FENTON-LIKE CATALYST MATERIAL WITH ELECTRON-POOR Cu CENTER, AND PREPARATION METHOD AND USE THEREOF

Abstract

A Fenton-like catalyst material with an electron-poor Cu center and a preparation method and use thereof are provided. The preparation method includes: step 1: dissolving bismuth nitrate pentahydrate in a nitric acid solution and diluting a resulting solution with deionized water to obtain a solution A; step 2: adding citric acid to the solution A and adjusting a pH of a resulting solution with ammonia water to obtain a solution B; step 3: dissolving aluminium isopropoxide (AIP), copper chloride dihydrate, and glucose in the solution B to obtain a suspension C; step 4: stirring the suspension C at a high temperature to allow evaporation until a solid D is completely precipitated; and step 5: subjecting the solid D to calcination in a muffle furnace to obtain the Fenton-like catalyst material. Under neutral conditions, the catalyst material exhibits a prominent removal effect for various toxic organic pollutants, especially for phenolic pollutants.

Claims

1. A preparation method of a Fenton-like catalyst material with an electron-poor Cu center, comprising the following steps: step 1: dissolving bismuth nitrate pentahydrate in a nitric acid solution, and diluting a first resulting solution with deionized water to obtain a solution A; step 2: adding citric acid to the solution A, and adjusting a pH of a second resulting solution with ammonia water to obtain a solution B; step 3: dissolving aluminium isopropoxide (AIP), copper chloride dihydrate, and glucose in the solution B to obtain a suspension C; step 4: stirring the suspension C at a high temperature to allow evaporation until a solid D is completely precipitated; and step 5: subjecting the solid D to calcination in a muffle furnace to obtain the Fenton-like catalyst material with the electron-poor Cu center.

2. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein in step 1, the nitric acid solution has a concentration of 1 mol/L to 2 mol/L, and a ratio of the bismuth nitrate pentahydrate to the nitric acid solution is (0.32-3.28) g:5 mL.

3. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein a ratio of the citric acid to the bismuth nitrate pentahydrate is (0.3-0.9) g:(0.32-3.28) g.

4. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein in step 2, the pH of the second resulting solution is adjusted with the ammonia water to 5 to 9.

5. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein in step 3, the AIP, the copper chloride dihydrate, and the glucose are added in a ratio of (6.0-9.0) g:(0.1-0.8) g:(4.0-8.0) g.

6. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein in step 4, the high temperature is 100° C. and a rotational speed of the stirring is 100 r/min to 200 r/min.

7. The preparation method of the Fenton-like catalyst material with the electron-poor Cu center according to claim 1, wherein in step 5, the calcination in the muffle furnace is conducted at 400° C. to 600° C. for 3 h to 7 h with a heating rate of 5° C./min to 10° C./min.

8. A Fenton-like catalyst material with an electron-poor Cu center prepared by the preparation method according to claim 1, wherein the Fenton-like catalyst material with the electron-poor Cu center has a structural formula of (Bi,Cu)Al.sub.2O.sub.3, wherein a mass fraction of Cu is 3.0% to 9.0% and a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 is 5.4% to 50.4%.

9. A method of using the Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein the Fenton-like catalyst material with the electron-poor Cu center is provided in combination with H.sub.2O.sub.2 in water to degrade an organic pollutant.

10. The method of the use of the Fenton-like catalyst material with the electron-poor Cu center according to claim 9, wherein the organic pollutant is any one selected from the group consisting of rhodamine B, bisphenol A (BPA), and dichlorophenol (DCP).

11. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein in step 1, the nitric acid solution has a concentration of 1 mol/L to 2 mol/L, and a ratio of the bismuth nitrate pentahydrate to the nitric acid solution is (0.32-3.28) g:5 mL.

12. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein a ratio of the citric acid to the bismuth nitrate pentahydrate is (0.3-0.9) g:(0.32-3.28) g.

13. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein in step 2, the pH of the second resulting solution is adjusted with the ammonia water to 5 to 9.

14. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein in step 3, the AIP, the copper chloride dihydrate, and the glucose are added in a ratio of (6.0-9.0) g:(0.1-0.8) g:(4.0-8.0) g.

15. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein in step 4, the high temperature is 100° C. and a rotational speed of the stirring is 100 r/min to 200 r/min.

16. The Fenton-like catalyst material with the electron-poor Cu center according to claim 8, wherein in step 5, the calcination in the muffle furnace is conducted at 400° C. to 600° C. for 3 h to 7 h with a heating rate of 5° C./min to 10° C./min.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] FIG. 1 is a scanning electron microscopy (SEM) image of (Bi,Cu)Al.sub.2O.sub.3;

[0032] FIGS. 2A-2B are energy-dispersive X-ray spectroscopy (EDS) spectra illustrating the distribution of elements in (Bi,Cu)Al.sub.2O.sub.3;

[0033] FIGS. 3A-3B show transmission electron microscopy (TEM) images of (Bi,Cu)Al.sub.2O.sub.3;

[0034] FIGS. 4A-4B show the N.sub.2 adsorption and desorption isotherm and a pore size distribution curve of (Bi,Cu)Al.sub.2O.sub.3.

[0035] FIG. 5 shows an X-ray diffraction (XRD) pattern of (Bi,Cu)Al.sub.2O.sub.3;

[0036] FIGS. 6A-6C show X-ray photoelectron spectroscopy (XPS) spectra of Bi 4f, Cu 2p, and Al 2p orbits of (Bi,Cu)Al.sub.2O.sub.3;

[0037] FIG. 7 shows an electron-spin resonance (ESR) spectrum of Cu in (Bi,Cu)Al.sub.2O.sub.3;

[0038] FIG. 8 shows infrared (IR) spectra of (Bi,Cu)Al.sub.2O.sub.3 in the degradation of BPA at various stages;

[0039] FIG. 9A shows electron paramagnetic resonance (EPR) signals of HO.sub.2.Math./O.sub.2.Math.— in a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) capture suspension and FIG. 9B shows EPR signals of .Math.OH in a DMPO capture suspension;

[0040] FIG. 10 shows the degradation effects of (Bi,Cu)Al.sub.2O.sub.3 samples with different Bi.sub.12O.sub.15Cl.sub.6 contents for BPA with an initial concentration of 20 ppm;

[0041] FIG. 11 shows the degradation effects of (Bi,Cu)Al.sub.2O.sub.3 samples with different H.sub.2O.sub.2 contents for BPA;

[0042] FIGS. 12A-12B show in situ Raman spectra of (Bi,Cu)Al.sub.2O.sub.3 under different organic systems; and

[0043] FIG. 13 shows a mechanism of interaction between (Bi,Cu)Al.sub.2O.sub.3 and a hydrogen peroxide aqueous solution.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The present disclosure will be further described below in conjunction with specific examples.

Example 1

[0045] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0046] Step 1: 0.32 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M), and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0047] Step 2: 0.3 g of citric acid was dissolved in solution A obtained in step 1, a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0048] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate, and 7.2 g of glucose were added to the solution B obtained in step 2, and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0049] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0050] Step 5: the solid D obtained in step (4) was placed in a corundum crucible, and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 5.4%.

[0051] The catalyst material prepared above was characterized by SEM and EDS. It can be seen from FIG. 1 that the catalyst obtained through the improved evaporation-induced self-assembly reaction and calcination has a fluffy and porous cotton-like amorphous structure; which provides a large number of active sites for a catalytic reaction. It can be seen from FIGS. 2A-2B that Cu, C, Bi, O, Cl, and Al elements are uniformly distributed in the bulk phase, indicating that the incorporated Cu and the generated Bi.sub.12O.sub.15Cl.sub.6 are well distributed in a structure of the matrix material Al.sub.2O.sub.3.

