This invention relates to using magnetic nanoparticles for water treatment.
Access to safe drinking water is extremely important to human beings' health. Currently, water facilities have been built worldwide to provide people in metropolitan areas with high-standard clean water. However, problems still remain in several aspects. First, the drinking water plants are not available in all corners of the world as these plants are usually built in cities with large populations. However, for travelers in natural areas far from civilization or people in countries where sanitation facilities are not so well-developed, a point-of-use water-treating equipment is necessary to provide high-standard drinking water. Second, in the current water-treating technology, chlorine disinfection for instance, undesirable disinfection byproducts have been reported, some of which are carcinogens. Finally, as demand for water resources increases ever more, reuse of waste water after removing contaminants is highly desirable, both ecologically and economically. These driving forces motivate an environment-friendly, regenerative water-treating strategy.
Nanoparticles have been reported to have promising properties for environmental applications. For example, silver nanoparticles can effectively kill bacteria. TiO2 nanoparticles have photo-catalytic properties and are therefore used to degrade many organic contaminants in water under ultraviolet (UV) light irradiation. Even for non-degradable chemicals, some of them can be removed by adsorption to some metal-oxide nanoparticles. Due to their high surface-to-volume ratio, these particles are much more efficient than their counterparts in bulk form. However, these particles have to be separated from water after the treatment because the toxicity of these nanoparticles is a serious concern. Moreover, the separation step is crucial for regenerative use of these nanoparticles as ideally all of the particles should be separated from water without any loss. In some conventional approaches, these nanoparticles are embedded in a porous matrix in order not to be flushed away with water, but this method sacrifices the effective surface areas of nanoparticles which can react with water contaminants. The porous matrix also increases the capital cost.
Accordingly, it would be an advance in the art to provide improved nanoparticle water treatment.
Separating these nanoparticles magnetically is an alternative to avoid the above-described problems, and we hereby disclose multifunctional, magnetically-responsive nanoparticles, and their fabrication and use for water treatment.
Multifunctional, magnetically-responsive nanoparticles are provided to decontaminate water for drinking purposes or for reuse of waste water. Based on the methods described herein, we can make multi-layered nanoparticles with magnetic cores and environmentally-functional surfaces for different water-decontamination purposes. The surfaces can be made up of different materials. In one embodiment, we coat these particles with Ag layers to do water disinfection. In another embodiment, we coat these particles with TiO2 layers to photo-catalytically degrade organic contaminants. In a third embodiment, we coat these particles with metal-oxide materials to absorb non-degradable contaminants, including perfluorinated compounds (PFCs).
These nanoparticles have multi-layered magnetic cores, which have two ferromagnetic layers separated by a spacer layer. They have negligible remanence and their moments will be saturated when the external field is larger than their saturation field. This is similar to the case of chemically synthesized iron-oxide nanoparticles. However, these multi-layered nanoparticles have at least 10× larger single-particle magnetic moment than conventional iron-oxide nanoparticles, which makes them extremely magnetically responsive. In one embodiment, a NdFeB magnet is placed close to the vial containing particle solution and over 99% of these particles can be separated away within 10 min. Since the toxicities of many kinds of nanoparticles are questionable, the complete removal of these nanoparticles to a level complying with the drinking water standard will have practical significance.
In fact, the complete removal of nanoparticles enables their regenerative use. In one embodiment, particles are recycled after they are used for water treatment. As long as the environmentally-functional surface materials are not consumed, these particles can still work in new cycles. These particles can therefore be used for multiple cycles in water treatment, greatly reducing the overall material cost for water treatment.
In one embodiment, non-degradable chemicals like perfluorinated compounds are adsorbed to synthetic nanoparticles coated with oxides. After the adsorption, we can employ two mechanisms to destroy these molecules by taking the advantage of the magnetic core. In one mechanism, we introduce an alternating magnetic field around these nanoparticles, and because of their failure to keep up with the external field, these particles will generate substantial amount of heat. This mechanism is known as hyperthermia, and the extra energy generated can potentially break the bonds in these non-degradable molecules attaching to the surface of these particles. In another mechanism, the nanoparticles are dried after adsorption, and subsequently subjected to a radio-frequency (RF) electromagnetic field. This generates eddy current flow within the metallic cores of these particles. The eddy current will in turn generate extra heat which can also potentially break the bonds in these non-degradable molecules.
