Copper-iron bimetallic oxide / acetylene black composite material and preparation method and application thereof

Abstract

The invention relates to the field of wastewater treatment, in particular to a copper-iron bimetallic oxide / acetylene black composite material and a preparation method and application thereof. The composite material comprises acetylene black and a copper-iron bimetallic oxide loaded on the acetylene black, can activate PDS to degrade bisphenol A in wastewater, improves the activation efficiency of PDS, and reduces the degradation reaction time and the dosage of PDS and a catalyst.

Description

Technical Field

[0001] The present invention relates to the field of wastewater treatment, and in particular to a copper-iron bimetallic oxide / acetylene black composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Acetylene black (AB) is a type of carbon black. It is a carbon nanomaterial produced by the high-temperature cracking of high-purity acetylene. Macroscopically, AB appears as a fluffy black powder. Microscopically, AB is composed of stacked chain-like or spherical particles measuring 2 to 3 nm. AB is lightweight and has a low specific gravity (<1). It has a large specific surface area and strong adsorption capacity. AB contains π bonds, allowing for electron flow, resulting in high electrical conductivity. It also boasts high purity, stable chemical properties, and low price. In established traditional industries, AB is primarily used to produce electrode materials, batteries, fax paper, and coatings. However, there are relatively few reported cases of acetylene black being used in wastewater treatment.

[0003] Advanced oxidation technology based on potassium persulfate (PDS) is a hot topic in wastewater deep treatment at this stage. Compared with the traditional Fenton reaction technology, it has the following advantages: (1) SO · 4 - It has a redox potential relative to the standard hydrogen electrode (2.5-3.1V), which is higher than that of ·OH; (2) SO · 4 - Reactions with organic compounds containing unsaturated bonds or aromatic π electrons via electron transfer are more selective and efficient, while OH may react with various components at high reaction rates via hydrogen abstraction or electrophilic addition; (3) SO · 4 - As the main active substance, it can react efficiently with pollutants in a wide pH range of 2-8; (4) SO · 4 - The half-life of SO is 30-40μs, while the half-life of OH is only 1μs. · 4 - It has a more stable mass transfer process and can better contact with the target compound. · 4 - The conventional method is to use transition metal oxides for activation, but there are problems such as low activation efficiency and large amounts of catalyst and oxidant. Therefore, how to improve the efficiency of activating PDS and reduce the amount of catalyst added becomes the problem to be solved by the present invention. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a copper-iron bimetallic oxide / acetylene black composite material and its preparation method and application. The composite material can activate PDS to degrade bisphenol A in wastewater, improve the activation efficiency of PDS, and reduce the degradation reaction time and the dosage of PDS and catalyst.

[0005] In order to achieve the above object, the present invention provides a copper-iron bimetallic oxide / acetylene black composite material in a first aspect. The composite material comprises acetylene black and a copper-iron bimetallic oxide supported on the acetylene black.

[0006] Preferably, the mass ratio of the acetylene black, copper and iron is 1:0.24-0.64:0.1-0.42, more preferably 1:0.3-0.5:0.2-0.3.

[0007] Preferably, the average pore diameter of the composite material is 5 to 20 nm, more preferably 6 to 10 nm.

[0008] Preferably, the specific surface area of ​​the composite material is 40 to 100 m 2 / g, more preferably 50 to 70 m 2 / g.

[0009] A second aspect of the present invention provides a method for preparing the composite material, comprising: mixing iron salt, copper salt, acetylene black and deionized water, centrifuging, filtering and drying the mixture in sequence, and then calcining the mixture under an inert atmosphere.

[0010] Preferably, the preparation method comprises:

[0011] 1) mixing an iron salt, a copper salt and deionized water to obtain a bimetallic salt mixture;

[0012] 2) mixing acetylene black with deionized water and then performing ultrasonic treatment to obtain an acetylene black suspension;

[0013] 3) The double metal salt mixture obtained in step 1) is mixed with the acetylene black suspension obtained in step 2) and the mixture is centrifuged, filtered, dried, and then calcined under an inert atmosphere.