[0052] The 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium. Then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and then 1 mL of a reaction solution was collected every 5 minutes filtered through a 0.45 μm filter membrane, and subjected to high-performance liquid chromatography (HPLC) analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

Example 2

[0053] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0054] Step 1: 0.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0055] Step 2: 0.3 g of citric acid was dissolved in solution A obtained in step 1, a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0056] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate, and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0057] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0058] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 10.3%.

[0059] The catalyst material obtained above was characterized by TEM. It can be seen from FIGS. 3A-3B that Bi.sub.12O.sub.15Cl.sub.6 nanoparticles adhere to a surface of γ-Cu—Al.sub.2O.sub.3 to form a heterogeneous structure. Notably, the high-resolution transmission electron microscopy (HRTEM) images clearly show that copper is completely embedded into the γ-Al.sub.2O.sub.3 lattice. Lattice fringes with an interplanar crystal spacing of 0.21 nm correspond to the (111) plane of Cu, and a cloud-like structure without lattice fringes is γ-Al.sub.2O.sub.3 of an amorphous structure.

[0060] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium; and then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and then 1 mL of a reaction solution was collected every 5 minutes, filtered through a 0.45 m filter membrane, and subjected to HPLC analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

Example 3

[0061] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0062] Step 1: 1.28 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M), and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0063] Step 2: 0.3 g of citric acid was dissolved in solution A obtained in step 1, a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0064] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2. A resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0065] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0066] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 29.6%.

[0067] The catalyst material prepared above was subjected to N.sub.2 adsorption and desorption isotherm and pore size distribution tests. It can be seen from FIGS. 4A-4B that the N.sub.2 absorption/desorption isotherm of (Bi, Cu)Al.sub.2O.sub.3 is an IV isotherm with an H3 hysteresis curve, indicating a slit-like mesoporous structure. The first hysteresis loop at a relative pressure P/PO of 0.4 to 0.8 indicates that there are mainly mesopores in the synthesized sample and the second small hysteresis loop at a relative pressure P/PO of 0.8 to 1.0 indicates that there are a small number of large mesopores in the catalyst. It can be seen from the pore size distribution curve that mesopore sizes of the cotton-like (Bi, Cu)Al.sub.2O.sub.3 are mainly distributed at about 7.1 nm, and according to nitrogen adsorption and desorption isotherm calculation, the (Bi, Cu)Al.sub.2O.sub.3 has an SSA of 240 m.sup.2/g and a pore volume of 0.454 cm.sup.3/g.

[0068] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium. Then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and then 1 mL of a reaction solution was collected every 5 minutes; filtered through a 0.45 m filter membrane and subjected to HPLC analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

Example 4

[0069] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0070] Step 1: 2 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M), and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0071] Step 2: 0.3 g of citric acid was dissolved in solution A obtained in step 1, a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0072] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0073] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0074] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 30.3%.

[0075] The catalyst material prepared above was subjected to an XRD test. It can be seen from FIG. 5 that a diffraction peak corresponding to copper cannot be observed in the XRD pattern of (Bi, Cu)Al.sub.2O.sub.3. However, new peaks appear in the XRD pattern of the catalyst doped with Bi.sub.12O.sub.15Cl.sub.6, most of which correspond to Bi.sub.12O.sub.15Cl.sub.6. The strongest diffraction peak at 20 of 30.12° is attributed to the (413) plane of Bi.sub.12O.sub.15Cl.sub.6, indicating that the (413) plane is a preferred orientation for the formation of a crystal plane of the crystal.

[0076] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium; and then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added. Then 1 mL of a reaction solution was collected every 5 minutes, filtered through a 0.45 m filter membrane, and subjected to HPLC analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

Example 5

[0077] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0078] Step 1: 2.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0079] Step 2: 0.3 g of citric acid was dissolved in solution A obtained in step 1, a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0080] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0081] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0082] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 42.1%.

