CN110681387B - Ce-based amorphous alloy-based nanocomposite and preparation method thereof and application of nanocomposite in treatment of dye wastewater - Google Patents
Ce-based amorphous alloy-based nanocomposite and preparation method thereof and application of nanocomposite in treatment of dye wastewater Download PDFInfo
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 48
- 239000002351 wastewater Substances 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 230000015556 catabolic process Effects 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
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- 238000004062 sedimentation Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
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- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
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- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 28
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- 238000000926 separation method Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
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- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052961 molybdenite Inorganic materials 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a Ce-based amorphous alloy-based nanocomposite and a preparation method thereof and application of the Ce-based amorphous alloy-based nanocomposite in dye wastewater treatment. The nano composite material of the invention can be used in dark at normal temperature and normal pressure without adding any chemical (H)2O2PS/PMS or O3) And under the condition of energy, the method has high-efficiency removal rate on the dye wastewater.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a Ce-based amorphous alloy-based nano composite material, a preparation method thereof and application thereof in treating dye wastewater.
Background
Amorphous alloys, also known as Metallic Glass (MG), have been extensively studied in recent years for the catalytic degradation of azo dyes. For example: fe reported by the L.C.Zhang topic group78Si9B13And Fe73.5Si13.5B9Cu1Nb3The amorphous alloy is used as a light-enhanced Fenton catalyst, and shows excellent catalytic activity and recycling stability in the aspect of degrading azo dye wastewater; wan of the Balong Shen topic groupg Qianqian reported Fe80P13C7The high-efficiency decolorization rate of the amorphous alloy to methylene blue is superior to that of Fe78Si9B13(ii) a Jian Lv topic group research finds Fe83Si2B11P3C1The glass strip has outstanding efficiency and use stability when degrading RhB, MB, MO and mixtures thereof, and has strong catalytic performance after being recycled for 35 times. In addition, Co-based, Mg-based, Cu-based and Al-based amorphous alloy ribbons, powders and products obtained by treating the same have been demonstrated to exhibit relatively satisfactory catalytic degradation performance in the treatment of wastewater, the removal of synthetic dyes and the degradation of other organic pollutants such as phenol. At present, the application of cerium-based amorphous alloy and a product obtained by processing the same in the aspect of dye wastewater treatment is rarely reported. Recently, 15M H was used for Qiang Li2SO4For Ti30Cu70-xMox(x ═ 0,1,2, and 3 at.%) of the amorphous ribbon was dealloyed to yield CuS/MoS2The composite catalyst has excellent photocatalytic activity on the degradation of methyl blue. Wang Ning reported Cu74Ce26The amorphous band is used as a precursor, and a method combining combustion strip and calcination is adopted to prepare p-CuO/n-CeO2A heterojunction photocatalyst.
The above catalysts all require external input during the reaction, such as light, chemical additives (H)2O2PS/PMS or O3) Or energized, etc. A more promising technical solution for degrading organic pollutants in wastewater is to degrade the pollutants without any external input. Some mixed metal oxides or perovskite-containing metal oxides have been reported to degrade textile dyes in the dark without the addition of external actives and input of energy. For example: according to H.Chen, CaxSr1-x CuO 380% of orange II (50ppm) was degraded in 10min under dark conditions with a TOC removal of 30%. The CaSrNiCu oxide degraded 50% of OII in the first 5 minutes, degraded 95% in 2 hours, and the TOC removal rate reaches 54%. However, there are many problems to be investigated with respect to the thermal catalysis of the dark reaction, such as unclear reaction mechanism and TOC removalThe removal rate is generally low, and the like.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a nano composite material based on Ce-based amorphous alloy, a preparation method thereof and application thereof in treating dye wastewater, and aims to obtain a high-efficiency catalytic material capable of catalytically degrading organic pollutants under the dark reaction condition.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention firstly discloses a nano composite material based on Ce-based amorphous alloy, which is characterized in that: the nano composite material is obtained by processing Ce-based amorphous alloy serving as a raw material.