In this work, functionalized synthetic nanoparticles are provided for water treatment.
In one embodiment, the synthetic nanoparticles have diameters of 160 nm with their multiple layers in the sequence of Ag 20 nm/Ti 5 nm/Fe 5 nm/Ti 3 nm/Fe 5 nm/Ti 5 nm/Ag 20 nm. Here, the two ferromagnetic layers made of Fe are separated by Ti and Ag is the environmentally-functional material designed for water disinfection.
Water from a contaminated or questionable source can have various contaminants, including micro-organisms and chemicals. These contaminants, although in trace amount sometimes, can cause serious health issue if people drink the water directly. In our design, the functional layers 116 and 118 can be made of different materials, thereby addressing different problems.
In one embodiment, the functional layers are chosen to be Ag in order to kill pathogens. Ag has long been known to have disinfection capabilities, as people in ancient times use silverware to store their food to retard bacterial growth. The role of Ag in disinfection will be amplified dramatically if Ag is in nanoparticle form and dispersed in water.
In another embodiment, the functional layers are chosen to be TiO2 for photocatalytic degradation. TiO2 can be in amorphous, anatase or rutile phase. Other than micro-organisms, contaminated/questionable water may also include organic compounds that can cause severe health issues. As shown in
In a further embodiment, some of the organic compounds are non-degradable, but they can be adsorbed by some oxides. In this case, suitable oxide materials are chosen to be the functionalized layer of the synthetic nanoparticles and we can add these particles into the water source contaminated by those compounds. After those organic compounds are adsorbed to oxide-capped synthetic nanoparticles, we can again use the magnet to separate these nanoparticles from water.
In a preferred embodiment, there are multiple kinds of contaminants in the contaminated/questionable water and each of the contaminants can be removed by one kind of synthetic nanoparticles. As illustrated in
In many cases, such as Ag for water disinfection and TiO2 for photo-catalytic degradation, the functional layers will not be consumed significantly after the nanoparticles are used for treating water for the first time. Also, due to the low remanence of the magnetic cores in synthetic nanoparticles, the particles can be redispersed well in aqueous solution once the external magnetic field is removed. These two properties indicate that we can use synthetic nanoparticles regeneratively, making this technique both cost-effective, environmentally friendly and sustainable. Specifically, we can design a reactor containing synthetic nanoparticles and the reaction has two states. At the ‘magnet OFF’ state, water from a contaminated or questionable source fills the reactor and nanoparticles redisperse in the water because there is no external magnetic field. These nanoparticles tackle the contaminants in the water by disinfection, degradation or other means. Then, the reactor switches to the ‘magnet ON’ state, and all the nanoparticles are attracted towards the magnet and aggregate. The treated water is collected for drinking or other purposes. The reactor can be switched between the ‘magnet OFF’ state and the ‘magnet ON’ state repeatedly, producing clean water automatically. There is no need to replace the synthetic nanoparticles except regenerating them periodically to maintain their chemical and photo-catalytic functionality.
Besides being ideal for magnetic separation, the cores of synthetic nanoparticles have additional properties (e.g., magnetic hyperthermia, see below) suitable for degrading trace chemicals that are otherwise difficult to degrade. Such chemicals include non-degradable and bio-accumulative, perfluorinated compounds (PFCs) which are of increasing public concern.
In one embodiment, these nanoparticles are dried on a substrate after the adsorption of the PFC molecules. The dried powders can be directly heated up for a sufficient duration until the PFC backbones are broken. In addition, an alternating magnetic field can be applied to generate extra energy in the nanoparticles through a mechanism known as magnetic hyperthermia. Moreover, an RF electromagnetic field can be applied and it can generate eddy currents within the nanoparticles and nanoparticle clusters because their cores are made of metallic materials. Again this extra energy generated by the eddy currents will potentially degrade the PFC molecules.