[0083] The catalyst material prepared above was characterized by XPS. It can be seen from FIGS. 6A-6C that the two binding energies (BEs) of Al.sup.3+ at 74.2 eV and 75.3 eV in the spectrum of (Bi, Cu)Al.sub.2O.sub.3 correspond to Al—O—Al and Al—O—Cu, respectively. In addition, an XPS spectrum of Cu in 0.64 CAB was determined. The three peaks 932.7 eV, 934.0 eV, and 942.4 eV obtained after fitting correspond to a reduced state, an oxidized state and a wave peak of copper, respectively. After Bi.sub.12O.sub.15Cl.sub.6 is doped into γ-Cu—Al.sub.2O.sub.3, Bi has two characteristic peaks of Bi 4f.sub.7/2 (158.3 eV) and Bi 4f.sub.5/2 (163.7 eV). In addition, oxygen vacancies (OVs) can be formed during the calcination of BiOCl, and with the generation of low-charge Bi ions (Bi.sup.(3-x)+) [28,29], local electrons on OVs are transferred to Bi.sup.3+. Therefore, new peaks with low binding energies (157.3 eV, 162.7 eV) will appear in the spectrum of Bi.sub.12O.sub.15Cl.sub.6.

[0084] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium. Then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and 1 mL of a reaction solution was collected every 5 minutes, filtered through a 0.45 μm filter membrane, and subjected to HPLC analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

[0085] It can be seen from FIG. 10 that the Fenton-like catalyst in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 is 9% has an excellent degradation effect for BPA under neutral pH conditions, and a removal rate within 30 minutes reaches 95% or more.

Example 6

[0086] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0087] Step 1: 3.28 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0088] Step 2: 0.3 g of citric acid was dissolved in the solution A obtained in step 1 a resulting solution was stirred at a rate of 100 r/min and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0089] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate, and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0090] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0091] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 50.4%.

[0092] The catalyst material prepared above was subjected to solid EPR characterization. It can be seen from FIG. 7 that the solid EPR of Cu shows a strong signal accompanied by an ultra-fine coupling structure, which is a typical feature of Cu (II) with the spin I=3/2. The g factor and the A value of the Bi Cu Al.sub.2O.sub.3 sample were shown in the table below:

TABLE-US-00001 Sample g// g⊥ A//(G) (Bi, Cu)Al.sub.2O.sub.3 2.403 2.130 130

[0093] g∥>g⊥>2.0023 (ge), indicating that the unpaired electrons present on the surface of the catalyst are located on the dx2-y2 orbit of Cu (II). A value range of the g factor and the shape of the EPR signal of (Bi, Cu)Al.sub.2O.sub.3 correspond to a form of Cu (II) present in the hexacoordinated octahedral geometry. The above results show that, due to a difference in electronegativity between Bi and Cu, the eutectic lattice doping of Cu in Al.sub.2O.sub.3 and the loading of Bi.sub.12O.sub.15Cl.sub.6 cause non-uniform distribution of electrons on the surface of the catalyst; and because the electronegativity of Bi is higher than that of Cu, a density of electron cloud around Cu is weakened to produce an electron-poor Cu center, which correspondingly leads to an electron-rich Bi center.

Example 7

[0094] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0095] Step 1: 0.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0096] Step 2: 0.6 g of citric acid was dissolved in solution A obtained in step 1 a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0097] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0098] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0099] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 10.3%.

[0100] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium. Then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and then 1 mL of a reaction solution was collected every 5 minutes, filtered through a 0.45 m filter membrane, and subjected to HPLC analysis to obtain BPA concentrations at different reaction time points. Test results were shown in FIG. 10.

