CN109202099B - Preparation method and application of high-dispersion ultra-small zero-valent iron nano-cluster - Google Patents
Preparation method and application of high-dispersion ultra-small zero-valent iron nano-cluster Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000006185 dispersion Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
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- -1 aromatic halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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Abstract
The invention discloses a preparation method and application of a high-dispersion ultra-small zero-valent iron nano cluster, and belongs to the technical field of preparation of environment nano materials and treatment of organic pollutants. The technical scheme provided by the invention has the key points that: firstly, encapsulating Fe in CTAB micelle serving as surfactant3+And then release S by controlling thiourea under alkaline conditions2‑Forming FeS nano-cluster as intermediate, then making the FeS nano-cluster pass through NaBH4Reducing to obtain the high-dispersion zero-valent iron nanocluster with the particle size less than 1 nm. The invention also discloses the application of the zero-valent iron nanocluster as a catalyst in NaBH4In the presence of a catalyst to reduce organic reactions. The preparation process of the zero-valent iron nanocluster has mild conditions, is simple and convenient to operate and easy to realize, and the prepared zero-valent iron nanocluster has very obvious catalytic reduction performance on p-nitrophenol in water and can be used in NaBH4The catalyst can be repeatedly recycled in the presence of the catalyst and can maintain higher catalytic activity.
Description
Technical Field
The invention belongs to the technical field of preparation of environment nano materials and treatment of organic pollutants, and particularly relates to a preparation method and application of a high-dispersion ultra-small zero-valent iron nano cluster.
Background
In recent years, nanometer zero-valent iron is widely concerned by researchers due to the advantages of high reduction activity, environmental protection, low economic cost and the like, and nanometer zero-valent iron particles are often applied to wastewater treatment and groundwater remediation. A large number of researches show that the nano zero-valent iron is an effective water treatment material and can be used for removing various pollutants, such as nitrite, selenate, antibiotics, aromatic halides and heavy metal pollutants. However, like other nanomaterials, the nano zero-valent iron particles are not only aggregated into larger-sized particles driven by strong magnetic and van der waals forces, but also easily oxidized in air, and these disadvantages result in drastic reduction in activity, durability, and efficiency. In order to solve these problems, various literature reports have proposed to prepare stable and dispersed nano zero-valent iron particles (particle size 20 to 100 nm) by various methods, such as: surface active agent, polyelectrolyte or natural biological polymer is used for coating and modifying the nano zero-valent iron or loading the nano zero-valent iron particles on an inorganic or organic carrier. Common coating and loading materials comprise carboxymethyl cellulose, polyacrylic acid/polyvinylidene fluoride, starch, copolymer, bentonite, carbon nano tubes, covalent organic polymer, boron nitride, magnesium hydroxide, silicon dioxide and the like, and all the modification materials can inhibit aggregation of nano zero-valent iron particles so as to improve the removal performance of the nano zero-valent iron particles on pollutants. However, various modifying materials reported at present cannot control the crystal growth of nano zero-valent iron to prepare ultra-small metal nanoclusters. The reactivity and catalytic ability of the ultrafine metal nanoclusters are greatly improved compared with those of ordinary nanoscale particles, and highly dispersed noble metal nanoparticles with the particle size of less than 1nm, such as palladium and gold, have been prepared, however, as the nanoscale zero-valent iron particles have strong van der waals force and magnetic attraction, the synthesis of the zero-valent iron nanoclusters with extremely small particle size, and simultaneously the maintenance of the surface activity and the avoidance of agglomeration is a challenging problem. In addition, the nano zero-valent iron particles are easily oxidized after removing contaminants even in an oxygen deficient environment, which makes the recovery and recycling of nano zero-valent iron very difficult.
So far, no relevant report about the preparation and application of the zero-valent iron nanocluster is found in the mastered data through search.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of the high-dispersion ultra-small zero-valent iron nano-cluster, which has mild condition, simple and convenient operation and easy realization, the method utilizes micelle to assist in preparing the ultra-small-particle-size zero-valent iron nano-cluster for the first time under the mild condition, and the prepared zero-valent iron nano-cluster is highly dispersed and has the particle size less than 1 nm.
