WO2022062801A1 - 一种具有缺电子Cu中心的类芬顿催化材料及其制备方法和应用 - Google Patents

一种具有缺电子Cu中心的类芬顿催化材料及其制备方法和应用 Download PDF

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WO2022062801A1
WO2022062801A1 PCT/CN2021/114262 CN2021114262W WO2022062801A1 WO 2022062801 A1 WO2022062801 A1 WO 2022062801A1 CN 2021114262 W CN2021114262 W CN 2021114262W WO 2022062801 A1 WO2022062801 A1 WO 2022062801A1
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solution
fenton
catalytic material
electron
deficient
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French (fr)
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王津南
谢志群
陈利芳
周嘉丽
吕治平
李爱民
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Nanhuan Yancheng Environmental Protection Technology Co Ltd
NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
Nanjing Tech University
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Nanhuan Yancheng Environmental Protection Technology Co Ltd
NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
Nanjing Tech University
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Priority to US18/028,229 priority Critical patent/US20230372910A1/en
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Definitions

  • the invention belongs to the field of materials, and relates to a Fenton-like catalytic material, in particular to a Fenton-like catalytic material with an electron-deficient Cu center, and a preparation method and application thereof.
  • Traditional Fenton oxidation includes homogeneous Fenton method and heterogeneous Fenton method, in which homogeneous Fenton is degraded by the reaction of Fe 2+ with H 2 O 2 to generate hydroxyl radicals (HO ) with super oxidizing ability Process of contaminants in water.
  • the traditional Fenton technology has many defects, such as strict acidic conditions (pH ⁇ 3), the production of iron sludge during the reaction process, and the extremely low utilization rate of the oxidant, which greatly limit the traditional Fenton method in practical wastewater treatment. application.
  • heterogeneous Fenton catalysis has attracted widespread attention.
  • the invention with the application number of 20110856060.7 discloses an electro-Fenton water treatment method based on iron-containing clay minerals supported palladium catalysts.
  • iron-integrated catalysts are obtained by loading iron-containing clay minerals into iron-containing clay minerals through reduction reactions, and palladium-iron is integrated.
  • the catalyst is added to the electro-Fenton water treatment device to catalyze the generation of free radicals, thereby degrading the organic pollutants in the water.
  • the catalyst can remove 92% of 0.5mmol/L sodium benzoate within 60 minutes.
  • the device needs a stable DC power supply and consumes a lot of electricity.
  • the use of precious metals makes the preparation cost of the catalyst extremely high, and the traditional Fenton-like electron transfer mechanism will inevitably cause serious loss of precious metals. These defects severely limit the application of this catalyst in practical wastewater treatment.
  • the invention with application number 201611147885.3 discloses a preparation method of an iron-copper bimetal supported mesoporous silicon heterogeneous Fenton catalyst material.
  • the mesoporous silicon-supported iron-copper composite metal oxide catalyst material prepared by this method has a pore size distribution Wide, large specific surface area, metal distribution is relatively uniform.
  • a large amount of oxidants and catalysts need to be added.
  • the degradation rate of 62.3% was obtained after adding 0.15M H 2 O 2 and 2 g/L catalyst to the dye wastewater to be degraded for 300 min.
  • Such catalytic efficiency will consume a large amount of oxidant, resulting in high treatment costs.
  • the treatment effect is not significant.
  • Application No. 201510939912.X discloses a preparation method of an iron-copper-aluminum oxide composite catalyst.
  • the invention obtains a good nano-layer by modifying the mesoporous material 1, continues to support the bimetallic component and after that, the active group The fractions continue to remain highly dispersed nanolayers.
  • the whole Fenton reaction process takes a long time to effectively remove the pollutants, and the whole reaction still follows the mechanism of the classical Fenton reaction.
  • this catalyst still relies on the redox reaction of a single metal site to realize the activation of hydrogen peroxide, and the utilization rate of hydrogen peroxide in the system is still very low.
  • the application number CN201811311154.7 discloses a preparation method of a Fenton-like catalytic material with dual-reaction active centers.
  • the catalytic material presents a complete spherical mesoporous structure with a large specific surface area, which can expose more catalytic active sites, so that H 2 O 2 can be reduced as much as possible in the electron-rich center during the reaction process to generate free hydroxyl groups.
  • the new catalytic material has a good removal effect on various toxic organic pollutants under neutral conditions, and can achieve high selective conversion of H 2 O 2 .
  • the salinity of this catalytic material is very low when it catalyzes the degradation of phenolic substances, and the catalytic effect is not good when it is used to degrade macromolecular substances such as dyes.
