In recent years, nanoparticles have become increasingly important in many industrial processes and products. For example nano-scale metals such as zero-valent iron nanoparticles can be used in removing environmental pollutants and for purifying contaminated water. Such nanoparticles can be effective at transformation and removal of organic contaminants and heavy metals such as tetrachloroethylene (TCE), trichloroethylene, chromium, lead, metalloid arsenic and other general environmental pollutants such as nitrate, chloroform, nitrobenzene, nitrotoluene and methane chloride.
Zero-valent iron nanoparticles can be produced by milling of aggregates or microscale particles. Another way of synthesizing zero-valent iron nanoparticles is by reacting ferric chloride (FeCl3) with sodium borohydride solution. Moreover, iron nanoparticles may also be formed by heating iron pentacarbonyl and by reacting iron oxides with hydrogen.
Commercially available zero-valent iron nanoparticles synthesized using the above techniques have poor air stability and are rapidly oxidized when exposed to air thereby losing their high reactivity. Moreover, these nanoparticles have substantially high particle agglomeration and are inflammable. Many techniques have been developed to suppress oxidation and protect the nanoparticles during drying after synthesis, such as use of an anaerobic chamber, lyophillization and vacuum drying techniques. However, most of these techniques are expensive, tedious and may hinder in various applications of nanoparticle such as in removing environmental pollutants.
The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description.
Briefly, in accordance with one aspect, methods of synthesizing metal nanoparticles from a metal oxide ore are provided. The methods include adding a metal compound and a reducing agent to the metal oxide ore and contacting the metal compound and the reducing agent to form zero-valent metal nanoparticles. The methods also include contacting the metal oxide ore and hydrogen (H2) in presence of the zero-valent metal nanoparticles to form zero-valent metal and metal nanoparticles.
In accordance with another aspect, methods of synthesizing iron nanoparticles from laterite ore are provided. The methods include mixing an iron compound with a solvent to form an iron compound solution and adding a solution of the laterite ore to the iron compound solution to form a laterite ore solution. The methods also include contacting a reducing agent with the laterite ore solution to form zero-valent iron nanoparticles and contacting the laterite ore and hydrogen (H2) in presence of the zero-valent iron nanoparticles to form zero-valent iron and iron nanoparticles.
In accordance with another aspect, iron nanoparticles are provided. The iron nanoparticles are synthesized from laterite ore by reacting an iron compound and a reducing agent with the laterite ore.
In accordance with another aspect, methods for treating contaminated water are provided. The methods include contacting zero-valent iron and iron nanoparticles with the contaminated water to remove contaminants from the water. The zero-valent iron and iron nanoparticles are synthesized from a laterite ore by reacting an iron compound and a reducing agent with the laterite ore.
In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be used, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the Figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.
It will also be understood that any compound, material or substance which is expressly or implicitly disclosed in the specification and/or recited in a claim as belonging to a group or structurally, compositionally and/or functionally related compounds, materials or substances, includes individual representatives of the group and all combinations thereof. While various compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of” or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.
Some embodiments are generally directed to techniques of synthesizing metal nanoparticles from metal oxide ores. The embodiments described below provide a method of synthesizing metal nanoparticles by reduction of respective metal oxide ores using a metal compound and a reducing agent. A variety of metal nanoparticles such as iron nanoparticles, aluminum nanoparticles, zinc nanoparticles and antimony nanoparticles can be synthesized from their respective metal oxide ores using the present technique. The disclosed technique facilitates synthesis of metal nanoparticles from their respective metal oxide ores under normal temperature and atmospheric conditions. The technique is environment friendly and is substantially cost effective. The metal nanoparticles synthesized using the technique disclosed herein are light in weight, are air stable and can be substantially dispersed in an aqueous medium. Such metal nanoparticles may be used in purification systems such as for treating contaminated water.
Referring now to
In one example embodiment, a concentration of the iron compound is about 0.1 M to about 10M.
In another example embodiment, the metal oxide ore includes bauxite, the metal compound includes an aluminum compound and the metal nanoparticles include zero-valent aluminum and aluminum nanoparticles respectively. Examples of the aluminum compound include, but are not limited to, aluminum chloride (AlCl3), aluminum (I) oxide (Al2O), aluminum (II) oxide, aluminum hydroxide, aluminum hydroxide oxide, or combinations thereof.