The invention solves another technical problem by providing the zero-valent iron nano cluster prepared by the method as a catalyst in sodium borohydride (NaBH)4) The application of catalytic reduction of p-nitrophenol in the presence of p-aminophenol is to prepare p-aminophenol, the zero-valent iron nano cluster has very obvious catalytic reduction performance on p-nitrophenol in water body, and can be used in NaBH4The catalyst can be repeatedly recycled in the presence of the catalyst and can maintain higher catalytic activity.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the high-dispersion ultra-small zero-valent iron nano cluster is characterized by comprising the following specific processes: firstly, encapsulating Fe in CTAB micelle serving as surfactant3+And then release S by controlling thiourea under alkaline conditions2-Forming FeS nano-cluster as intermediate, then making the FeS nano-cluster pass through NaBH4Reducing to obtain the high-dispersion zero-valent iron nanocluster with the particle size less than 1 nm.
The preparation method of the high-dispersion ultra-small zero-valent iron nano cluster is characterized by comprising the following specific steps of:
step S1: adding a surfactant CTAB into deionized water and stirring to form a micelle solution, and adding FeCl3·6H2Dissolving O in hydrochloric acid solution to form Fe3+Mixing the solution with hydrochloric acid, and adding Fe3+Dripping hydrochloric acid mixed solution into the micellar solution to obtainTo mixed solution A;
step S2: adding thiourea into deionized water, stirring to form a thiourea solution, dissolving sodium hydroxide into the deionized water to form a sodium hydroxide solution, dropwise adding the sodium hydroxide solution into the thiourea solution, and stirring and mixing uniformly to obtain a mixed solution B;
step S3: dropwise adding the mixed solution B into the mixed solution A, stirring and mixing uniformly to obtain a mixed solution C, and adding NaBH4Adding the mixture into the mixed solution C to react to prepare the high-dispersion zero-valent iron nanocluster with the particle size less than 1 nm.
Preferably, the concentration of the surfactant CTAB in the micellar solution in the step S1 is greater than the critical micelle concentration by 0.9mmol/L, and the surfactant CTAB and FeCl are3·6H2The molar ratio of O is 5-20: 1.
Preferably, the molar ratio of the sodium hydroxide to the thiourea in the step S2 is 1-10: 1.
Preferably, the thiourea in the mixture B and the FeCl in the mixture a in step S33·6H2The molar ratio of O is 1-6: 1.
Preferably, the NaBH is performed in step S34With FeCl3·6H2The molar ratio of O is 5-50: 1.
The high-dispersion ultra-small zero-valent iron nano cluster is used as a catalyst in NaBH4In the presence of a catalyst to reduce organic reactions.
The invention relates to application of a high-dispersion ultra-small zero-valent iron nano cluster in treatment of wastewater containing p-nitrophenol.
The high-dispersion ultra-small zero-valent iron nano cluster is used as a catalyst in NaBH4Use of catalytic reduction of p-nitrophenol in the presence of p-aminophenol, wherein the conversion of p-nitrophenol into p-aminophenol can be carried out within 60s, with a corresponding reaction activity coefficient of up to 68.3s-1g-1And the zero-valent iron nano cluster is repeatedly recycled.
Compared with the prior art, the invention has the following beneficial effects: the preparation process of the zero-valent iron nanocluster has mild conditions, is simple and convenient to operate and easy to realize, and the prepared zero-valent iron nanoclusterThe iron nano-cluster is cheap and easy to obtain, and can replace a noble metal catalyst to be applied to catalytic reduction organic reactions. Due to the unique structure and surprisingly ultra small particle size of the zero-valent iron nanoclusters (<1nm), the zero-valent iron nano cluster shows very high catalytic reduction performance, the reaction of converting p-nitrophenol into p-aminophenol can be completed within 60s, and the corresponding reaction activity coefficient is as high as 68.3s-1g-1. Meanwhile, in a circulation test, the zero-valent iron nano cluster shows good circulation stability and high catalytic activity, and the reduction activity and the reusability of the zero-valent iron nano cluster can be comparable with those of the currently widely used noble metal catalyst.
