Peroxymonosulfate-Activation-Induced Phase Transition of Mn3O4 Nanospheres on Nickel Foam with Enhanced Catalytic Performance.

The transformations of physicochemical properties on manganese oxides during peroxymonosulfate (PMS) activation are vital factors to be concerned. In this work, Mn3O4 nanospheres homogeneously loaded on nickel foam are prepared, and the catalytic performance for PMS activation is evaluated by degrading a target pollutant, Acid Orange 7, in aqueous solution. The factors including catalyst loading, nickel foam substrate, and degradation conditions have been investigated. Additionally, the transformations of crystal structure, surface chemistry, and morphology on the catalyst have been explored. The results show that sufficient catalyst loading and the support of nickel foam play significant roles in the catalytic reactivity. A phase transition from spinel Mn3O4 to layered birnessite, accompanied by a morphological change from nanospheres to laminae, is clarified during the PMS activation. The electrochemical analysis reveals that more favorable electronic transfer and ionic diffusion occur after the phase transition so as to enhance catalytic performance. The generated SO4•- and •OH radicals through redox reactions of Mn are demonstrated to account for the pollutant degradation. This work will provide new understandings of PMS activation by manganese oxides with high catalytic activity and reusability.

A superwetting stainless steel mesh with Janus surface charges for efficient emulsion separation.

Design of charged materials for demulsification of ionic surfactant-stabilized oil-in-water emulsions is emerging in recent years. Herein, a superwetting stainless steel mesh with Janus surface charges (Janus SSM) was prepared by respectively brush-coating polyethyleneimine/aminated carbon nanotubes (PEI/CNTs-NH2) coating and polyacrylic acid (PAA) coating on its two sides. Two demulsification mechanisms, i.e., electrostatic attraction-repulsion and electrostatic repulsion-attraction based on the synergism of two oppositely charged sides were proposed. Combined with the superwettability and optimized pore size, the Janus SSM can successfully be used to demulsify, coalesce and separate emulsions. In detail, the Janus SSM exhibited separation efficiencies of up to 99.29%, 97.12% for SDS- and DTAC-stabilized oil-in-water emulsions respectively under the electrostatic attraction-repulsion mechanism, and up to 97.10%, 98.57% under the electrostatic repulsion-attraction mechanism. The results indicated that the electrostatic attraction-repulsion mechanism proposed in this study is conductive to achieving higher efficiency in emulsion separation. Furthermore, excellent durability extend the operation life of Janus SSM. This Janus SSM, which combines opposite charges on its two sides, may advance the development of charged materials for emulsion separation.

A novel Janus sponge fabricated by a green strategy for simultaneous separation of oil/water emulsions and dye contaminants.

A novel Janus sponge with the ability to remove complex contaminants from water is reported. Firstly, a superhydrophilic sponge (PA@PEI-sponge) is prepared via synthesizing negatively charged phytic acid@polyethyleneimine (PA@PEI) nanoparticles and assembling them on the surface of polydopamine (PDA) and PEI-modified polyurethane (PU) sponge through electrostatic adsorption. The Janus sponge is generated by modifying one side of the PA@PEI-sponge with PDMS, which exhibits superior separation efficiency and high filtration flux toward both water-in-oil and oil-in-water emulsions due to its multiplex selective wettability and the interconnected and tortuous 3D porous channels. The numerous negatively charged active sites of PA@PEI nanoparticles and PDA layer impart the superhydrophilic PA@PEI-sponge with the removal efficiency of 39.95 ± 0.27% for malachite green (MG) via simple flow-through filtration, which can be improved to 99.92 ± 0.07% by Janus modification. More importantly, the Janus sponge exhibits an excellent treatment capacity for complex mixtures containing emulsified oil and dye, with the separation efficiency above 99.59%. The Janus sponge also demonstrates the effective separation of real industrial wastewater collected from an acrylic dyeing plant. Together with a facile and green preparation strategy, this Janus sponge shows excellent application potential for simultaneous dye removal and oil/water emulsion separation.

Stable Zr-UiO-67 constructed through polymeric network assisted post-synthetic modification and its wettability modulation.

Stable Zr-UiO-67 is prepared by introducing a fluorine-containing layer on its surface through a polymeric network assisted post-synthetic modification (PSM) strategy. The stability of the MOFs in acidic, alkaline and saline environments is improved because of the existence of a protective layer. The MOFs are superlyophobic towards liquids with a surface tension threshold of over 48 mN m-1, making them a potential choice for separating various liquid-liquid mixtures and emulsions.

Janus sand filter with excellent demulsification ability in separation of surfactant-stabilized oil/water emulsions: An experimental and molecular dynamics simulation study.

Developing efficient separation materials for surfactant-stabilized oil/water emulsions is of great importance while significantly challenging. In this work, a sand filter with Janus channels was prepared by simply mixing superhydrophilic and superhydrophobic quartz sand in a mass ratio of 1:1. Due to the imbalanced force of droplets in those Janus channels, better separation performance under gravity was achieved for both surfactant-stabilized oil-in-water and water-in-oil emulsions than the superhydrophilic or superhydrophobic sand filter alone. It also received high flux (1080.13 L m-2 h-1 for dichloroethane-in-water emulsion and 1378.07 L m-2 h-1 for water-in-dichloroethane emulsion) and high separation efficiency (99.80% for dichloroethane-in-water emulsion and 99.98% for water-in-dichloroethane emulsion). Molecular dynamics based computational work and experimental studies revealed that the Janus channels of mixed sand layer exhibited greater interaction energy with emulsion droplets for more efficient adsorption, resulting in better demulsification capability and separation performance. The as-prepared Janus sand filters retained excellent separation performance after 50 cycles of the stability test. Together with the needs on only cheap and easily accessible raw materials and its environmentally friendly preparation method, this Janus sand filtration process exhibits its great potential for the separation of surfactant-stabilized oil/water emulsions.