[0014] Preferably, in step 1), the iron salt is Fe(NO3)3·9H2O and / or FeSO4·7H2O.

[0015] Preferably, in step 1), the copper salt is Cu(NO)·3HO and / or CuSO4·5H2O.

[0016] Preferably, the concentration of iron ions in the double metal salt mixture is 1 to 10 mol / L, more preferably 5 to 6 mol / L.

[0017] Preferably, the concentration of copper ions in the double metal salt mixture is 2 to 20 mol / L, more preferably 10 to 12 mol / L.

[0018] Preferably, in step 2), the mass concentration of acetylene black in the acetylene black suspension is 5 to 20 g / L, more preferably 10 to 16 g / L.

[0019] Preferably, in step 3), the volume ratio of the bimetallic salt mixture to the acetylene black suspension is 1:1-10, more preferably 1:3-5.

[0020] Preferably, the calcination temperature is 400-1200°C, more preferably 600-900°C.

[0021] Preferably, the calcination time is 1 to 4 hours, more preferably 2 to 3 hours.

[0022] Preferably, the heating rate of the calcination is 2 to 10° C. / min, more preferably 6 to 8° C. / min.

[0023] A third aspect of the present invention provides use of the composite material in treating wastewater containing bisphenol A.

[0024] Preferably, the application comprises: mixing the wastewater, potassium persulfate and the composite material;

[0025] Preferably, the concentration of potassium persulfate in the wastewater is 0.3 to 1 mmol / L, more preferably 0.4 to 0.6 mmol / L.

[0026] Preferably, the concentration of the composite material in the wastewater is 0.25 to 1.25 g / L, more preferably 0.4 to 0.6 g / L.

[0027] Preferably, the pH value of the wastewater is 3 to 11, more preferably 7 to 8.5.

[0028] Preferably, the concentration of bisphenol A in the wastewater is 5 to 50 mg / L; more preferably, it is 10 to 20 mg / L.

[0029] Compared with the existing technology, this application has the following advantages:

[0030] 1) The present application uses acetylene black as a carrier and loads copper-iron bimetallic oxide to prepare a copper-iron bimetallic oxide / acetylene black composite material. When using this composite material to treat bisphenol A pollution, the potential difference between the two metal elements of copper and iron is used to adjust the electron cloud distribution of the catalyst. The carrier acetylene black effectively adsorbs potassium persulfate (PDS) and pollutants. At the same time, because acetylene black is rich in π bonds, it can promote electron transfer between metal oxides, PDS and pollutants, thereby improving the efficiency of activating PDS and promoting the degradation reaction of bisphenol A.

[0031] 2) Using the copper-iron bimetallic oxide / acetylene black composite material of the present application as a catalyst, PDS is activated to break the OO bond of the peroxydisulfate ion and generate sulfate radicals (SO · 4 - ) and then degrade bisphenol A in wastewater. The removal rate of bisphenol A can reach more than 80%, and for every 50 mg / L of bisphenol A degraded, only 0.5 g / L of composite material and 0.5 mM PDS are needed, and the removal time is less than or equal to 30 minutes, which greatly reduces the degradation reaction time and the dosage of PDS and catalyst.

[0032] 3) After the copper-iron bimetallic oxide / acetylene black composite material of the present application was recycled for 5 times, the removal rate of bisphenol A was still as high as over 75%. After each cycle, the copper mass loss was less than or equal to 2.5%, and the iron mass loss was less than or equal to 3.5%, showing good catalytic stability.

[0033] 4) The copper-iron bimetallic oxide / acetylene black composite material of the present application has a wide range of applications, and is particularly effective in treating wastewater with a pH value of 3 to 11 and a bisphenol A concentration of 5 to 50 mg / L. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a schematic diagram of the preparation process in Example 1 of the present invention.

