Nanomaterial-based processing of dyes and organic compounds
By contacting the metal oxide nanowire composition with dyes and organic compounds and illuminating under partial decomposition conditions, the problem of difficulty in decomposing these substances in the prior art is solved, and an effective decomposition effect and a reusable nanowire system are achieved.
Patent Information
- Application Number
- CN202380021379.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-02-11
- Filing Date
- 2023-02-10
- Publication Date
- 2025-03-25
AI Technical Summary
Certain dyes and organic compounds pose health and the environment threat, and prior art is difficult to effectively decompose these substances.
By contacting the composition containing metal oxide nanowires with dyes and/or organic compounds, it is associated under partial decomposition or degradation conditions, and light treatment can be performed to accelerate the decomposition process.
Effective decomposition of dyes and organic compounds is achieved, reducing their health and environmental threats, and providing a reusable nanowire system for adsorption and decomposition of other dyes and organic compounds.
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Abstract
Description
[0001] Cross-references to related material
[0002] This application claims priority to and the benefit of U.S. Patent Application No. 63 / 309,411, filed February 11, 2022, for Nanomaterial-Based Processing of Dyes and Organic Compounds. All of the above applications are incorporated herein by reference in their entirety for any and all purposes. Technical Field
[0003] The present disclosure relates to the field of one-dimensional nanomaterials. Background Art
[0004] Certain dyes and organic compounds may be undesirable because they may cause health effects to humans exposed to them and may pose other environmental risks.Therefore, there has long been a need for methods of decomposing dyes and / or organic compounds. Summary of the invention
[0005] To meet the long-standing need, the present disclosure provides a method, comprising: contacting a composition comprising metal oxide nanowires with a dye and / or an organic compound under conditions where the dye and / or the organic compound undergo at least partial decomposition or degradation, the metal oxide nanowires optionally comprising titanium, the metal oxide nanowires optionally having a one-dimensional anatase structure, the metal oxide nanowires optionally comprising carbon, the structure of the oxide nanowires optionally being a lepidocrocite structure or even a 1-dimensional lepidocrocite (1DL) structure; and optionally also comprising irradiating the composition and the dye and / or the organic compound with light.
[0006] Also provided is a system comprising a conduit and a quantity of a composition comprising metal oxide nanowires, the metal oxide nanowires optionally comprising titanium, the metal oxide nanowires optionally comprising carbon, the structure of the oxide nanowires optionally being a lepidocrocite structure, the conduit fluidly connecting the composition to a process stream comprising a dye and / or an organic compound. BRIEF DESCRIPTION OF THE DRAWINGS
[0007] In the drawings, which are not necessarily drawn to scale, like numbers may describe similar components in different views. Like numbers with different letter suffixes may represent different instances of similar components. The accompanying drawings generally illustrate various aspects discussed in this document by way of example and not by way of limitation. In the drawings:
[0008] Figure 1Provided (left) are exemplary wavelength versus absorbance data for 1DL and Rhodamine 6G aqueous solutions, as well as exemplary time versus residual dye data for the 1DL and Rhodamine 6G aqueous solutions.
[0009] Figure 2 A calibration curve for an aqueous solution of Rhodamine 6G is provided.
[0010] Figure 3 Exemplary data of suspended flocs of 1DL and Rhodamine 6G in water before (left) and after (right) illumination are provided.
[0011] Figure 4 A qualitative representation of the decolorization of Rhodamine 6G in 1 DL of aqueous solution is provided before (right) and after (left) filtration.
[0012] Figure 5 The wavelength and absorbance data of 1DL and Rhodamine 6G aqueous solution at different exposure times and filtering to remove all 1DL are provided. The exemplary wavelength and absorbance data correspond to Figure 4 The solution in the picture on the right. DETAILED DESCRIPTION
[0013] The present disclosure may be understood more readily by reference to the following detailed description of desired embodiments and the Examples included therein.