In another example embodiment, the metal oxide ore includes sphalerite, the metal compound includes a zinc compound and the metal nanoparticles comprise include zero-valent zinc and zinc nanoparticles respectively. Examples of the zinc compound include, but are not limited to, zinc chloride (ZnCl2), zinc oxide (ZnO), zinc hydroxide (Zn(OH)2), zinc sulphide (ZnS), or combinations thereof.
In another example embodiment, the metal oxide ore includes stibnite (Sb2S3), the metal compound includes antimony (Sb) compound and the metal nanoparticles include zero-valent antimony and antimony nanoparticles respectively. Examples of the antimony compound include, but are not limited to, antimony trichloride (SbCl3), antimony pentachloride (SbCl5), antimony pentaoxide (Sb2O5), antimony tetraoxide (Sb2O4), antimony pentasulfide, or combinations thereof.
In the illustrated embodiment, the metal compound is mixed with a solvent to form a metal compound solution. Examples of the solvent include, but are not limited to, ethanol, water, pentane (C5H12), cyclopentane (C5H10), hexane (C6H14), cyclohexane (C6H12), benzene (C6H6), toluene 1,4 dioxane, chloroform (CHCl3), diethylether (C2H5)2O, dichloromethane (CH2Cl2), tetrahydrofuran (C4H8O), ethyl acetate (C4H8O2), acetone (C3H6O), dimethylformamide (C3H7NO), acetonitrile (C2H3N), dimethyl sulfoxide, propylene carbonate (C4H6O), formic acid (CH2O2), acetic acid (C2H4O2), n-butanol, isopropanol, n-propanol, methanol, or combinations thereof. In one example embodiment, the solvent includes ethanol and water to minimize oxidation during synthesis of the metal nanoparticles.
Further, a colloidal solution of the metal oxide ore is added to the metal compound solution. For example, laterite ore solution may be added to an iron compound solution for synthesis of iron nanoparticles from the laterite ore. In this example, the laterite ore is present in the laterite ore solution at a concentration of about 2% (w/v) to about 20% (w/v). In one example embodiment, the iron nanoparticles are synthesized from the laterite ore at a temperature of about 10° C. to about 100° C. The reducing agent is then gradually added to contact the metal compound solution while stirring the solution to form zero-valent metal nanoparticles (block 104).
Examples of reducing agent include, but are not limited to, carbon monoxide (CO), sodium borohydride (NaBH4), lithium borohydride (LiBH4), hydroquinone (C6H4(OH)2), hydrazine hydrate (H6N2O), glycol ethylene (C2H6O2), formaldehyde (CH2O), ethanol (C2H6O), hydroxyl radicals, sugar pyrolysis radicals, saccharide, N,N-dimethylformamide, sodium citrate or a combination thereof. In one example embodiment, a concentration of the reducing agent is about 1 M to about 10 M. Moreover, a reaction time for contacting the reducing agent with the metal oxide ore solution is about 1 minute to about 5 minutes.
At block 106, the metal oxide ore and hydrogen are contacted in presence of the zero-valent metal nanoparticles to form zero-valent metal and metal nanoparticles. In this example embodiment, the hydrogen is generated from contacting the metal compound and the reducing agent. In some embodiments, a reaction time for reducing the metal oxide ore in presence of the zero-valent metal nanoparticles is about 1 hour to about 7 days. The zero-valent metal and metal nanoparticles are subsequently extracted from the solution and the extracted nanoparticles may be washed and dried.
Moreover, a solution of laterite ore is added to the iron compound solution to form a laterite ore solution 204. A reducing agent such as sodium borohydride (NaBH4) is contacted with the laterite ore solution 204 to form the zero-valent iron nanoparticles 202. The reaction of the reducing agent (NaBH4) and ferric chloride is represented by the following equation:
2FeCl3+6NaBH4+18H2O→2Fe0+6B(OH)3+21H2+6NaCl (1)
In the illustrated embodiment, the resultant black colloidal solution is then left for spontaneous autocatalytic activity of zero-valent iron nanoparticles 202. As can be seen, hydrogen (H2) (generally represented by reference numerals 206 and 208) is generated from contacting the laterite ore solution 204 and the reducing agent. This released hydrogen 206 and 208 facilitates further reduction of the laterite ore to form zero-valent iron and iron nanoparticles.
