A metal oxide-heterojunction photocatalyst is developed to harvest sunlight, store the energy in electrons, and apply the stored energy in water treatment. Light-absorbing nanoparticular and nanotubular TiO2 are hybridized with electron-storing WO3 at different weight ratios of TiO2 to WO3 (e.g., TW25 represents a composite of 25 wt% TiO2 and 75 wt% WO3). The ability of the TW composite to utilize the stored electrons is examined for the reduction of hexavalent chromium (Cr(vi)). In the photoelectrochemical (PEC) tests, irradiation using simulated sunlight (AM 1.5, 100 mW cm-2) leads to a rapid shift in the open-circuit potential (OCP) of the TW electrodes to the negative potential region (photocharging process). The termination of irradiation causes a gradual shift of the OCP to the positive potential region over 20 h (discharging process). Spiked Cr(vi) added to the solution with pre-photocharged TW electrodes is efficiently removed; the kinetics of this process depends on the TW composition (25, 50, or 75 wt%), TiO2 morphology (particular or tubular), initial Cr(vi) concentration (0.125 or 0.25 ppm), and whether the conditions are aerated or non-aerated. Based on this knowledge, TW composite-embedded inorganic membranes are synthesized and charged using sunlight. For Cr(vi) removal, single-pass and continuous circulation filtration systems are employed. The fraction of Cr(vi) removed from the circulation system is ∼30% in 4 h, which is 1.5 times that removed using the single-pass filtration system (∼20%). An X-ray photoelectron spectroscopy analysis of the TW membranes used for Cr(vi) removal reveals that Cr is not sorbed in the membrane. The W(vi) in WO3 is partially reduced to W(6-x)+ upon photocharging and is oxidized during the reduction of Cr(vi), leading to the co-existence of W6+ and W(6-x)+.
Although it is still a great challenge, developing oil-/water-separating membranes that combine the advantages of high separation efficiency, salty environments tolerance, and fouling resistance are highly demanded for marine oil spill cleanups and oil-/gasproduced water treatment. Here, we report a new type of all-inorganic nanostructured membrane, which is composed of titanate nanofibers and SiO 2 particulate gel for efficient and stable oil/saltwater separation. The nanoporous and interconnected network structure constructed with titanate nanofibers is the key to ensure the high separation efficiency and high water flux of the new membrane. The SiO 2 gel is used as a binder to offer mechanical flexibility and integrity for this type of all-inorganic membrane. The new membrane displays a high oil/water separation efficiency of above 99.5% with oil content in treated effluent lower than US environmental discharge standards (42 ppm) and high water permeation flux of 1600 LMH/bar under low operation pressure. The new membrane also demonstrates outstanding durability in the environment of different salinities, and it has a good resistance for oil fouling due to its excellent underwater superoleophobicity with an oil contact angle above 150°. Most importantly, the underwater superoleophobic properties can be well maintained after being repeatedly reused. The excellent environmental durability, oil-fouling resistance, high separation efficiency, and facile fabrication process for this new type of membrane render great potential for industrial application in treating produced water.
There is a large amount of oil-contaminated wastewater caused by oil/gas production and marine oil spills. It is still a major challenge for the development of oil/water separating membranes that have excellent separation efficiency, can withstand saline environments, and have long-term durability. We present a new membrane made of ultralong titanate nanofibers (TNF) (with diameter of 200 nm and length of 60 µm) and carbon nanofibers (CNF) (with a diameter of 150 nm and length of 50 µm) for efficient and consistent oil/saltwater separation. The intertwined structure of titanate and carbon nanofibers is critical to ensuring a high mechanical strength and durability for the new membrane. The carbon nanofiber works as a scaffold in this membrane to maintain mechanical integrity during multiple cycles of reuses, which is an important merit for its practical applications. The ultralong titanate nanofibers work as functional component to provide high hydrophilicity of the membrane. The new membrane has an oil/water separation efficiency of more than 99%, an oil content in treated effluent that is lower than US environmental discharge standards (42 ppm), and a high water flux of 1520 LMH/bar, due to its excellent superhydrophilicity and inter-connected pore structure. The new membrane also exhibits outstanding durability in a variety of salinity environments, as well as good resistance to oil fouling. This new type of membrane has a high potential for industrial application in treating oily wastewater due to its excellent environmental durability, oil-fouling resistance, high separation efficiency, and easy scalability.
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