[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those of ordinary skill in the art. In the event of a conflict, the present document (including definitions) shall prevail. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein may be used in practice or testing. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and embodiments disclosed herein are illustrative only and are not intended to be limiting.
[0015] Unless the context clearly indicates otherwise, references without a specific number include plural references.
[0016] As used in this specification and claims, the term "comprising" may include the embodiments "consisting of" and "consisting essentially of." As used herein, the terms "comprising," "including," "having," "having," "may," "containing," and variations thereof are intended to be open transitional phrases, terms, or words that require the presence of specified ingredients / steps and allow for the presence of other ingredients / steps. However, such descriptions should be interpreted as also describing a composition or method as "consisting of" and "consisting essentially of the listed ingredients / steps," which allows for the presence of only the specified ingredients / steps, and any impurities that may result therefrom, without including other ingredients / steps.
[0017] As used herein, the terms "about" and "equal to or about" mean that the amount or value in question may be a value that is indicated as being approximately or roughly the same as some other value. It is generally understood that, as used herein, unless otherwise indicated or inferred, it is a nominal value indicated with a ±10% variation. The term is intended to convey that similar values contribute to the equivalent results or effects described in the claims. That is, it is understood that the amount, size, formula, parameter, and other amounts and characteristics are not and need not be precise, but may be approximate and / or larger or smaller as needed, thereby reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. Typically, an amount, size, formula, parameter, or other amount or characteristic is "about" or "approximately", whether or not there is a clear such description. It should be understood that, unless otherwise specifically stated, when "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself.
[0018] Unless indicated to the contrary, numerical values should be understood to include the same value when reduced to the same number of significant figures and values that differ from the stated value by less than the experimental error of ordinary measurement techniques of the type described in this application for determining the value.
[0019] All ranges disclosed herein are inclusive of and independent of the endpoints (e.g., "between 2 grams and 10 grams and all intermediate values include 2 grams, 10 grams, and all intermediate values"). The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are imprecise enough to include values approximating these ranges and / or values. All ranges are combinable.
[0020] As used herein, approximate language can be applied to modify any quantitative representation that can change without causing the basic function associated therewith to change. Therefore, in some cases, the value modified by terms such as "about" and "substantially" may not be limited to the specified exact value. In at least some cases, the approximate language may correspond to the precision of the instrument used to measure the value. The modifier "about" should also be considered to disclose the range limited by the absolute values of the two endpoints. For example, the expression "about 2 to about 4" also discloses the range of "from 2 to 4". The term "about" can refer to the plus or minus 10% of the specified number. For example, "about 10%" can represent a range of 9% to 11%, and "about 1" can mean from 0.9 to 1.1. Other meanings of "about" can be obvious from the context, such as rounding, so, for example, "about 1" can also mean from 0.5 to 1.4. In addition, the term "comprising" should be understood to have its open meaning "including", but the term also includes the term closed meaning "consisting of...". For example, a composition comprising components A and B may be a composition comprising A, B and other components, but may also be a composition made only of A and B. Any document cited herein is incorporated by reference in its entirety for any and all purposes.
[0021] Exemplary Embodiments
[0022] The following exemplary embodiments are merely illustrative and are not intended to limit the scope of the disclosure or the claims.
[0023] Example
[0024] Example 1 - Synthesis of 1DL
[0025] 10 g binary titanium precursor (e.g. TiB2, TiN, TiC) powder was mixed with 100 mL tetramethylammonium hydroxide aqueous solution (25 w / w) at 80 °C for 72 hours. Washed with ethanol until the resulting supernatant solution was neutral. The neutral material was suspended in water to produce a stable colloidal suspension.
[0026] Example 2 - Contacting 1DL with Rhodamine 6G - Adsorption Protocol
[0027] Add 0.4 mL of 1 g / L colloidal 1DL to 38.8 mL of deionized water and mix for 1 minute to combine. Then add 0.8 mL of 500 mg / L dye solution to the 1DL aqueous solution. Stir at 400 RPM for 5 minutes to form 1DL-dye aggregates or flocs, such as Figure 5 The floccules can be removed from the solution using a 0.45 um PTFE syringe filter, and the overall kinetics of dye removal can be monitored by ultraviolet-visible (UV-Vis) light ( Figure 1-dark) spectrometer using the calibration curve ( Figure 2 ) for monitoring.
