Homogenous Oxidizing Oligomerization Coupled with Coagulation for Water Purification.

Natural manganese oxides could induce the intermolecular coupling reactions among small-molecule organics in aqueous environments, which is one of the fundamental processes contributing to natural humification. These processes could be simulated to design novel advanced oxidation technology for water purification. In this study, periodate (PI) was selected as the supplementary electron-acceptor for colloidal manganese oxides (Mn(IV)aq) to remove phenolic contaminants from water. By introducing polyferric sulfate (PFS) into the Mn(IV)aq/PI system and exploiting the flocculation potential of Mn(IV)aq, a post-coagulation process was triggered to eliminate soluble manganese after oxidation. Under acidic conditions, periodate exists in the H4IO6- form as an octahedral oxyacid capable of coordinating with Mn(IV)aq to form bidentate complexes or oligomers (Mn(IV)-PI*) as reactive oxidants. The Mn(IV)-PI* complex could induce cross-coupling process between phenolic contaminants, resulting in the formation of oligomerized products ranging from dimers to hexamers. These oligomerized products participate in the coagulation process and become stored within the nascent floc due to their catenulate nature and strong hydrophobicity. Through coordination between Mn(IV)aq and H4IO6-, residual periodate is firmly connected with manganese oxides in the floc after coagulation and could be simultaneously separated from the aqueous phase. This study achieves oxidizing oligomerization through a homogeneous process under mild conditions without additional energy input or heterogeneous catalyst preparation. Compared to traditional mineralization-driven oxidation techniques, the proposed novel cascade processes realize transformation, convergence, and separation of phenolic contaminants with high oxidant utilization efficiency for low-carbon purification.

Whose Oxygen Atom Is Transferred to the Products? A Case Study of Peracetic Acid Activation via Complexed MnII for Organic Contaminant Degradation.

Identifying reactive species in advanced oxidation process (AOP) is an essential and intriguing topic that is also challenging and requires continuous efforts. In this study, we exploited a novel AOP technology involving peracetic acid (PAA) activation mediated by a MnII-nitrilotriacetic acid (NTA) complex, which outperformed iron- and cobalt-based PAA activation processes for rapidly degrading phenolic and aniline contaminants from water. The proposed MnII/NTA/PAA system exhibited non-radical oxidation features and could stoichiometrically oxidize sulfoxide probes to the corresponding sulfone products. More importantly, we traced the origin of O atoms from the sulfone products by 18O isotope-tracing experiments and found that PAA was the only oxygen-donor, which is different from the oxidation process mediated by high-valence manganese-oxo intermediates. According to the results of theoretical calculations, we proposed that NTA could tune the coordination circumstance of the MnII center to elongate the O-O bond of the complexed PAA. Additionally, the NTA-MnII-PAA* molecular cluster presented a lower energy gap than the MnII-PAA complex, indicating that the MnII-peroxy complex was more reactive in the presence of NTA. Thus, the NTA-MnII-PAA* complex exhibited a stronger oxidation potential than PAA, which could rapidly oxidize organic contaminants from water. Further, we generalized our findings to the CoII/PAA oxidation process and highlighted that the CoII-PAA* complex might be the overlooked reactive cobalt species. The significance of this work lies in discovering that sometimes the metal-peroxy complex could directly oxidize the contaminants without the further generation of high-valence metal-oxo intermediates and/or radical species through interspecies oxygen and/or electron transfer.

Adsorption property and mechanism of polyacrylate-divinylbenzene microspheres for removal of trace organic micropollutants from water.

In this study, polyacrylate-divinylbenzene (PADVB) microspheres were facilely prepared via the precipitation polymerization method, and the microspheres were used as an efficient adsorbent for the removal of trace level organic micropollutants (OMPs) from environmental waters. Preparation conditions of PADVB microspheres were optimized, and the characterizations of the microspheres were performed using a scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and N2 adsorption/desorption isotherms. The microspheres had broad-spectrum adsorption ability for various organic micropollutants containing hydroxy, amidogen, aromatic or heteroaromatic ring in their chemical structure, such as atrazine, 2,4 dichlorophenol, 2,4 dibromophenol, 2,6 dichlorophenol, sulfamethoxazole, estradiol, and bisphenol A. Besides, the effects of initial concentration, initial pH value, adsorption time, and the type of adsorbates on the adsorption performance were investigated systematically. PADVB microspheres could be used for removing trace OMPs from environmental water. Monolayer and homogeneous sorption process occurred on the surface of PADVB microspheres through chemisorption mechanisms. The X-ray photoelectron spectroscopy (XPS) and FT-IR spectrum of PADVB microspheres before and after adsorption proved that the OMPs adsorption onto PADVB microspheres was mainly due to the formation of the hydrogen bond and π-π electron-donor-acceptor (EDA) interactions. Besides, PADVB microspheres can be recovered for reuse via (low-pressure) microfiltration and could be regenerated sufficiently by using 80% (v/v) ethanol.

Runge-Kutta Numerical Method Followed by Richardson's Extrapolation for Efficient Ion Rejection Reassessment of a Novel Defect-Free Synthesized Nanofiltration Membrane.

A defect-free, loose, and strong layer consisting of zirconium (Zr) nanoparticles (NPs) has been successfully established on a polyacrylonitrile (PAN) ultrafiltration substrate by an in-situ formation process. The resulting organic-inorganic nanofiltration (NF) membrane, NF-PANZr, has been accurately characterized not only with regard to its properties but also its structure by the atomic force microscopy, field emission scanning electron microscopy, and energy dispersive spectroscopy. A sophisticated computing model consisting of the Runge-Kutta method followed by Richardson extrapolation was applied in this investigation to solve the extended Nernst-Planck equations, which govern the solute particles' transport across the active layer of NF-PANZr. A smart, adaptive step-size routine is chosen for this simple and robust method, also known as RK4 (fourth-order Runge-Kutta). The NF-PANZr membrane was less performant toward monovalent ions, and its rejection rate for multivalent ions reached 99.3%. The water flux of the NF-PANZr membrane was as high as 58 L · m-2 · h-1. Richardson's extrapolation was then used to get a better approximation of Cl- and Mg2+ rejection, the relative errors were, respectively, 0.09% and 0.01% for Cl- and Mg2+. While waiting for the rise and expansion of machine learning in the prediction of rejection performance, we strongly recommend the development of better NF models and further validation of existing ones.