Further, the Ce-based amorphous alloy is CexMyCu(100-x-y)An amorphous alloy ribbon, wherein: x is more than or equal to 50, y is more than or equal to 0, 100-x-y is not equal to 0, and M is Al or Ga. CexMyCu(100-x-y)The amorphous alloy strip can be completely amorphous alloy and can also contain a small amount of nanocrystalline.
Further, after the treatment, Ce in the Ce-based amorphous alloy is completely converted into cerium-based oxide, and other metal elements in the Ce-based amorphous alloy are completely or partially converted into corresponding oxides. Therefore, the nano composite material comprises cerium-based oxide, and also comprises oxides of other metal elements in the Ce-based amorphous alloy and/or metal simple substances of other metal elements in the Ce-based amorphous alloy. Wherein the other metal element refers to the rest of the elements in the alloy except Ce.
Further, the treatment is to react the Ce-based amorphous alloy with dilute acid, then add alkali to settle to obtain turbid liquid, and then carry out hydrothermal treatment on the turbid liquid to obtain the nano composite material.
The invention also discloses a preparation method of the Ce-based amorphous alloy-based nanocomposite, which comprises the following steps:
(1) at room temperature, placing the Ce-based amorphous alloy strip in a container, adding dilute acid, and reacting until no bubbles emerge;
(2) under the condition of magnetic stirring, dropwise adding NaOH solution into the container until the reaction solution is alkaline to form suspension;
(3) transferring the suspension into a reaction kettle, and carrying out heat preservation reaction at 80-120 ℃ for 6-24 h; and after the reaction is finished, separating, washing and drying the obtained product to obtain the target product, namely the Ce-based amorphous alloy-based nanocomposite.
Further, in the step (1), the concentration of the dilute acid is greater than 0.5M, and the ratio of the mass of the Ce-based amorphous alloy strip to the volume of the dilute acid is 0.4g: 15-25 mL. Too low a concentration of dilute acid may result in the failure of Cu to convert to CuO, and too high a concentration may affect the degradation properties of the resulting composite. The dilute acid refers to dilute HCl and H2SO4Dilute HNO3And dilute strong acids, preferably dilute HCl is used.
Further, in the step (2), the pH value of the alkalinity is between 8.0 and 12.0, and preferably between 8.0 and 10.5.
Further, in the step (3), after adding water-soluble alcohol (such as methanol, ethanol or propanol) or surfactant into the suspension, hydrothermal reaction is carried out, so as to regulate the morphology of the obtained nano composite material.
Further, the condition of the hydrothermal reaction in the step (3) is preferably that the reaction is carried out at 100 ℃ for 8-16 h under heat preservation.
Further, in step (3): the separation is to separate the product by utilizing the separation mode commonly used in the current industrial production, such as solid-liquid separation, centrifugal separation, filtration or extraction, and the like, and the preferred mode is centrifugal separation; the washing is at least three times with at least one solvent, preferably water, alcohol or a mixture thereof; the drying is direct drying or vacuum drying, preferably vacuum drying.
The Ce-based amorphous alloy-based nanocomposite disclosed by the invention can be used as a catalyst for degrading organic pollutants, and can degrade organic azo dyes such as orange II, methyl orange and the like without adding external substances and energy. The nanocomposite material of the present invention can also be degraded in the presence of an external input, such as the application of light.
Compared with the prior art, the invention has the beneficial effects that:
1. the nanometer composite material consists of spherical nanometer particles with small particle size, has good dispersibility, mainly comprises cerium-based oxide and copper oxide, also comprises oxides of other metal elements in the Ce-based amorphous alloy and/or metal simple substances of other metal elements in the Ce-based amorphous alloy, has synergistic effect of all the components, can be used at the dark normal temperature and the normal pressure, and does not add any chemicals (H)2O2PS/PMS or O3) And the dye wastewater is degraded under the condition of energy, and the dye wastewater has high-efficiency decolorization rate.