[0028] Example 3 - Contacting 1DL with Rhodamine 6G - Adsorption Protocol
[0029] 4 mL of 1 g / L colloid 1DL was added to 35.2 mL of deionized water and mixed for 1 minute to combine. 0.8 mL of 500 mg / L dye solution was then added to the 1DL aqueous solution. The 1DL-dye complex was immediately formed when stirred at 400 RPM, as shown in Figure 6. The complex can be removed from the solution by filtration with a Celgard ion exchange membrane, and the removal can be detected by UV-Vis ( Figure 1 -dark) using the calibration curve ( Figure 2 ) for monitoring.
[0030] Example 4 - Contacting 1DL with Rhodamine 6G - Degradation in the Solar Spectrum
[0031] After the adsorption protocol, a xenon lamp (a solar simulator) or sunlight can be applied to the solution system. There is significant decolorization without any aliquot removal. The decolorization rate is proportional to the ratio of 1DL to Rhodamine 6G and the power of the light source. Figure 1 (illustration) and Figure 4 Decolorization as a function of irradiation time is illustrated.
[0032] aspect
[0033] The following aspects are merely illustrative and do not limit the scope of the disclosure or claims.Any one or more parts of any one or more aspects may be combined with any one or more parts of any one or more other aspects.
[0034] Aspect 1. A method comprising: contacting a composition comprising metal oxide nanowires with a sample comprising a dye and / or an organic compound under conditions such that the dye and / or the organic compound associate with the composition; and the metal oxide nanowires optionally comprise titanium, the metal oxide nanowires optionally comprise carbon, and the oxide nanowires optionally have a lepidocrocite structure.
[0035] The metal oxide nanowires may optionally have a titanium oxide lepidocrocite structure. The metal oxide nanowires may optionally be one-dimensional nanowires (which may be lepidocrocite) having a cross section of 1 nm or less.
[0036] The association between the dye and / or organic compound and the metal oxide nanowires may be adsorption.
[0037] Titanium oxide nanowires are considered particularly suitable. Examples of one-dimensional nanowires are described in the following literature: Badr et al., "Bottom-Up, Scalable Synthesis Of Anatase Nanofilament-Based Two-Dimensional Titanium Carbo-Oxide Flakes", Materials Today 2021 (https: / / doi.org / 10.1016 / j.mattod.2021.10.033); and Badr et al., "On the structure of one-dimensional TiO2 lepidocrocite", Matter 2023 (https: / / doi.org / 10.1016 / j.matt.2022.10.015). It should be understood that the nanowires can be included in the form of mesoporous materials (e.g., powders), sheets, and other forms. It should be understood that the nanowires may be tubular in nature.
[0038] The composition and the dye and / or the organic compound may be present in a solvent, such as water. Other solvents (polar solvents, non-polar solvents, alcohols, etc.) may be used. The contact may be carried out at about 20°C to about 95°C, or about 25°C to about 75°C, or about 30°C to about 70°C, or about 35°C to about 65°C, or about 40°C to about 60°C, or about 45°C to about 55°C, or even about 50°C. The contact may last for, for example, about 5 minutes to about 5 hours, about 10 minutes to about 4.5 hours, about 15 minutes to about 4 hours, about 20 minutes to about 3.5 hours, about 30 minutes to about 3 hours, about 45 minutes to about 2 hours, or any combination or sub-range thereof.
[0039] Aspect 2. The method of claim 1, further comprising achieving at least partial decomposition or degradation of the dye and / or the organic compound, and optionally comprising irradiating the composition and the dye and / or the organic compound with light. Without being bound by any particular theory or embodiment, the irradiation with light may cause at least partial decomposition or degradation of the dye and / or the organic compound.