In the illustrated embodiment, some hydrogen atoms 206 remain attached to the zero-valent iron nanoparticles 202, while some hydrogen atoms 208 diffuse into the laterite ore solution 204. These hydrogen atoms 208 contact the laterite ore in presence of the zero-valent iron nanoparticles 202 to form zero-valent iron and iron nanoparticles. The stepwise reduction of the laterite ore containing iron oxide (Fe2O3) into zero-valent iron and iron nanoparticles is represented by the following equations:
3Fe2O3+H2→2Fe3O4+H2O (2)
Fe3O4+4H2→3Fe0+4H2O (3)
In this embodiment, the catalysis by zero-valent iron nanoparticles to reduce laterite is due to dissociation of molecular hydrogen 206 from the metal followed by diffusion of adsorbed hydrogen atoms. The hydrogen atoms 206 and 208 facilitate stepwise transformation of laterite (Fe2O3) into magnetite and to flatter wusite and finally into finger-shaped, connected iron nanoparticles across the laterite interface. In certain embodiments, heterocatalytic effects of other metal oxides such as oxides of aluminum (Al), copper (Cu), molybdenum (Mo) and titanium (Ti) present in the laterite ore further facilitate reduction of ferrous oxide into iron nanoparticles. During the transformation process, initial spherical magnetite nanoparticles first turn into flatter nanoparticles and finally into spherical zero-valent iron nanoparticles.
In certain embodiments, parameters such as pH of the solution, concentrations of the iron compound and the reducing agent, a stirring speed, a titration rate, a reaction time and reaction temperature may be adjusted to control composition, properties and the morphology of the synthesized iron nanoparticles.
A variety of zero-valent metal and metal nanoparticles can be synthesized from their respective metal oxide ores. In one example embodiment, iron nanoparticles are synthesized from laterite ore using the process described above. The zero-valent iron nanoparticles synthesized from the laterite ore are substantially dispersed particles. In one example embodiment, the zero-valent iron nanoparticles have about 30% to about 60% more dispersion as compared to nanoparticles synthesized from ferric chloride solution. Moreover, a rate of oxidation of the zero-valent iron nanoparticles under ambient conditions is less than about 10%. In certain embodiments, the synthesized zero-valent iron nanoparticles have an average size of about 10 nanometers to about 100 nanometers.
The zero-valent metal and metal nanoparticles such as zero-valent iron and iron nanoparticles synthesized using the process described above may be used in purification systems such as for treating contaminated water. The zero-valent iron and iron nanoparticles are contacted with the contaminated water to remove contaminants from the water. Such zero-valent iron and iron nanoparticles synthesized from the laterite ore have enhanced adsorption potential that facilitates removal of contaminants from water.
Examples of contaminants include, but are not limited to, lead (Pb), arsenic (As), cadmium (Cd), chromium (Cr), nickel (Ni), tetrachloroethylene (PCE), tricholoroethylene (TCE), nitrates, phosphates, sulphides, perchlorate, chlorinated hydrocarbons, trinitrotoluene, halogenated organics, pesticides, organo-arsenicals, organo-mercurials, organic dyes, detergents, inorganic anions, or combinations thereof.
The core of the zero-valent iron and iron nanoparticles includes elemental iron that slowly oxidizes to ferrous iron and releases two electrons. The oxidation of elemental iron can be represented by the following equation:
Fe0(s)→Fe2*(aq)+2e−1(aq) (4)
These released electrons facilitate transformation of target contaminants in water. For example, several toxic contaminants such as tetrachloroethylene and trichloroethylene are reductively dechlorinated to an essentially non-toxic mixture of ethane, ethene, and acetylene. It should be noted that, laterite is a mixed valence of iron oxide and aluminum oxide. Aluminum oxide is largely insoluble under neutral pH conditions and may protect the zero-valent nanoparticles core from rapid oxidation. In particular, aluminum oxide facilitates disruption of inter-particle attractive forces and mechanical degradation of aggregates thereby resulting in slow particle agglomeration of the zero-valent nanoparticles. In addition, laterite is an effective adsorption material for removing arsenic, phosphate and other heavy metal contaminants from contaminated water and may also be used to remove odor (H2S) from contaminated water.
In certain example embodiments, the zero-valent iron nanoparticles synthesized using the process described above may be used as a reducing agent for sequestration of metal ions such as lead (Pb), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), mercury (Hg), nickel (Ni) and selenium (Se) having reduction potential greater than that of iron. The surface of the zero-valent iron nanoparticles is negatively charged that attracts the metal ions. The metal ions are adsorbed on the surface and are gradually reduced to zerovalent ions.