[0035] Figure 2 This is the XRD pattern of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0036] Figure 3 BET diagram and pore size distribution diagram of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0037] Figure 4 This is an SEM image of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0038] Figure 5 TEM image and element distribution diagram of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0039] FIG6 (a) is an XPS spectrum of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention before and after the reaction.

[0040] FIG6( b ) is a high-resolution C1s spectrum of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention before and after the reaction.

[0041] FIG6( c ) is a high-resolution O1s spectrum of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention before and after the reaction.

[0042] FIG6( d ) is a high-resolution Cu 2p spectrum of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention before and after the reaction.

[0043] FIG6( e ) is a high-resolution spectrum of Fe 2p before and after the reaction of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0044] FIG7( a ) is a schematic diagram showing the cycle test results of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention.

[0045] FIG7( b ) is an XRD pattern of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention before and after the reaction.

[0046] FIG7( c ) is a schematic diagram of ion leaching concentration after each cycle of the copper-iron bimetallic oxide / acetylene black composite material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0047] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0048] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0049] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate relative importance or implicitly specify the quantity of the technical features indicated. Therefore, unless otherwise specified, a feature specified as "first" or "second" may explicitly or implicitly include one or more of such features; "plurality" means two or more. The term "comprising" and any variations thereof are intended to be non-exclusive inclusion, and one or more other features, integers, steps, operations, units, components, and / or combinations thereof may be present or added.

[0050] The copper-iron bimetallic oxide / acetylene black composite material of the present invention comprises acetylene black and a copper-iron bimetallic oxide supported on the acetylene black. The mass ratio of acetylene black, copper, and iron in the composite material is 1:0.24-0.64:0.1-0.42, preferably 1:0.3-0.5:0.2-0.3.

[0051] The composite material of the present invention has a porous spherical structure, copper-iron bimetallic oxides are dispersed on the spherical surface, and the average pore diameter of the composite material is 5-20 nm, preferably 6-10 nm.

[0052] Since the present invention uses acetylene black as a carrier to load copper-iron bimetallic oxide, a copper-iron bimetallic oxide / acetylene black composite material is prepared. The composite material also has an excellent specific surface area, specifically 40 to 100 m 2 / g, preferably 50 to 70 m 2 / g, has strong adsorption capacity.

[0053] The preparation method of the composite material of the invention comprises: mixing iron salt, copper salt, acetylene black and deionized water, centrifuging, filtering and drying in sequence, and then calcining under an inert atmosphere.

[0054] In order to obtain a better mixing effect, the preparation method of the present invention may further include:

[0055] 1) mixing an iron salt, a copper salt and deionized water to obtain a bimetallic salt mixture;

[0056] 2) mixing acetylene black with deionized water and then performing ultrasonic treatment to obtain an acetylene black suspension;

[0057] 3) The double metal salt mixture obtained in step 1) is mixed with the acetylene black suspension obtained in step 2) and the mixture is centrifuged, filtered, dried, and then calcined under an inert atmosphere.

[0058] In the above step 1), there are many options for the iron salt, which may be Fe(NO3)3·9H2O and / or FeSO4·7H2O. Similarly, the copper salt may be Cu(NO3)·3HO and / or CuSO4·5H2O.

[0059] The potential difference between the two metal elements of copper and iron in the present invention can adjust the electron cloud distribution of the catalyst. Therefore, in the bimetallic salt mixture, the concentration of iron ions is preferably 1 to 10 mol / L, more preferably 5 to 6 mol / L; the concentration of copper ions is 2 to 20 mol / L, preferably 10 to 12 mol / L.

[0060] In the above step 2), acetylene black is dispersed in deionized water by ultrasonic treatment. The mass concentration of acetylene black in the acetylene black suspension is 5 to 20 g / L, preferably 10 to 16 g / L.