  • Cu(II) in ⁇ -Cu(II) complexes can be reduced to Cu(I) by oxidizing HO-addition radicals to hydroxylation products, which not only prevents Cu(II) from oxidizing H2O2 to HO2 . /O 2 ⁇ - , and also promotes the redox cycle of Cu(II)/Cu(I)[2].
  • ⁇ -Cu-ligand interaction plays an important role in the selective degradation of phenolic compounds and the efficient utilization of H2O2.
  • the construction of traditional electron-rich Cu center Fenton-like catalysts will hinder the interaction between phenolic substances and surface Cu, which limits the ⁇ -Cu-ligand effect;
  • a sufficiently strong polarization difference can realize the dual-reaction active center mechanism, so appropriate metals or metal oxides should be selected for loading or doping;
  • Cu is doped in the lattice of the catalyst.
  • the heteroform plays an important role in the establishment of double-reactive active centers, and how to improve and enhance the lattice doping of Cu is a difficult problem.
  • the present invention provides a Fenton-like catalytic material with electron-deficient Cu center, a preparation method and application thereof, so as to overcome the defects of the prior art.
  • the present invention provides a preparation method of a Fenton-like catalytic material with an electron-deficient Cu center, which has the characteristics of comprising the following steps:
  • Step 1 dissolve bismuth nitrate pentahydrate in nitric acid solution, and use deionized water to dilute the solution to form solution A;
  • Step 2 adding citric acid to solution A, and adjusting the solution with ammonia water to form solution B;
  • Step 3 aluminum isopropoxide, cupric chloride dihydrate and glucose are dissolved in solution B to form suspension C;
  • Step 4 the suspension liquid C is stirred and evaporated at high temperature until the solid is completely separated out to form the solid D;
  • Step 5 Put the solid D into a muffle furnace and calcine to obtain the Fenton-like catalytic material.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein, in step 1, the concentration of the nitric acid solution is 1mol/L-2mol/L, The ratio of the bismuth nitrate pentahydrate to the nitric acid solution is 0.32-3.28g:5mL.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein the addition ratio of the citric acid to the bismuth nitrate pentahydrate is 0.3-0.9 g : 0.32-3.28g.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein, in step 2, the pH of the solution is adjusted to 5-9 by ammonia water.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which can also have the following characteristics: wherein, in step 3, the aluminum isopropoxide, the copper chloride dihydrate and the glucose are prepared The ratio of the addition amount is 6.0-9.0g:0.1-0.8g:4.0-8.0g.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein, in step 4, the high temperature temperature is 100°C, and the stirring speed is 100-200r/min.
  • the present invention provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein, in step 5, the calcination temperature of the muffle furnace is 400-600° C., and the calcination time is 3 -7h, the heating rate during calcination is 5-10°C/min.
  • the Fenton-like catalytic material with electron-deficient Cu center prepared by the above preparation method is also within the protection scope of the present invention, and the catalytic material as a whole exhibits a fluffy cotton-like porous morphology.
  • the synthesized Fenton-like catalyst mainly has mesoporous structure, and the pore size distribution is about 7.1 nm;
  • the structural formula of the catalytic material is (Bi,Cu)Al 2 O 3 , in which the mass fraction of Cu is 3.0-9.0%, and the mass fraction of Bi 12 O 15 Cl 6 is 5.4-50.4%;
  • the catalytic material can achieve catalytic degradation of phenolic pollutants due to the formation of electron-deficient Cu centers. Synergy of double-reactive active centers with ⁇ -Cu-ligand.
  • the present invention also provides the application of the above-mentioned Fenton-like catalytic material with electron-deficient Cu center, which has the characteristics that the Fenton-like catalytic material is combined with H 2 O 2 in water to treat and degrade organic pollutants.
  • the present invention provides an application of a Fenton-like catalytic material having an electron-deficient Cu center, which may also have the following characteristics: wherein the organic pollutant is any one of Rhodamine B, bisphenol A and dichlorophenol. A sort of.
  • the invention discloses an electron-deficient Cu center-like Fenton-like catalytic material and a preparation method thereof. Based on the doping of two catalysts, ⁇ -Cu-Al 2 O 3 and Bi 12 O 15 Cl 6 , self-assembly is induced by improved evaporation.
  • the one-step reaction is to synthesize ⁇ -Cu-Al 2 O 3 and support Bi 12 O 15 Cl 6 , using the strongly electronegative Bi and the catalyst to form an electron-deficient Cu center.
  • the electron-deficient copper centers are favorable for the formation of ⁇ -Cu-ligand interactions with phenolic compounds.