2. The preparation method of the nano composite material has the characteristics of simple reaction method, easily controlled reaction conditions, low energy consumption and the like. The preparation method can control and adjust the composition of the composite material and the morphology structure of the product by controlling the conditions of sedimentation pH, hydrothermal time, hydrothermal temperature and the like.
Drawings
FIG. 1 shows Ce used in example 150Al10Cu40XRD patterns of amorphous alloy ribbon (MG) and nanocomposite (C1) obtained by processing the same.
FIG. 2 is an SEM photograph of the nanocomposite (C1) obtained in example 1.
FIG. 3 is a graph of degraded orange II of the nanocomposite (C1) of example 1 and comparative CC1 material.
FIG. 4 is a graph of the UV-VIS absorption spectra of C1 at various times during the degradation of orange II in example 1.
FIG. 5 is a graph of degradation of orange II from nanocomposites obtained under different sedimentation pH conditions in example 2.
FIG. 6 is a graph of the fitted reaction kinetics for degradation of orange II of the nanocomposite obtained under different sedimentation pH conditions in example 2.
FIG. 7 is a graph of orange II degradation curves of nanocomposites obtained with different amorphous alloy starting materials from example 3, and the inset is a TOC removal rate plot of each nanocomposite after 20min reaction with orange II.
Fig. 8 is a graph of the degradation of Methyl Orange (MO) by the nanocomposite (C1) of example 4, with inset uv-vis absorption spectra at different times during MO degradation.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1 based on Ce50Al10Cu40Amorphous alloy nanocomposite
This example uses Ce50Al10Cu40The preparation method of the nano composite material by using the amorphous alloy strip as a raw material comprises the following specific steps:
(1) at room temperature, about 0.4g of Ce was weighed50Al10Cu40Placing the amorphous alloy strip into a container, adding 20mL of dilute HCl (1M), and reacting until no bubbles emerge (black CuO is generated in the reaction in the step);
(2) under the condition of magnetic stirring at 200rpm, dropwise adding 1.5M NaOH solution into the container until the pH value is 8.5 to form suspension;
(3) transferring the suspension into a 50mL reaction kettle with a polytetrafluoroethylene lining, and carrying out heat preservation reaction at 100 ℃ for 12 hours; after the reaction is finished, naturally cooling to room temperature, centrifuging the obtained product at 15000rpm for 5min, respectively washing the obtained precipitate with water and alcohol for 4 times, and drying at 60 ℃ to obtain the nano composite material (marked as C1), wherein the nano composite material is ground before use.
FIG. 1 shows Ce used in this example50Al10Cu40XRD patterns of the amorphous alloy ribbon (MG) and of the nanocomposite (C1) obtained by treatment thereof, from which it can be seen: amorphous Ce50Al10Cu40The XRD of the alloy has a wide and scattered diffraction peak at 2 theta 15-45 degrees, which indicates that the structure is amorphous. The XRD spectrum of C1 shows that C1 contains CeO2、Cu、Cu2O、γ-Al2O3And CuO, these diffraction peaks can be assigned to CeO of cubic fluorite structure2(
JCPDS,75-0076), cubic phase Cu (
PDF#04-0836)、γ-Al2O3(PDF #47-1308), cubic phase Cu2O(
PDF #78-2076) and monoclinic CuO (a-4.685, b-3.426, m,
PDF#45-0937)。
FIG. 2 is an SEM image of the nanocomposite (C1) obtained in this example, and it can be seen that C1 is composed of many fine spherical nanoparticles, the size of which is several to ten and several nanometers, and the size is uniform. The XRD pattern of C1 showed a broader and lower intensity of crystalline peaks, indicating that the product was not highly crystalline and that the particle size formed may be smaller, which is consistent with SEM.