[0061] In the above step 3), in order to achieve effective loading of copper-iron double oxide and activation performance of the composite material, the volume ratio of the double metal salt mixture to the acetylene black suspension is 1:1-10, preferably 1:3-5.

[0062] In order to ensure that the bimetallic salt mixture and the acetylene black suspension are fully mixed, the mixture can be placed in a heat-collecting constant temperature heating magnetic stirrer at room temperature and stirred for 6 to 28 hours, and then centrifuged, filtered and dried in sequence.

[0063] The calcination of the present invention can be carried out in a tubular furnace in an inert atmosphere at a temperature of 400 to 1200° C., preferably 600 to 900° C., for 1 to 4 hours, preferably 2 to 3 hours, and at a heating rate of 2 to 10° C. / min, preferably 6 to 8° C. / min. The inert atmosphere is provided by nitrogen.

[0064] The composite material of the present invention can be used to treat wastewater containing bisphenol A. The specific application includes: mixing the wastewater, potassium persulfate and the composite material. The composite material of the present invention is used as a catalyst to activate potassium persulfate to generate sulfate radicals (SO · 4 - ) and then degrade bisphenol A in wastewater.

[0065] In the present invention, in order to achieve effective removal of bisphenol A, the dosages of potassium persulfate and the composite material are preferably as follows: in the wastewater, the concentration of potassium persulfate is 0.3-1 mmol / L, preferably 0.4-0.6 mmol / L; in the wastewater, the concentration of the composite material is 0.25-1.25 g / L, preferably 0.4-0.6 g / L.

[0066] The composite material of the present invention has a wide range of applications and can be used to treat wastewater with a pH value of 3 to 11, preferably 7 to 8.5. It has a particularly good treatment effect on wastewater with a bisphenol A concentration of 5 to 50 mg / L, preferably 10 to 20 mg / L.

[0067] The copper-iron bimetallic oxide / acetylene black composite material of the present invention is further illustrated by the following examples. The examples are implemented based on the technical solution of the present invention and provide detailed implementation methods and specific operating processes, but the scope of protection of the present invention is not limited to the following examples.

[0068] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.

[0069] Example 1

[0070] according to Figure 1 The composite material was prepared by the following process:

[0071] 1) Dissolve 6 mmol of Fe(NO₃)₃·9H₂O and 12 mmol of Cu(NO₃)·3HO in 20 mL of deionized water to obtain a double metal salt mixture.

[0072] 2) 1.6 g of acetylene black was ultrasonically dispersed in 80 mL of deionized water to obtain an acetylene black suspension.

[0073] 3) The bimetallic salt mixture obtained in step 1) and the acetylene black suspension obtained in step 2) were mixed and stirred in a heat-collecting constant-temperature magnetic stirrer for 12 hours. The stirred solution was centrifuged, filtered, and dried, and then calcined in a nitrogen-filled tubular furnace at 800°C for 2 hours at a heating rate of 5°C / min to obtain a composite material.

[0074] The composite material obtained in Example 1 was characterized, and the results were as follows: Figure 2 -6 shown.

[0075] Depend on Figure 2 As can be seen, the acetylene black (AB) material exhibits a strong, single diffraction peak at 26.2°, corresponding to the (002) interface of graphitic carbon, indicating a high degree of graphitization of AB. The composite material of Example 1 of the present invention exhibits a faint peak at the same location, indicating that loading the copper-aluminum bimetallic oxide on the acetylene black weakens the graphitization of the acetylene black. No peaks attributable to copper or iron oxides are observed in the figure, indicating that the synthesized copper-aluminum bimetallic oxide is amorphous.

[0076] Depend on Figure 3 As can be seen, the composite material of the present invention exhibits low adsorption capacity at relatively low pressures and high adsorption capacity at relatively high pressures. Furthermore, the curves in the figure lack a clear hysteresis loop, indicating that the material has an asymmetric, slit-like pore structure. The composite material also has a narrow average pore size distribution, which facilitates PDS degradation of pollutants.