Drawings
FIG. 1 is a transmission electron micrograph of a zero-valent iron nanocluster prepared in example 1;
FIG. 2 is a histogram of the particle size distribution of the zero-valent iron nanoclusters prepared in example 1 (obtained by counting the particle sizes of 100 particles by statistical software);
FIG. 3 shows the zero-valent iron nanoclusters and pure NaBH prepared in example 14Curve of removal effect of p-nitrophenol in water at 20 ℃, zero-valent iron nanoclusters, p-nitrophenol and NaBH4The initial reaction concentrations of (1) were 0.44mM, 0.14mM and 3.2mM, respectively, and the stirring rate was 180 rpm.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: adding CTAB (10 mmol) serving as a surfactant into deionized water, stirring for 30 minutes to form a micelle solution (the concentration of the micelle solution is more than 0.9mmol/L of critical micelle concentration), and adding FeCl3·6H2O (1 mmol) dissolved in hydrochloric acid solution to form Fe3 +Mixing the solution with hydrochloric acid, and adding Fe3+Dripping the hydrochloric acid mixed solution into the micellar solution to obtain a mixed solution A;
step S2: adding thiourea (1 mmol) into deionized water, stirring for 30 minutes to form thiourea solution, dissolving sodium hydroxide (5 mmol) into the deionized water to form sodium hydroxide solution, dropwise adding the sodium hydroxide solution into the thiourea solution, and stirring and mixing uniformly to obtain mixed solution B;
step S3: dropwise adding the mixed solution B into the mixed solution A, stirring and mixing uniformly to obtain a mixed solution C, and adding NaBH4(25 mmol) is added into the mixed solution C to react to prepare zero-valent iron nano-cluster suspension.
As can be seen from FIGS. 1 and 2, the average particle diameter of the zero-valent iron nanoclusters is 0.8nm, and each nanocluster is surrounded by a layer of gray substances (the thickness is less than 1nm), because the nanoclusters are wound and coated by the carbon hydrocarbon chains of CTAB, and the nanoclusters are difficult to be aggregated into large particles through the winding and coating of the carbon hydrocarbon chains, so that the nanoclusters have good dispersibility.
Example 2
In order to evaluate the reactivity of the synthesized zero-valent iron nano-cluster, the zero-valent iron nano-cluster is used for removing p-nitrophenol in a solution by catalytic reduction, and the method comprises the following specific steps:
step S1: 40mL of the prepared zero-valent iron nanocluster suspension (0.46 mM) and 0.005g of NaBH were added into a 50mL conical flask4And 1.4mL of p-nitrophenol (4 mM), the solution being magnetically stirred at 20 ℃;
step S2: stirring for 1min, filtering 1.4mL of reaction solution, and scanning and analyzing by using an ultraviolet-visible spectrophotometer;
step S3: 0.005g of NaBH was added before the next cycle experiment4Then 1.4mL of p-nitrophenol aqueous solution (4 mM), NaBH4And the concentration of p-nitrophenol remains constant at the beginning of each cycle. In the same NaBH4At concentration, the same zero-valent iron nanoclusters were reacted cyclically 8 times.
The results are shown in FIG. 3. The results show that pure NaBH in the absence of zero-valent iron nanoclusters4P-nitrophenol can not be reduced in the reaction process, which is consistent with the research result reported in the literature. However, under the action of 0.44mmol/L zero-valent iron nanocluster,the color of the suspension immediately changed from yellow to colorless, indicating complete reduction of the p-nitrophenol. UV-Vis spectral analysis showed a rapid decrease in the peak intensity of p-nitrophenol at 400nm and a new peak at 296nm indicating the formation of p-aminophenol. Due to the ultra-small particle size of the zero-valent iron nanoclusters (<1nm), the zero-valent iron nanoclusters exhibit surprising reactivity towards the reduction of p-nitrophenol. In NaBH4In the presence of the catalyst, the zero-valent iron nano cluster can completely catalyze and reduce p-nitrophenol into p-aminophenol within 60 s.