The nanocomposite (C1) obtained in this example was used to degrade 20ppm orange II while burning Ce directly50Al10Cu40For comparison, a sample obtained from MG (labeled CC1) was prepared as follows: under the conditions of no addition of any chemicals and no input of energy under normal temperature and pressure and darkness, 0.05g of catalyst is added into a 100mL beaker containing 50mL of 20ppm orange II, and the outside of the beaker is wrapped by tinfoil to simulate a dark environment. The reaction is carried out under magnetic stirring, the rotating speed is 600rpm, samples (2-3mL) are taken once when the reaction is carried out for 2 minutes, samples are taken once every 3 minutes after 2 minutes, the extracted suspension is filtered in a cuvette by a filter membrane of 0.45 mu m in time, then an Shimadzu UV-2600 type ultraviolet visible spectrometer is adopted to measure the absorbance and calculate the decolorization rate, and a TOC tester is adopted to measure and calculate the TOC removal rate.
In the formula: c0、A0The concentration of the orange II solution before the reaction and the absorbance at the maximum absorption wavelength, Ct、C0Is a reaction ofConcentration and absorbance of orange II solution after time.
In the formula: TOC0Total organic carbon content, TOC, of orange II solution prior to reactiontIs the total organic carbon content of the orange II solution after the reaction time t.
FIG. 3 is a graph of orange II degradation from C1 and CC1 materials, showing that: the CC1 has no degradation performance to the orange II basically under the dark reaction condition of normal temperature and pressure without adding any chemical. The degradation effect of C1 on orange II is particularly remarkable, the decolorization rate in the first 2 minutes is up to 87%, the decolorization rate in 20 minutes is 100%, and the removal rate of TOC after 20 minutes is about 79% (figure 7). Compared with the reported dark reaction thermal catalyst, the C1 has the characteristics of high decolorization speed and high TOC removal rate.
FIG. 4a is a graph of the UV-Vis absorption spectrum of C1 at various times during the degradation of orange II (FIG. 4b is an enlarged view of the dashed line in a), showing two absorption bands at 410nm and 484nm, corresponding to the two isomers of azo and hydrazone, respectively, of orange II in aqueous solution. Furthermore, the absorptions at 230nm and 310nm correspond to the benzene and naphthalene ring structures of the orange II molecule. The intensity of all bands of orange II in the first 2min is obviously reduced (the decolorization rate is 85-90 percent), and almost no absorption peak reappears after 20 min. It can be seen from the figure that the intensity of the absorption band at 410nm is obviously weak at 2 minutes, while a weak absorption band appears at 375nm, probably because by-products are generated, and a weak absorption peak still exists at 250nm after 8 minutes and up to 20 minutes, and an incompletely degraded aromatic ring possibly remains, so that after C1 adsorbs OII molecules to the surface, the-N-double bond can be firstly broken, small-molecule organic matters are generated in the middle, and then CO is finally generated under the oxidation of ROS (such as hydroxyl free radicals)2And H2O。
Example 2 comparison of nanocomposites obtained with different sedimentation pH
This example was carried out in the same manner as in example 1 using Ce50Al10Cu40The amorphous alloy strip is used as a raw material to prepare the nano composite material, and the differences are only that: in the step (2), NaOH solution is added to adjust the pH value to be different.
The nanocomposites obtained under different sedimentation pH conditions were used for the degradation of orange II in the same way as in example 1.
FIG. 5 is a graph of orange II degradation curves of nanocomposites obtained under different sedimentation pH conditions, and FIG. 6 is a graph of the reaction kinetics (ln (C) fitted thereto0/Ct) Kt) diagram. As can be seen from FIGS. 5 and 6, the change of the decolorization ratio and the reaction kinetic constant k is not obvious within the range of pH 8.0-10.5 (the decolorization ratio after 2 minutes has a good linear relationship with the reaction kinetic k, so that the data of only 2-18 minutes are fitted in the invention). The product obtained by settling the pH value of 8.0-10.5 can have a decolorization rate of over 90% after 5min, and the decolorization rate of orange II is obviously reduced along with the increase of the pH value, especially when the pH value is 12.0. The reason may be that under the sedimentation conditions of pH > 10, Ce (OH)4The cerium oxide content in the final product is reduced due to the reverse dissolution, which is not beneficial to the catalytic degradation.