[0077] Depend on Figure 4 The composite material exhibits a porous spherical structure, with copper-iron bimetallic oxides loosely dispersed on the spherical surface and further agglomerated to form distinct particle chains. EDS analysis confirmed the successful loading of copper and iron on the acetylene black support, with the surface elemental composition comprising 90.31% C, 7.86% O, 1.18% Cu, and 0.65% Fe.

[0078] Depend on Figure 5 As can be seen in Figure (a), the (002) plane of acetylene black is observed, with a lattice spacing of d = 0.298 nm, corresponding to the (022) plane of CuO. The (113) plane of Fe2O3, with a lattice spacing of d = 0.2 nm, corresponds to the (002) plane of acetylene black, with a lattice spacing of d = 0.20 nm. This fully demonstrates the successful synthesis of two metal oxides, CuO and Fe2O3, on the acetylene black surface. The EDS results shown in Figure (b) also confirm the presence of C, O, Cu, and Fe in the composite material.

[0079] Example 2

[0080] The difference from Example 1 is that the amount of Cu(NO)·3HO used is 6 mmol.

[0081] Example 3

[0082] The difference from Example 1 is that the amount of Cu(NO)·3HO used is 3 mmol.

[0083] Example 4

[0084] The difference from Example 1 is that the calcination temperature is 600°C.

[0085] Example 5

[0086] The difference from Example 1 is that the calcination temperature is 900°C.

[0087] Example 6

[0088] The difference from Example 1 is that the amount of acetylene black used is 0.5 g.

[0089] Example 7

[0090] The difference from Example 1 is that the amount of Fe(NO3)3·9H2O used is 1 mmol.

[0091] Example 8

[0092] 1) Dissolve 20 mmol of Fe(NO₃)₃·9H₂O and 40 mmol of Cu(NO₃)·3HO in 20 mL of deionized water to obtain a double metal salt mixture.

[0093] 2) 0.1 g of acetylene black was ultrasonically dispersed in 20 mL of deionized water to obtain an acetylene black suspension.

[0094] 3) The bimetallic salt mixture obtained in step 1) and the acetylene black suspension obtained in step 2) were mixed and stirred in a heat-collecting constant-temperature magnetic stirrer for 12 hours. The stirred solution was centrifuged, filtered, and dried, and then calcined in a nitrogen-filled tubular furnace at 800°C for 2 hours at a heating rate of 5°C / min to obtain a composite material.

[0095] Example 9

[0096] 1) Dissolve 200 mmol of Fe(NO3)3·9H2O and 400 mmol of Cu(NO3)·3HO in 20 mL of deionized water to obtain a double metal salt mixture.

[0097] 2) 4 g of acetylene black was ultrasonically dispersed in 200 mL of deionized water to obtain an acetylene black suspension.

[0098] 3) The bimetallic salt mixture obtained in step 1) and the acetylene black suspension obtained in step 2) were mixed and stirred in a heat-collecting constant-temperature magnetic stirrer for 12 hours. The stirred solution was centrifuged, filtered, and dried, and then calcined in a nitrogen-filled tubular furnace at 800°C for 2 hours at a heating rate of 5°C / min to obtain a composite material.

[0099] Example 10

[0100] 1) Dissolve 100 mmol of Fe(NO₃)₃·9H₂O and 200 mmol of Cu(NO₃)·3HO in 20 mL of deionized water to obtain a double metal salt mixture.

[0101] 2) 0.8 g of acetylene black was ultrasonically dispersed in 80 mL of deionized water to obtain an acetylene black suspension.

[0102] 3) The bimetallic salt mixture obtained in step 1) and the acetylene black suspension obtained in step 2) were mixed and stirred in a heat-collecting constant-temperature magnetic stirrer for 12 hours. The stirred solution was centrifuged, filtered, and dried, and then calcined in a nitrogen-filled tubular furnace at 800°C for 2 hours at a heating rate of 5°C / min to obtain a composite material.

