD interactions on GDCM filtration. The possible "trade-off" of pore blocking-cake fouling with operation height decreasing demonstrated potential enhancement for both rejection and antifouling performance by electrically modified membrane under ultralow pressure. This study provides insight on membrane selection/preparation/modification and performance control of ultralow pressure-driven filtration.

Peracetic acid integrated catalytic ceramic membrane filtration for enhanced membrane fouling control: Performance evaluation and mechanism analysis.

Endowing ceramic membrane (CM) catalytic reactivity can enhance membrane fouling control in the aid of in situ oxidation process. Peracetic acid (PAA) oxidant holds great prospect to integrate with CM for membrane fouling control, owing to the prominent advantages of high oxidation efficacy and easy activation. Herein, this study, for the first time, presented a PAA/CM catalytic filtration system achieving highly-efficient protein fouling alleviation. A FeOCl functionalized CM (FeOCl-CM) was synthesized, possessing high hydrophilicity, low surface roughness, and highly-efficient activation towards PAA oxidation. Using bovine serum albumin (BSA) as the model protein foulant, the PAA/FeOCl-CM catalytic filtration notably alleviated fouling occurring in both membrane pores and surface, and halved the flux reduction degree as compared with the conventional CM filtration. The PAA/FeOCl-CM catalytic oxidation allows quick and complete disintegration of BSA particles, via the breakage of the amide I and II bands and the ring opening of the aromatic amino acids (e.g., Tryptophan, Tyrosine). In-depth investigation revealed that the in situ generated •OH and 1O2 were the key reactive species towards BSA degradation during catalytic filtration, while the organic radical oxidation and the direct electron transfer pathway from BSA to PAA via FeOCl-CM played minor roles. Overall, our findings highlight a new PAA/CM catalytic filtration strategy for achieving highly-efficient membrane fouling control and provide an understanding of the integrated PAA catalytic oxidation - membrane filtration behaviors.

Magnetic aminated lignin/CeO2/Fe3O4 composites with tailored interfacial chemistry and affinity for selective phosphate removal.

Phosphorus (P) has brought a series of environmental problems while benefiting mankind. To reclaim phosphorus from wastewater efficiently and conveniently, a novel magnetic adsorbent with aminated lignin/CeO2/Fe3O4 composites (AL-NH2@Fe3O4-Ce) possessing a high affinity to phosphate and easily separated from aqueous solutions was developed in this work. The characterization results revealed that Fe and Ce elements have been doped into the aminated lignin successfully. Batch experiment results convinced that the maximum phosphate adsorption capacity of AL-NH2@Fe3O4-Ce was 183.72 mg P/g at pH = 3, which was roughly 4.5 times greater than aminated lignin and 8.5 times greater than cerium oxide, respectively. The adsorption isotherm was fitted well by the Langmuir model, and the adsorption kinetics was in line with the pseudo-second-order model. The adsorption thermodynamics indicated the adsorption process was spontaneous and naturally exothermic. Additionally, AL-NH2@Fe3O4-Ce exhibited high selectivity towards phosphate over common coexisting anions (Cl-, NO3-, HCO3-, SO42- and F-). After five consecutive cycles, the adsorption performance of AL-NH2@Fe3O4-Ce decreased by only 16% compared with the fresh adsorbent, indicating that AL-NH2@Fe3O4-Ce exhibited excellent recycling ability. The results of XPS analysis and batch experiments showed that the possible mechanisms were electrostatic attraction and inner-sphere complexation. The tailored interfacial chemistry affinity to phosphate as well as endowed magnetic property reveled AL-NH2@Fe3O4-Ce could be adopted as an up and coming adsorbent in phosphate removal process.

Network interior and surface engineering of alginate-based beads using sorption affinity component for enhanced phosphate capture.

In order to alleviate the environmental problems caused by excessive discharge of phosphate, an environmental friendly and highly efficient bio-sorbent (SA-La@PEI) for phosphate was fabricated by combing strategies of sorption affinity component mediated and poly(ethylenimine) surface engineering of alginate beads. Various characterization methods like SEM, FTIR, XRD and XPS were adopted to examine the morphology and functional group composition of SA-La@PEI. Through detailed tests, SA-La@PEI exhibited excellent adsorption performance of 121.2 mg/g, which was better than most published materials. More importantly, the outstanding phosphate selectivity of SA-La@PEI was exposed when NO3-, HCO3-, SO42- and Cl- were added to the phosphate solution. Considering the integrated components in composites, both chemical precipitation and electrostatic attraction can be considered as the dominant mechanisms of phosphate adsorption. Totally, as-prepared SA-La@PEI beads might be a promising sorbent for the decontamination of excessive phosphate because of its low-cost, excellent adsorption performance and mechanical strength.

Synergistic oxidation - filtration process analysis of catalytic CuFe2O4 - Tailored ceramic membrane filtration via peroxymonosulfate activation for humic acid treatment.

This work synthesized catalytic CuFe2O4 tailored ceramic membrane (CuFeCM), and systematically investigated the intercorrelated oxidation - filtration mechanism of peroxymonosulfate (PMS)/CuFeCM catalytic filtration for treating humic acid (HA). PMS/CuFeCM filtration exhibited enhanced HA removal efficiency while reduced the irreversible fouling resistance as compared with the conventional CM filtration. Results from HA characterizations showed that PMS/CuFeCM catalytic filtration oxidized HA into conjugated structures of smaller molecular weight. The unsaturated bonds further caused the re-agglomeration of HA, hence enhancing the size exclusion of CuFeCM. Meanwhile, oxidized HA particles with changing physicochemical properties reduced the total attractive interaction energy between CuFeCM and HA, mainly attributed to the reduced acid-base interaction energy according to the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis. The changing of HA properties and HA-CuFeCM physicochemical interactions rendered more re-agglomerated HA particles retained above membrane with less attachment, which induced decreasing irreversible fouling resistance and facilitated easier external fouling removal by hydraulic cleaning. Overall, the PMS/CuFeCM configuration demonstrated in this study could provide a new insight into the synergistic oxidation - filtration interaction mechanism of hybrid catalytic ceramic membrane filtration process.