Example 3 comparison of nanocomposites obtained with different amorphous alloy starting materials
This example prepares a nanocomposite in the same manner as in example 1, except that: the raw materials are respectively changed into Ce60Al10Cu30、Ce70Al10Cu20、Ce70Cu30Amorphous alloy ribbon, the respective resulting nanocomposites are labeled C2, C3, C4, respectively.
Each sample was used to degrade orange II in the same manner as in example 1. FIG. 7 is a graph of the degradation of orange II for each sample (including C1). It can be seen from the figure that C2 and C3 have little difference in decolorization speed compared with C1, but the treated Ce has no difference in decolorization speed70Cu30The rate of decolorization of product C4 obtained in MG on orange II was significantly lower than the first three, and the decolorization rate at 2min was only about 70%, probably because C4 contains no Al2O3Due to Al2O3The adsorption capacity of the catalyst to the dye molecules can be enhanced. In FIG. 7The inset is a graph of the TOC removal rate of 1g/L C1, C2, C3 after 20min reaction with 20ppm orange II.
Example 4 catalytic degradation of C1 on other dye wastewaters
In the same manner as in example 1, C1 was used to degrade a 20ppm solution of Methyl Orange (MO) in the presence of a catalyst in an amount of 1 g/L. Fig. 8 is a graph of C1 degradation MO and an ultraviolet-visible absorption spectrum (inset graph), from which it can be seen that the decoloring rate after 5min of adding the catalyst can reach more than 80%, and the decoloring rate after 20min can reach 100%, which indicates that C1 also has efficient degradation performance for MO.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A nanometer composite material based on Ce-based amorphous alloy is characterized in that: the nano composite material is obtained by processing Ce-based amorphous alloy serving as a raw material; the Ce-based amorphous alloy is CexMyCu(100-x-y)An amorphous alloy ribbon, wherein: x is more than or equal to 50, y is more than 0, 100-x-y is not equal to 0, and M is Al or Ga;
after treatment, the Ce in the Ce-based amorphous alloy is completely converted into cerium-based oxide, and other metal elements in the Ce-based amorphous alloy are completely or partially converted into corresponding oxides, so that the nanocomposite comprises the cerium-based oxide, oxides of other metal elements in the Ce-based amorphous alloy and/or metal simple substances of other metal elements in the Ce-based amorphous alloy;
the treatment is to react the Ce-based amorphous alloy with dilute acid, then add alkali for sedimentation to obtain turbid liquid, and then carry out hydrothermal treatment on the turbid liquid to obtain the nano composite material.
2. The method for preparing the Ce-based amorphous alloy-based nanocomposite material according to claim 1, comprising the following steps:
(1) at room temperature, placing the Ce-based amorphous alloy strip in a container, adding dilute acid, and reacting until no bubbles emerge;
(2) under the condition of magnetic stirring, dropwise adding NaOH solution into the container until the reaction solution is alkaline to form suspension;
(3) transferring the suspension into a reaction kettle, and carrying out heat preservation reaction at 80-120 ℃ for 6-24 h; and after the reaction is finished, separating, washing and drying the obtained product to obtain the target product, namely the Ce-based amorphous alloy-based nanocomposite.
3. The method of claim 2, wherein: in the step (1), the concentration of the dilute acid is more than 0.5M, and the ratio of the mass of the Ce-based amorphous alloy strip to the volume of the dilute acid is 0.4g: 15-25 mL.
4. The method of claim 2, wherein: in the step (2), the pH value of the alkalinity is between 8.0 and 12.0.
5. The method of claim 2, wherein: in the step (3), after water-soluble alcohol or surfactant is added into the suspension, hydrothermal reaction is carried out, and the morphology of the obtained nano composite material can be regulated and controlled.
6. Use of a nanocomposite material based on a Ce-based amorphous alloy according to claim 1, characterized in that: the catalyst is used for degrading organic pollutants, and can complete degradation under the condition of no external input.
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