Several experiments have been performed using synthetic nanoparticles described above for water disinfection. Here, the synthetic nanoparticles are 160 nm in diameter and they have layer sequences of: Ag 20 nm/Ti 5 nm/Fe 5 nm/Ti 3 nm/Fe 5 nm/Ti 5 nm/Ag 20 nm. The nanoparticles are designed for treating water sources potentially containing pathogens. Here, we choose E. Coli as the sample pathogen and prepare the water sample by adding E. Coli to DI water.
Here, aliquots of synthetic-nanoparticle solution are placed in identical vials. The volume of each sample is 200 μl. A NdFeB magnet is placed underneath each vial and the synthetic nanoparticles are attracted downward in response to the external magnetic field. Each vial is set to have a different magnetic-separation time duration and right after this separation time, 170 μl of the bulk solution is transferred to a new vial, leaving the old vial containing 30 μl of solution. The amounts of particles in both new and old vials are expressed in terms of Ag amount and this amount is measured by inductively-coupled plasma mass-spectrometry (ICPMS). Generally, a known amount of particle solution is mixed with at least equal amount of 70 wt % concentrated nitric acid and incubated overnight. During this time, Ag, Ti and Fe from the particles will all be dissolved into the solution. Then the mixture is further diluted with ultrapure distilled water to a known amount, when the concentrations of these elements are measured by ICPMS.
The percentage of particles remaining in the bulk solution is calculated as the ratio between Ag amount in the new vial and the total Ag amount in both old and new vials. The percentages for different samples are plotted vs. the separation time, as shown in
Here, synthetic nanoparticles with a series of dosages are mixed with water samples with different active E. Coli concentrations. The dosage of the nanoparticles is expressed in terms of the total amount of Ag in the solution, which can be again measured by ICPMS. The active E. Coli concentration is measured by taking a known portion of water sample and spreading it onto an agar plates for culturing. Typically after one day of incubation under 30° C., each active E. Coli cell will reproduce to form a colony and E. Coli concentration in the original sample can be obtained by counting the number of colony forming units (CFUs).
After mixing synthetic nanoparticles with water sample, the solution is set aside for 10 min. Then, the nanoparticles are separated from water using a magnet using the previous setup. The separation time is set to be 10-20 min, since over 99% of nanoparticles can be separated from the bulk solution within this amount of time according to the previous result. The disinfection effect is characterized by the removal rate after disinfection, which is the ratio between the inactivated E. Coli number and the total E. Coli number.
In the previous two experiments, Ag-capped synthetic nanoparticles have shown encouraging performance for both magnetic separation and water disinfection. Also in the previous work, we show that these synthetic nanoparticles can be redispersed well in water once the external magnetic field is removed. These important aspects are the building blocks for a practical portable point-of-use water disinfection device, where nanoparticles are used regeneratively. Here, in order to demonstrate the regenerative use of Ag-capped synthetic nanoparticles, a certain amount of nanoparticles is mixed with DI water containing E. Coli for the first cycle to make a total solution volume of 1 ml, where the Ag concentration is 14.4 ppm. This setup is incubated for 20 min and a magnet is used to separate the particles from bulk solution for 20 min. Then 900 μl of the bulk solution is removed, followed by the addition of 900 μl fresh DI water containing E. Coli. And again this setup is incubated for 20 min in order to start the second cycle and the process is repeated for 9 cycles. In all of these cycles, the initial E. Coli concentration is varying above 105/ml level.
A synthetic nanoparticle with a multi-layered disk-shaped structure, where the diameter of the synthetic nanoparticle in is a range from 50 nm to 200 nm. Here the synthetic nanoparticle includes: a) a multi-layered synthetic antiferromagnetic core; and b) environmentally functional layers on at least one side of the magnetic core.