[0040] Aspect 3. The method of claim 2, wherein the illumination comprises xenon lamp illumination. Other forms of illumination may also be used, such as natural light or UV light.
[0041] Aspect 4. The method according to any one of claims 2 to 3, wherein the at least partial decomposition produces one or more fragments. For example, the fragments may be fragments of dyes and / or organic compounds.
[0042] Aspect 5. The method according to any one of claims 1 to 4, wherein the dye comprises any one or more of rhodamine 6G, methylene blue, methyl orange and crystal violet. Other suitable dyes include, for example, Alcian Blue 8GX, Alcian Yellow GXS, Alizarin, Alizarin Red S, Alizarin Yellow GG, Alizarin Yellow R, Azo Flame Red, Bismarck Brown R, Bismarck Brown Y, Phenylene Brown, Brilliant Cresol Blue, Chrysidine R, Chrysidine Y, Congo Red, Crystal Violet, Ethyl Green, Fuchsinic Acid, Gentian Violet, Janus Green, Lissamine Fast Yellow, Malachite Green, Matthew Yellow, Meldola Blue, Metamin Yellow, Methyl Orange, Methyl Red, Methylene Blue, Naphthalene Black, Naphthol Green B, Naphthol Yellow S, Orange G, Purpurin, Bengal Rose Red, Sudan II, Titanium Yellow, Trophium Orange O, Trophium Orange OO, Trophium Orange OOO, Victoria Blue 4R, Victoria Blue B, Victoria Blue R, Xylene Cyanol FF or any combination thereof.
[0043] Aspect 6. The method according to any one of claims 1 to 5, wherein the organic compound comprises any one or more of benzene, phenol, phthalate, methine, azo, phthalocyanine, triarylmethane, and a compound containing an amino group and / or a nitro group.
[0044] Aspect 7. The method according to any one of claims 1 to 6, wherein the contacting is performed in a recycling manner.
[0045] Aspect 8. The method according to any one of claims 1 to 7, wherein the contacting is performed in a single pass.
[0046] Aspect 9. The method of any one of claims 1 to 8, further comprising determining the level of the dye and / or organic compound in the sample before contacting the sample with the composition comprising metal oxide nanowires.
[0047] Aspect 10. The method of any one of claims 1 to 9, further comprising determining the level of the dye and / or organic compound in the sample after contacting the sample with the composition comprising metal oxide nanowires.
[0048] Aspect 11. The method of any one of claims 9 to 10, further comprising, if the level is above a threshold level, further contacting the sample with the composition comprising metal oxide nanowires.
[0049] Aspect 12. The method of claim 11, wherein the level is determined spectrally.
[0050] Aspect 13. The method of claim 12, wherein the level is determined by comparing the absorbance at a certain wavelength with a standard value.
[0051] Aspect 14. The method of claim 13, wherein the level is determined by comparing the absorbance at a first wavelength to the absorbance at a second wavelength.
[0052] Aspect 15. The method according to any one of claims 2 to 14, further comprising collecting the at least partially decomposed product. The collecting can be performed, for example, by filtration or centrifugation.
[0053] Aspect 16. A system comprising a conduit and a quantity of a composition comprising metal oxide nanowires, the conduit fluidically connecting the composition to a process stream comprising a dye and / or an organic compound. The system can be configured to associate, such as adsorb, the dye and / or organic compound with the metal oxide nanowires.
[0054] Suitable metal oxide nanowires are described elsewhere herein.The composition comprising metal oxide nanowires may be, for example, an aqueous solution.
[0055] As an example, the metal oxide nanowire cartridge can be positioned so that an effluent stream from a chemical processing plant flows through the metal oxide nanowires, thereby giving the metal oxide nanowires an opportunity to adsorb / decompose dyes and / or organic compounds that may be present in the effluent. The system can also include a source of illumination (e.g., xenon lamp, UV light); without being bound by any particular theory, illumination can improve the decomposition properties of the metal oxide nanowires.
[0056] Aspect 17. The system of claim 16, wherein the system operates in a continuous manner.