  • Such ⁇ -Cu-ligand can be oxidized by H 2 O 2 to generate HO-addition radicals to generate OH, and simultaneously reduce Cu(II) in Cu(II) complexes to form OH by HO-addition radicals Cu(I). It is worth noting that although the ⁇ -Cu-ligand effect gradually weakened due to the reduction of phenolic compounds with the prolongation of reaction time, the double reaction center then played a dominant role in the catalytic reaction. Through the degradation of simulated bisphenol A and dichlorophenol wastewater experiments, it is shown that the new ⁇ -Cu-Al 2 O 3 -Bi 12 O 15 Cl 6 has extremely high Fenton catalytic effect and stability.
  • the prepared Fenton-like catalytic material has a fluffy and porous structure and a large specific surface area, which can expose more effective active sites.
  • the prepared catalytic material can exhibit good catalytic activity and stability against organic pollutants such as bisphenol A (BPA), rhodamine B and dichlorophenol under neutral conditions.
  • organic pollutants such as bisphenol A (BPA), rhodamine B and dichlorophenol under neutral conditions.
  • Fig. 1 is the scanning electron microscope image of (Bi,Cu)Al 2 O 3 ;
  • Fig. 2 is the EDS spectrum of each element distribution in (Bi,Cu)Al 2 O 3 ;
  • Figure 3 is a transmission electron microscope image of (Bi,Cu)Al 2 O 3 ;
  • Figure 4 is the N 2 adsorption and desorption curve and pore size distribution map of (Bi,Cu)Al 2 O 3 ;
  • Fig. 5 is the X-ray diffraction pattern of (Bi, Cu)Al 2 O 3 ;
  • Figure 6 is the XPS spectrum of Bi 4f, Cu 2p and Al 2p orbitals of (Bi,Cu)Al 2 O 3 ;
  • Fig. 7 is the electron spin resonance spectrum of Cu element in (Bi,Cu)Al 2 O 3 ;
  • Fig. 8 is the infrared spectrum of each stage of (Bi,Cu)Al 2 O 3 degradation of bisphenol A;
  • A is the EPR signal diagram of HO 2 ⁇ /O 2 ⁇ - in the DMPO capture suspension
  • B is the EPR signal diagram of ⁇ OH in the DMPO capture suspension
  • Figure 10 is a graph showing the degradation effect of (Bi,Cu)Al 2 O 3 with different contents of Bi 12 O 15 Cl 6 on bisphenol A with an initial concentration of 20 ppm;
  • Figure 11 is a graph showing the effect of (Bi,Cu)Al 2 O 3 on the degradation of bisphenol A with different H 2 O 2 contents;
  • Figure 12 is the in-situ Raman spectrum of (Bi,Cu)Al 2 O 3 in different organic systems
  • Figure 13 is a schematic diagram of the mechanism of the interaction between (Bi,Cu)Al 2 O 3 and aqueous hydrogen peroxide.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 5.4%.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 10.3%.
  • the above-prepared catalytic materials were characterized by transmission electron microscopy, and it can be seen from Figure 3 that the Bi 12 O 15 Cl 6 nanoparticles adhered to the surface of ⁇ -Cu-Al 2 O 3 to form a heterostructure.
  • the HRTEM images clearly show that the copper is fully embedded in the ⁇ - Al2O3 lattice.
  • the lattice fringes with the interplanar spacing of 0.21 nm correspond to the (111) plane of Cu, and the cloud-like structure without lattice fringes is ⁇ -Al 2 O 3 of amorphous structure.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 29.6%.
  • N2 adsorption/desorption curve and pore size distribution of the prepared catalytic materials were tested. From Figure 4, it can be seen that the N2 adsorption/desorption isotherm of ( Bi,Cu) Al2O3 is the IV with the H3 hysteresis curve.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 30.3%.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 42.1%.
  • Bi 12 O 15 Cl 6 When Bi 12 O 15 Cl 6 is doped into ⁇ -Cu-Al 2 O 3 , Bi has two characteristic peaks Bi 4f 7/2 (158.3eV) and Bi 4f 5/2 (163.7eV)).
  • oxygen vacancies (OVs) can be formed during the calcination of BiOCl, and with the generation of low-charge Bi ions (Bi (3-x)+ ) [28, 29], the localized electrons on OVs are transferred to Bi 3 + . Therefore, new peaks (157.3 eV, 162.7 eV) with lower binding energies appear in the spectrum of Bi 12 O 15 Cl 6 .
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 50.4%.
  • the g-factor and A values of the (Bi,Cu)Al 2 O 3 samples are shown in the table below:
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 10.3%.
  • the FT-IR spectra of (Bi,Cu)Al 2 O 3 with different reaction times were used to analyze the surface reaction process of the catalysts (Fig. 8).