[0103] Comparative Example 1

[0104] The difference from Example 1 is that Cu(NO)·3HO is not added.

[0105] Comparative Example 2

[0106] The difference from Example 1 is that Fe(NO3)3·9H2O is not added.

[0107] Comparative Example 3

[0108] The difference from Example 1 is that acetylene black is replaced by silicon dioxide.

[0109] The composite materials obtained in Examples 1-7 and Comparative Examples 1-3 were used to treat bisphenol A-containing wastewater, and the results are shown in Table 1. The amounts of the composite materials and PDS used are the amounts of the composite materials and PDS added per liter of wastewater.

[0110] Table 1

[0111]

[0112]

[0113] As can be seen from Table 1 above, Examples 1-10 of the present application show that the removal rate of bisphenol A can reach more than 80% when the composite material of the present invention is used to treat bisphenol A-containing wastewater, and the amount of PDS and catalyst (i.e., the composite material of the present invention) used is small and the reaction time is short.

[0114] As shown in Example 1 and Comparative Examples 1-3, when using a copper or iron monometallic oxide / acetylene black composite material to treat bisphenol A in wastewater, not only do the PDS and catalyst usage levels exceed those of the copper-iron bimetallic oxide / acetylene black composite material used in this application, but the reaction time is also longer and the bisphenol A removal rate is lower. Furthermore, when using a copper-iron bimetallic oxide / silicon dioxide composite material to treat bisphenol A in wastewater, the PDS usage far exceeds that used in this application, resulting in material costs far exceeding those used in this application.

[0115] The composite material obtained in Example 1 was used to treat wastewater with different pH values ​​and bisphenol A concentrations. The results are shown in Table 2.

[0116] Table 2

[0117]

[0118] As can be seen from Table 2 above, the composite material of the present application has a wide range of applications. When treating wastewater with a pH of 3-11 and a bisphenol A concentration of 5-50 mg / L, the treatment effect is particularly good, and the bisphenol A removal rate can reach more than 80%.

[0119] Test example: Composite material stability test

[0120] The composite material prepared in Example 1 was subjected to 5 cycle tests, and the results are shown in Figures 6-7.

[0121] As shown in the XPS total spectrum of Figure 6(a), before the reaction, the proportions of C, O, Cu and Fe elements were 92.45%, 1.69%, 5.79% and 0.07%, respectively. After the reaction, the proportions were 92.81%, 3.61%, 3.50% and 0.08%, respectively. The changes in the proportions of the various elements were not obvious, which to some extent illustrates that the composite material of the present invention has good stability.

[0122] Figure 6(b) shows the C1s high-resolution spectrum of the composite material before and after the reaction. The peak position is at 284.79 eV, and the peak is the CC group. The peak area does not change significantly, which indicates that the CC bond is not consumed during the reaction. Figure 6(c) shows the O1s high-resolution spectrum of the composite material before and after the reaction. Two peaks were detected in the spectrum, namely the surface hydroxyl group (·OH) at 532.3 eV and the chemically adsorbed oxygen (O) at 533.5 eV. H ), the ratio of ·OH decreases before and after the reaction, which indicates that ·OH is consumed during the reaction. Figure 6(d) shows the Cu 2p high-resolution spectrum of the composite material before and after the reaction. At 932.44eV and 952.34eV, two peaks representing Cu + and Cu 0 and Cu 2+ , which accounted for 88.33% and 11.67% respectively. After the reaction, the proportions changed significantly. + and Cu 0 The proportion of Cu 2+ The ratio increased to 91.32%, which indicates that during the reaction, Cu + and Cu 0 Will be oxidized to Cu 2+ Due to the low content of Fe, its peak is not obvious (Figure 6(e)). Even though the proportions of Fe elements in different valence states changed before and after the reaction, the peak area of ​​Fe did not change much, which indicates that Fe can maintain a relatively stable state in the CF-AB+PDS system.