Fabrication of superhydrophilic PVDF membranes by one-step modification with eco-friendly phytic acid and polyethyleneimine complex for oil-in-water emulsions separation.

Superhydrophilic membranes with simultaneous underwater superoleophobicity are highly desirable and worth exploring for separation of emulsified oil from water. In this work, combining the strong negative charges of phytic acid (PA) and the high cationic charge density of polyethyleneimine (PEI), an eco-friendly PA@PEI polyelectrolyte complex was synthetized in aqueous solution. And then the polyelectrolyte complex was deposited onto hydrophobic PVDF membranes through a one-step assembly approach with high convenience, endowing the membranes with superhydrophilic and underwater superoleophobic property. The as-prepared PA@PEI/PVDF membrane shows outstanding static and dynamic water stability, and was successfully used to separate multiple oil-in-water emulsions, with an average rejection rate exceeding 98.5% and a water flux up to 12203.6 L m-2∙h-1∙bar-1. Furthermore, the water flux can be recovered to a high level after four separation-washing cycles, showing excellent antifouling performance and recovery capability. Together with its natural raw materials and environmentally friendly preparation strategy, the PA@PEI/PVDF membrane shows great potential in practical treatment of emulsified oily wastewater.

Hard-and-Soft Integration Strategy for Preparation of Exceptionally Stable Zr(Hf)-UiO-66 via Thiol-Ene Click Chemistry.

UiO-66 metal-organic frameworks (MOFs) are unstable in some harsh aqueous environments, which limit their practical applications. We demonstrate a postsynthetic modification methodology to transform hydrophilic Zr(Hf)-UiO-66 into superhydrophobic Zr(Hf)-UiO-66-SH-y (SH = thiol, y = fluoroalkyl) by introducing long fluoroalkyl chains into organic linkers through a thiol-ene click reaction. Water contact angles of the four modified UiO-66 MOFs are all larger than 150°. The grafted low-surface-energy fluorine-containing groups become an effective protective shield for the MOFs, making them exhibit remarkable stability in extreme conditions such as alkaline (pH = 12), saturated HCl, and high concentration of NaCl solution (20 wt %). The Zr-UiO-66 MOFs grafted with 1H,1H,2H-perfluoro-1-hexene have high CO2 adsorption contents of 1.54 and 2.88 mmol·g-1 at 298 and 273 K, respectively. Moreover, the superhydrophobic MOFs also showed potential application in oil/water separation.

Nature-Inspired Strategy toward Superhydrophobic Fabrics for Versatile Oil/Water Separation.

Phytic acid, which is a naturally occurring component that is widely found in many plants, can strongly bond toxic mineral elements in the human body, because of its six phosphate groups. Some of the metal ions present the property of bonding with phytic acid to form insoluble coordination complexes aggregations, even at room temperature. Herein, a superhydrophobic cotton fabric was prepared using a novel and facile nature-inspired strategy that introduced phytic acid metal complex aggregations to generate rough hierarchical structures on a fabric surface, followed by PDMS modification. This superhydrophobic surface can be constructed not only on cotton fabric, but also on filter paper, polyethylene terephthalate (PET) fabric, and sponge. AgI, FeIII, CeIII, ZrIV, and SnIV are very commendatory ions in our study. Taking phytic acid-FeIII-based superhydrophobic fabric as an example, it showed excellent resistance to ultraviolet (UV) irradiation, high temperature, and organic solvent immersion, and it has good resistance to mechanical wear and abrasion. The superhydrophobic/superoleophilic fabric was successfully used to separate oil/water mixtures with separation efficiencies as high as 99.5%. We envision that these superantiwetting fabrics, modified with phytic acid-metal complexes and PDMS, are environmentally friendly, low cost, sustainable, and easy to scale up, and thereby exhibit great potentials in practical applications.

Inspired by Stenocara Beetles: From Water Collection to High-Efficiency Water-in-Oil Emulsion Separation.

Inspired by the water-collecting mechanism of the Stenocara beetle's back structure, we prepared a superhydrophilic bumps-superhydrophobic/superoleophilic stainless steel mesh (SBS-SSM) filter via a facile and environmentally friendly method. Specifically, hydrophilic silica microparticles are assembled on the as-cleaned stainless steel mesh surface, followed by further spin-coating with a fluoropolymer/SiO2 nanoparticle solution. On the special surface of SBS-SSM, attributed to the steep surface energy gradient, the superhydrophilic bumps (hydrophilic silica microparticles) are able to capture emulsified water droplets and collect water from the emulsion even when their size is smaller than the pore size of the stainless steel mesh. The oil portion of the water-in-oil emulsion therefore permeates through pores of the superhydrophobic/superoleophilic mesh coating freely and gets purified. We demonstrated an oil recovery purity up to 99.95 wt % for surfactant-stabilized water-in-oil emulsions on the biomimetic SBS-SSM filter, which is superior to that of the traditional superhydrophobic/superoleophilic stainless steel mesh (S-SSM) filter lacking the superhydrophilic bump structure. Together with a facile and environmentally friendly coating strategy, this tool shows great application potential for water-in-oil emulsion separation and oil purification.