The magnetic core can include a layer stack C/F/S/F/C, where F stands for ferromagnetic layers (same or different materials), S stands for a non-magnetic spacer layer, and C stands for capping layers (same or different materials). Suitable materials for the S layer include, but are not limited to: ruthenium and titanium. Preferably, the thickness of the S layer is 10 nm or less. Suitable materials for the F layers include, but are not limited to: iron and cobalt-iron alloys. Preferably, the F layers have a thickness ranging from 5 nm to 30 nm. Suitable materials for the C layers include but are not limited to: titanium. Preferably, the C layers have a thickness ranging from 3 nm to 10 nm. Preferably, the environmentally functional layer (or layers) has a thickness ranging from 10 nm to 50 nm.
Suitable materials for the environmentally functional layer (or layers) include, but are not limited to: silver. Such silver-containing nanoparticles are suitable for water disinfection. For example, a disinfection method can include: i) adding the synthetic nanoparticles into water source containing micro-organisms, and incubating for a certain amount of time; and ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the water disinfected and free of synthetic nanoparticles.
Suitable materials for the environmentally functional layer (or layers) include, but are not limited to: titanium dioxide, in the form of rutile, anatase or amorphous phase. Such nanoparticles are suitable for photodegradation of hazardous organic compounds. For example, a remediation method can include: i) adding the synthetic nanoparticles into water source containing hazardous organic compounds, and incubating for a certain amount of time while irradiating with ultraviolet light; and ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the hazardous organic compounds degraded and the water free of synthetic nanoparticles. This approach is suitable for remediation of compounds such as: trichloroethylene and its derivatives, N-Nitrosodimethylamine and its derivatives, dye molecules, or other organic compounds.
Suitable materials for the environmentally functional layer (or layers) include, but are not limited to: silica or metal oxides. Such nanoparticles are suitable for remediation of non-degradable organic compounds. For example, a remediation method can include: i) adding the synthetic nanoparticles into a water source containing non-degradable organic compounds, and incubating for a certain amount of time; and ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the water free of both synthetic nanoparticles and non-degradable organic compounds. Further processing can break down non-degradable compounds, e.g., by heating or hyperthermia. For example, a method can include: i) adding the synthetic nanoparticles into water source containing non-degradable perfluorinated compounds, and incubating for certain amount of time; ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the water free of both synthetic nanoparticles and perfluorinated compounds; and iii) drying the particles out on a substrate after they are separated from the bulk water source, and applying an external alternating magnetic field (hysteresis loss heating), heat, external RF electromagnetic field (to induce eddy currents which heat the nanoparticles) or other means to introduce extra energy to break the backbone of the perfluorinated compounds.
The treatment approaches of embodiments 3, 4 and 5 can be practiced individually or in any combination. For example, multiple kinds of nanoparticles can be employed to simultaneously disinfect, degrade and/or segregate biological and/or chemical contaminants in water. For example, a method can include: i) adding all kinds of synthetic nanoparticles together into a water source possibly containing micro-organisms as well as degradable and non-degradable organic compounds, and incubating for certain amount of time, including irradiation with ultraviolet light if/as needed; and ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the water disinfected and free of synthetic nanoparticles as well as degradable and non-degradable hazardous organic compounds.
In practicing embodiments 1-6, the nanoparticles can be used in a regenerative manner. For example, a treatment method can include: i) adding all kinds of synthetic nanoparticles together into a water source possibly containing micro-organisms as well as degradable and non-degradable organic compounds, and incubating for a certain amount of time, including irradiation with ultraviolet light if/as needed; ii) magnetically separating the synthetic nanoparticles from the water source, and leaving the water disinfected and free of synthetic nanoparticles as well as degradable and non-degradable hazardous organic compounds; and iii) redispersing the synthetic nanoparticles after they are separated from bulk water source and adding them into new water source containing micro-organisms as well as degradable and non-degradable organic compounds and repeating the process starting from
In any of the preceding methods, the incubation time can be between 10 minutes and two days, according to the different situations. The magnetic separation time can be between 10 minutes and 5 hours, according to the different situations.
This application claims the benefit of U.S. provisional patent application 61/703,068, filed on Sep. 19, 2012, and hereby incorporated by reference in its entirety.
This invention was made with Government support under contract number CA151459 awarded by the National Institutes of Health. The Government has certain rights in this invention.
Number | Date | Country | |
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61703068 | Sep 2012 | US |