[0123] As shown in Figure 7(a), after five cycles of experiments, the removal rate of BPA is still greater than 75%, which shows the stability of the material.

[0124] As shown in Figure 7(b), the positions and intensities of the characteristic peaks of the composite material before and after PDS activation show no significant changes, indicating that the material's crystal structure is highly stable.

[0125] As shown in Figure 7(c), the average leaching concentration of Cu after each experiment is 1.626 mg / L, which is equivalent to a copper loss of 2.12%; the average leaching concentration of Fe is 1.033 mg / L, which is equivalent to an iron loss of 3.07%. This result also illustrates the stability of the copper-iron bimetallic oxide.

[0126] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A copper-iron bimetallic oxide / acetylene black composite material, characterized in that: The composite material comprises acetylene black and copper-iron bimetallic oxide supported on the acetylene black.

2. The composite material according to claim 1, characterized in that The mass ratio of the acetylene black, copper and iron is 1:0.24-0.64:0.1-0.42, preferably 1:0.3-0.5:0.2-0.

3.

3. The composite material according to claim 1 or 2, characterized in that The average pore size of the composite material is 5 to 20 nm, preferably 6 to 10 nm; and / or The specific surface area of ​​the composite material is 40 to 100 m 2 / g, preferably 50 to 70 m 2 / g.

4. The method for preparing the composite material according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: mixing iron salt, copper salt, acetylene black and deionized water, centrifuging, filtering and drying the mixture in sequence, and then calcining the mixture under an inert atmosphere.

5. The preparation method according to claim 4, characterized in that The preparation method comprises: 1) mixing an iron salt, a copper salt and deionized water to obtain a bimetallic salt mixture; 2) mixing acetylene black with deionized water and then performing ultrasonic treatment to obtain an acetylene black suspension; 3) The double metal salt mixture obtained in step 1) is mixed with the acetylene black suspension obtained in step 2) and the mixture is centrifuged, filtered, dried, and then calcined under an inert atmosphere.

6. The preparation method according to claim 5, characterized in that In step 1), The iron salt is Fe(NO3)3·9H2O and / or FeSO4·7H2O; and / or The copper salt is Cu(NO)·3HO and / or CuSO4·5H2O; and / or The concentration of iron ions in the double metal salt mixture is 1 to 10 mol / L, preferably 5 to 6 mol / L; and / or In the double metal salt mixed solution, the concentration of copper ions is 2 to 20 mol / L, preferably 10 to 12 mol / L.

7. The preparation method according to claim 5 or 6, characterized in that: In step 2), the mass concentration of acetylene black in the acetylene black suspension is 5 to 20 g / L, preferably 10 to 16 g / L.

8. The preparation method according to any one of claims 5 to 7, characterized in that In step 3), The volume ratio of the double metal salt mixture to the acetylene black suspension is 1:1 to 10, preferably 1:3 to 5; and / or The calcination temperature is 400-1200° C., preferably 600-900° C.; the calcination time is 1-4 hours, preferably 2-3 hours; and the heating rate is 2-10° C. / min, preferably 6-8° C. / min.

9. Use of the composite material according to any one of claims 1 to 3 in treating wastewater containing bisphenol A.

10. The use according to claim 9, characterized in that The application comprises: mixing wastewater, potassium persulfate and the composite material; Preferably, In the wastewater, the concentration of potassium persulfate is 0.3 to 1 mmol / L, preferably 0.4 to 0.6 mmol / L; and / or The concentration of the composite material in the wastewater is 0.25 to 1.25 g / L, preferably 0.4 to 0.6 g / L; and / or The pH value of the wastewater is 3 to 11, preferably 7 to 8.5; and / or The concentration of bisphenol A in wastewater is 5 to 50 mg / L, preferably 10 to 20 mg / L.

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