The reaction kinetics research in the zero-valent iron nano cluster activity test shows that the kinetics rate constant k of the reaction is 0.0683s-1. Coefficient of reaction activity KaIs 68.3s-1g-1The reaction activity coefficient is far higher than that of most noble metal catalysts reported in the literature at present, and in addition, NaBH used for catalytic reduction reaction in the research4The molar ratio to p-nitrophenol (23: 1) is lower than in most noble metal catalyst catalyzed reactions. In addition, in the presence of the zero-valent iron nanocluster, the reaction for reducing p-nitrophenol into p-aminophenol can be completed in only 60 s.
The cyclic experiment research shows that no reduction activity is reduced in 8 cyclic reaction cycles, and the removal rate is 100% in 60s reaction cycle. These results can be generalized to the design of low cost, environmentally friendly, highly active and stable nanoclustered metal particles to degrade environmental pollutants.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (9)
1. A method for preparing high-dispersion ultra-small zero-valent iron nano-cluster is characterized in thatThe process is as follows: firstly, encapsulating Fe in CTAB micelle serving as surfactant3+And then release S by controlling thiourea under alkaline conditions2-Forming FeS nano-cluster as intermediate, then making the FeS nano-cluster pass through NaBH4Reducing to obtain the high-dispersion zero-valent iron nanocluster with the particle size less than 1 nm.
2. The method for preparing highly dispersed ultra-small zero-valent iron nanoclusters according to claim 1, comprising the following steps:
step S1: adding a surfactant CTAB into deionized water and stirring to form a micelle solution, and adding FeCl3·6H2Dissolving O in hydrochloric acid solution to form Fe3+Mixing the solution with hydrochloric acid, and adding Fe3+Dripping the hydrochloric acid mixed solution into the micellar solution to obtain a mixed solution A;
step S2: adding thiourea into deionized water, stirring to form a thiourea solution, dissolving sodium hydroxide into the deionized water to form a sodium hydroxide solution, dropwise adding the sodium hydroxide solution into the thiourea solution, and stirring and mixing uniformly to obtain a mixed solution B;
step S3: dropwise adding the mixed solution B into the mixed solution A, stirring and mixing uniformly to obtain a mixed solution C, and adding NaBH4Adding the mixture into the mixed solution C to react to prepare the high-dispersion zero-valent iron nanocluster with the particle size less than 1 nm.
3. The method of preparing highly dispersed ultra small zero valent iron nanoclusters of claim 2, wherein: in the step S1, the concentration of the surfactant CTAB in the micelle solution is greater than the critical micelle concentration by 0.9mmol/L, and the surfactants CTAB and FeCl3·6H2The molar ratio of O is 5-20: 1.
4. The method of preparing highly dispersed ultra small zero valent iron nanoclusters of claim 2, wherein: in the step S2, the molar ratio of the sodium hydroxide to the thiourea is 1-10: 1.
5. The highly dispersed ultra-small zero-valent iron sodium of claim 2The preparation method of the rice clusters is characterized by comprising the following steps: in step S3, thiourea in the mixed solution B and FeCl in the mixed solution A3·6H2The molar ratio of O is 1-6: 1.
6. The method of preparing highly dispersed ultra small zero valent iron nanoclusters of claim 2, wherein: the NaBH in step S34With FeCl3·6H2The molar ratio of O is 5-50: 1.
7. The method of any one of claims 1-6, wherein the highly dispersed ultra-small zero-valent iron nanoclusters prepared by the method are used as catalysts in NaBH4In the presence of a catalyst to reduce organic reactions.
8. Use of highly dispersed ultra-small zero-valent iron nanoclusters prepared according to the method of any one of claims 1 to 6 for treating wastewater containing p-nitrophenol.
9. The method of any one of claims 1-6, wherein the highly dispersed ultra-small zero-valent iron nanoclusters prepared by the method are used as catalysts in NaBH4Use of catalytic reduction of p-nitrophenol in the presence of p-aminophenol, wherein the conversion of p-nitrophenol into p-aminophenol can be carried out within 60s, with a corresponding reaction activity coefficient of up to 68.3s-1g-1And the zero-valent iron nano cluster is repeatedly recycled.
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