[0101] Fourier transform-infrared spectroscopy (FTIR) spectra of (Bi, Cu)Al.sub.2O.sub.3 at different reaction time points were determined to analyze a surface reaction process of the catalyst (FIG. 8). The two absorption bands of the freshly-prepared (Bi, Cu)Al.sub.2O.sub.3 at 3,500.9 cm.sup.−1 and 1,643 cm.sup.−1 correspond to a stretching vibration of OH and a mixed vibration of H—O—H, respectively. Characteristic peaks of —OH and —CH.sub.3 of BPA appear at 3,339.7 cm.sup.−1 and 2,970 cm.sup.−1, respectively. The peaks at 1,446.8 cm.sup.−1, 1,510 cm.sup.−1, and 1,610 cm.sup.−1 are attributed to a skeletal vibration of an aromatic ring of BPA; and the characteristic peaks in a range from 1,177 cm.sup.−1 to 1,238 cm.sup.−1 indicate a C—O stretching vibration of phenolic hydroxyl. After BPA is adsorbed, the phenolic hydroxyl of BPA forms a first coordination phase with Cu (II). Due to a difference between a deprotonation environment of phenolic hydroxyl of BPA and a surrounding environment, the characteristic peak of —OH shifts from 3,339.7 cm.sup.−1 to 3,423 cm.sup.−1. In addition, some characteristic peaks of BPA also appear in the spectrum of (Bi, Cu)Al.sub.2O.sub.3 after adsorption. With the extension of reaction time, the characteristic peaks of the aromatic ring of BPA (1,446.8 cm.sup.−1, 1,510 cm.sup.−1, and 1,610 cm.sup.−1) gradually disappear. After 12 h of reaction, the characteristic peaks of all organic matters disappear, and the v(OH) band of (Bi, Cu)Al.sub.2O.sub.3 (0.64 CAB) shifts back to 3,500.3 cm.sup.−1, indicating the complete mineralization of BPA and an intermediate thereof.

Example 8

[0102] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0103] Step 1: 0.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0104] Step 2: 0.9 g of citric acid was dissolved in solution A obtained in step 1 a resulting solution was stirred at a rate of 100 r/min, and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0105] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0106] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0107] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 600° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 10.3%.

[0108] To further elucidate a catalysis mechanism, DMPO-captured EPR signals were detected in different dispersions of a corresponding sample (FIGS. 9A-9B). In the absence of H.sub.2O.sub.2, no signal was detected in a methanol dispersion of pure Al.sub.2O.sub.3 and Bi.sub.12O.sub.15Cl.sub.6. However, intensities of the six characteristic peaks of DMPO—O.sub.2.Math..sup.− are as follows: γ-Cu—Al.sub.2O.sub.3>(Bi, Cu)Al.sub.2O.sub.3. Other peaks correspond to carbon-centered radicals produced by a reaction between DMPO and O.sub.2.Math..sup.−. These peaks overlap with the characteristic peaks of DMPO—O.sub.2.Math..sup.−, and thus can hardly be identified in the EPR spectrum. The reaction between the electron-rich center and O.sub.2 can produce O.sub.2.Math..sup.−. Therefore, in the methanol dispersion system of (Bi, Cu)Al.sub.2O.sub.3, Bi.sub.12O.sub.15Cl.sub.6 can be used as an electron-rich center to reduce O.sub.2 into O.sub.2.Math..sup.−. Since the electron-poor Cu center oxidizes H.sub.2O into .Math.OH, the characteristic peak of DMPO—OH.Math. is observed in the γ-Cu—Al.sub.2O.sub.3 aqueous solution and the (Bi, Cu)Al.sub.2O.sub.3 aqueous solution, and the intensity of the characteristic peak is as follows: (Bi, Cu)Al.sub.2O.sub.3>γ-Cu—Al.sub.2O.sub.3. In addition, OH attacks the carbon-containing compound (DMPO) to form a carbon-centered radical adduct [45], and six other peaks appear.

Example 9

[0109] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0110] Step 1: 0.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0111] Step 2: 0.6 g of citric acid was dissolved in solution A obtained in step 1 a resulting solution was stirred at a rate of 100 r/min and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0112] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0113] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0114] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 550° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 10.3%.