In some example embodiments, the zero-valent iron nanoparticles synthesized from laterite ore are used to adsorb odor such as from contaminated water. Here, alumina removed during laterite reduction may remove contaminants from water and may also remove bad odor from the contaminated water. In this application, alumina acts as a catalyst in the Clauss process for converting hydrogen sulfide waste gases into elemental sulfur. The chemical reactions for the odor removal process are represented by the following equations:
Fe+2+H2S→FeS+2H+ (5)
Fe2O3H2O+3H2S→Fe2S3+4H2O (6)
2Fe2S3+3O2+2H2O→Fe2O3H2O+6S (7)
After removing contaminants and/or odor from the water, iron nanoparticles may be recovered to restore the adsorption capacity of the exhausted adsorbent. The iron nanoparticles may be removed from treated water by precipitation followed by washing and removal of adsorbed heavy metals. These may further be reduced by a reducing agent followed by separation by magneto-separation process.
The present invention will be described below in further detail with examples and comparative examples thereof, but it is noted that the present invention is by no means intended to be limited to these examples.
Zero-valent iron nanoparticles were synthesized from laterite ore using the example method of
About 0.75 M of borohydride solution was added to the laterite ore solution in a dropwise manner while stirring vigorously at a speed of about 400 revolutions per minute (rpm) using a magnetic stirrer. A few more drops of the borohydride solution were added to the solution to reduce higher laterite concentrations. The process of reduction of the laterite ore was initiated immediately as the reducing agent was contacted with the ferric chloride solution.
As the reducing agent was contacted with the laterite ore solution, hydrogen was released by catalytic decomposition of the aqueous borohydride solution. This released hydrogen further reduced the laterite ore in presence of the zero-valent iron nanoparticles to form zero-valent iron and iron nanoparticles. This reduction of the laterite ore by the spill-over hydrogen continued for several days. The synthesis of the zero-valent iron and iron nanoparticles from the laterite ore was performed at a temperature of about 30° C.
As can be seen, a peak 1002 in the XRD pattern 1000 was observed indicating the presence of laterite in the solution. The peak 1002 was observed as the nanoparticles sample was obtained before completion of the reduction process by the spill-over hydrogen.
Rate of oxidation of zero-valent iron nanoparticle containing solutions was measured by a simple drop test method on filter paper. Here, about 1 ml of zero-valent iron nanoparticle containing solution was dispensed on a filter paper and time taken for a change in color of the filter paper under ambient conditions was noted. It was observed the laterite reduced zero-valent iron nanoparticles retained their black color even after about 60 days, whereas zero-valent iron nanoparticles synthesized from ferric chloride (FeCl3) solution alone oxidized within about 60 seconds. The zero-valent iron nanoparticles synthesized from laterite were observed to be about 1000 times more air stable than zero-valent iron nanoparticles synthesized from ferric chloride (FeCl3) solution alone.
The prepared samples were treated with zero-valent iron nanoparticles over a time period of 6 hours, 12 hours, 24 hours and 48 hours respectively and were tested for presence of lead in the samples using an atomic absorption spectrophotometer. The percentage removal of lead from the samples after 6 hours, 12 hours, 24 hours and 48 hours are represented by reference numerals 1402, 1404, 1406 and 1408.
Here, the results for zero-valent iron nanoparticles synthesized from FeCl3 solution (new and aged samples) are represented by reference numerals 1410 and 1412 respectively. Moreover, results for zero-valent iron nanoparticles synthesized from FeCl3 and laterite having a weight ratio of about 1:5 (new and aged samples) are represented by reference numerals 1414 and 1416 respectively. Results for zero-valent iron nanoparticles synthesized from FeCl3 and laterite having a weight ratio of about 1:10 (new and aged samples) are represented by reference numerals 1418 and 1420 respectively. Further, results for zero-valent iron nanoparticles synthesized from FeCl3 and laterite having a weight ratio of about 1:20 (new and aged samples) are represented by reference numerals 1422 and 1424 respectively. As can be seen, the zero-valent iron nanoparticles synthesized from laterite had enhanced adsorption potential.
The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims.
The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.
It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present.
For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations.
In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of“two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone. A and B together, A and C together, B and C together, and/or A, B, and C together, etc.).
It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”
As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub ranges and combinations of sub ranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc.
As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like include the number recited and refer to ranges which can be subsequently broken down into sub ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.
While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
Number | Date | Country | Kind |
---|---|---|---|
227/KOL/2013 | Feb 2013 | IN | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/IB2013/052975 | 4/15/2013 | WO | 00 |