[0057] Aspect 18. The system of claim 16, wherein the system operates in a batch or semi-batch manner.
[0058] As an example, an aqueous colloidal suspension of metal oxide nanowires may be added to a process stream (e.g., an effluent stream) to give the metal oxide nanowires an opportunity to adsorb dyes and / or organic compounds that may be in the process stream. The adsorbed material may then be separated by centrifugation or filtration or by allowing the adsorbed / deflocculated material to settle. The system may also include a light source (e.g., a xenon lamp); without being bound by any particular theory, the light may decompose the adsorbed dyes and / or organic compounds on the metal oxide nanowires, thereby allowing the nanowires to be re-added, reused, and / or recycled into the process stream, where the nanowires may adsorb other dyes and / or organic compounds. In this manner, the nanowires adsorb the dyes, the dyes are decomposed into components, and then the "clean" nanowires are reintroduced into the process stream to adsorb other dyes in the process stream. Without being bound by any particular theory or embodiment, the above method may be repeated to decompose a given dye into CO2 and / or water and / or nitrogen and / or nitrates.
[0059] As an example, the disclosed method may include (a) dye molecules adsorbed to nanostructures; (b) under light, the dye decomposes into fragments and the fragments of the dye molecules can or cannot be separated from the nanostructure; (c) the separated dye fragments are then re-adsorbed to the nanostructure; (d) under light, the dye subfragments are separated from the nanostructure; (e) steps c and d are repeated until only CO2 and / or water and / or nitrogen and / or nitrate are left of the dye.
Claims
1. A method, comprising: contacting a composition comprising metal oxide nanowires with a sample comprising a dye and / or an organic compound under conditions such that the dye and / or the organic compound associate with the composition; and The metal oxide nanowires optionally contain titanium, the metal oxide nanowires optionally contain carbon, and the oxide nanowires optionally have a lepidocrocite structure.
2. The method of claim 1, further comprising achieving at least partial decomposition or degradation of the dye and / or the organic compound, and optionally further comprising irradiating the composition and the dye and / or the organic compound with light. The method of claim 2 , wherein the illumination comprises xenon lamp illumination.
4. The method according to any one of claims 2 to 3, wherein the at least partial decomposition produces one or more fragments.
5. The method according to any one of claims 1 to 3, wherein the dye comprises any one or more of rhodamine 6G, methylene blue, methyl orange and crystal violet.
6. The method according to any one of claims 1 to 3, wherein the organic compound comprises any one or more of benzene, phenol, phthalate, methine, azo, phthalocyanine, triarylmethane and a compound containing an amino group and / or a nitro group.
7. The method according to any one of claims 1 to 3, wherein the contacting is performed in a recirculating manner.
8. The method according to any one of claims 1 to 3, wherein the contacting is performed in a single pass.
9. The method of any one of claims 1 to 3, further comprising determining the level of the dye and / or organic compound in the sample prior to contacting the sample with the composition comprising metal oxide nanowires.
10. The method of any one of claims 1 to 3, further comprising determining the level of the dye and / or organic compound in the sample after contacting the sample with the composition comprising metal oxide nanowires.
11. The method of claim 9, further comprising, if the level is above a threshold level, further contacting the sample with the composition comprising metal oxide nanowires.
12. The method of claim 11, wherein the level is determined spectrally.
13. The method of claim 12, wherein the level is determined by comparing the absorbance at a certain wavelength with a standard value.
14. The method of claim 13, wherein the level is determined by comparing the absorbance at a first wavelength to the absorbance at a second wavelength.
15. The method according to any one of claims 2 to 3, further comprising collecting the at least partially decomposed products.
16. A system comprising a conduit and a quantity of a composition comprising metal oxide nanofilaments, the conduit fluidly connecting the composition to a process stream comprising a dye and / or an organic compound.
17. The system of claim 16, wherein the system operates in a continuous manner.
18. The system of claim 16, wherein the system operates in a batch or semi-batch manner.