Example 10

[0115] In this example, a preparation method of a Fenton-like catalyst material with an electron-poor Cu center was provided, including the following steps: [0116] Step 1: 0.64 g of bismuth nitrate pentahydrate was dissolved in 5 mL of a nitric acid solution (2 M) and a resulting solution was diluted with deionized water to 100 mL to obtain a solution A; [0117] Step 2: 0.6 g of citric acid was dissolved in solution A obtained in step 1 a resulting solution was stirred at a rate of 100 r/min and a pH was adjusted with ammonia water to 6.5 to obtain a solution B; [0118] Step 3: 8.4 g of AIP, 0.4 g of copper chloride dihydrate and 7.2 g of glucose were added to the solution B obtained in step 2 and a resulting mixture was stirred at a rate of 100 r/min for 12 h to obtain a solution C; [0119] Step 4: the solution C obtained in step 3 was placed in an electrothermal furnace and then heated and stirred at 100° C. until the water was completely evaporated to obtain a solid D; and [0120] Step 5: the solid D obtained in step 4 was placed in a corundum crucible and then heated at a heating rate of 5° C./min to 650° C. and kept at the temperature for 6 h in a muffle furnace for calcination to obtain the Fenton-like catalyst material with an electron-poor Cu center in which a mass fraction of Bi.sub.12O.sub.15Cl.sub.6 was 10.3%.

[0121] A 20 mg/L BPA solution was prepared in a 150 mL Erlenmeyer flask, 0.1 g of the catalyst material obtained in step 5 was added to the Erlenmeyer flask, and a resulting mixture was stirred in a constant-temperature water bath at 35° C. for 30 minutes to achieve an adsorption equilibrium. Then 0.1 mL of a hydrogen peroxide solution with a mass fraction of 30% was added and 1 mL of a reaction solution was collected every 5 minutes, filtered through a 0.45 μm filter membrane, and subjected to IPLC analysis to obtain BPA concentrations at different reaction time points. It can be seen from FIG. 11 that the Fenton-like catalyst can rapidly degrade BPA at a hydrogen peroxide concentration of 8 mmol/L under neutral pH conditions, and a removal rate within 30 minutes reaches 95% or more.

[0122] An experimental principle is as follows: Unlike the traditional catalyst with an electron-rich copper center, as shown in FIG. 13, in the [(Bi, Cu)Al.sub.2O.sub.3+H.sub.2O.sub.2+ phenolic compound] system, the electron-poor copper center is conducive to the formation of σ-Cu-ligand with a phenolic compound. Such σ-Cu-ligand were preferentially oxidized by H.sub.2O.sub.2 with the generation of .Math.OH and HO-adduct radicals, and the HO-adduct radicals reduced Cu(II) to Cu(I) subsequently. Therefore, σ-Cu-ligand can not only prevent Cu (II) from oxidizing H.sub.2O.sub.2 into HO.sub.2.Math./O.sub.2.Math..sup.−, but also enhance the oxidation-reduction cycle of Cu (II)/Cu (I). Notably, although the σ-Cu-ligand is gradually decreased over time due to the degradation of the phenolic compound, the dual-reaction center can still play an important role in the subsequent catalysis reaction. The electron-rich Bi center can reduce H.sub.2O.sub.2 into .Math.OH to degrade an organic matter. Therefore, during the degradation of a phenolic compound, three electron transfer routes can produce .Math.OH: (1) A first transfer route is from σ-Cu-ligand to H.sub.2O.sub.2, which is accompanied by the generation of .Math.OH and the reduction of Cu (II) into Cu (I). (2) A second transfer route is from Cu (I) to H.sub.2O.sub.2, which is accompanied by the generation of .Math.OH. (3) A third transfer route refers to the transfer from the electron-rich Bi center to H.sub.2O.sub.2 with the generation of OH. Due to the synergistic effect between the σ-Cu-ligand and the dual-reaction center, (Bi, Cu)Al.sub.2O.sub.3 has high catalytic activity and hydrogen peroxide utilization (i).