  • the two absorption bands at 3500.9 and 1643 cm ⁇ 1 of the freshly prepared (Bi,Cu)Al 2 O 3 correspond to the stretching vibration of OH and the mixed vibration of HOH, respectively.
  • the characteristic peaks of -OH and -CH3 of BPA appeared at 3339.7 and 2970 cm -1 , respectively.
  • the peaks at 1446.8, 1510 and 1610 cm -1 are attributed to the skeletal vibrations of the aromatic ring of bisphenol A, while the characteristic peaks in the range of 1177 to 1238 cm -1 represent the CO stretching vibrations of the phenolic hydroxyl groups.
  • the phenolic hydroxyl group of BPA forms the first coordination phase with Cu(II). Due to the deprotonation of the phenolic hydroxyl group of bisphenol A and the difference in the surrounding environment, the characteristic peak of –OH shifts from 3339.7 cm -1 to 3423 cm -1 . In addition, some characteristic peaks also appeared in the (Bi,Cu)Al 2 O 3 spectrum of BPA after adsorption. With the prolongation of the reaction time, the characteristic peaks (1446.8, 1510 and 1610 cm -1 ) of the aromatic ring of BPA gradually disappeared.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 600°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 10.3%.
  • DMPO-captured EPR signals were detected in different dispersions of the corresponding samples ( Figure 9).
  • No signal was detected in methanol dispersions of pure Al2O3 and Bi12O15Cl6 in the absence of H2O2 .
  • the intensities of the six characteristic peaks of DMPO-O2 ⁇ - are ⁇ -Cu-Al 2 O 3 >(Bi,Cu)Al 2 O 3 .
  • the other peaks correspond to the carbon-centered radicals produced by the reaction of DMPO and O2 ⁇ - . Since these peaks overlap with the characteristic peaks of DMPO-O2 ⁇ - , it is difficult to identify them from the EPR spectrum.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 550°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu center class Fenton catalytic material, wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 10.3%.
  • the present embodiment provides a preparation method of a Fenton-like catalytic material having an electron-deficient Cu center, comprising the following steps:
  • step (3) the obtained solution C obtained in step (3) is placed on the electric heating furnace with heating and stirring at 100 ° C until the moisture is completely evaporated to dryness to obtain solid D;
  • step (4) Put the solid D obtained in step (4) into a corundum crucible, and in a muffle furnace at a heating rate of 5°C/min, the temperature is raised to 650°C for calcination and then kept for 6 hours to obtain the electron-deficient Cu centers.
  • Fenton catalytic material wherein the mass fraction of Bi 12 O 15 Cl 6 in the system is 10.3%.
  • the experimental principle is: different from the traditional electron-rich copper center catalyst, as shown in Fig. 13, in the [(Bi,Cu)Al2O3 + H2O2 + phenolic compound] system, the electron-deficient copper center is beneficial to the interaction with phenolic compounds.
  • Compounds form ⁇ -Cu-ligand interactions.
  • Such ⁇ -Cu-ligand is preferentially oxidized by H 2 O 2 to generate OH and HO-adduct radicals, which subsequently reduce Cu(II) to Cu(I). Therefore, ⁇ -Cu-ligand not only prevents Cu(II) from oxidizing H 2 O 2 to HO 2 ⁇ /O 2 ⁇ - , but also enhances the Cu(II)/Cu(I) redox cycle.
  • the electron-rich Bi center can reduce H 2 O 2 to OH, degrading organic matter. Therefore, there are three electron transfer routes to generate OH during the degradation of phenolic compounds: (1) The first transfer route is from ⁇ -Cu-ligand to H 2 O 2 , accompanied by the generation of OH and Cu (II) reduction to Cu(I); (2) the second transfer route is from Cu(I) to H 2 O 2 with the formation of ⁇ OH; (3) the third transfer route with ⁇ OH The generation of , transfers from the electron-rich Bi center to H 2 O 2 . Due to the synergistic effect of ⁇ -Cu-ligand and dual reaction centers, (Bi,Cu)Al 2 O 3 obtained high catalytic activity and hydrogen peroxide utilization ( ⁇ ).

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Abstract

本发明公开了一种有缺电子Cu中心的类芬顿催化材料及其制备方法和应用，制备方法包括如下步骤：步骤一、将五水合硝酸铋溶解于硝酸溶液中，并使用去离子水将溶液稀释形成溶液A；步骤二、将柠檬酸加入到溶液A中，并用氨水调节溶液形成溶液B；步骤三、将异丙醇铝、二水合氯化铜和葡萄糖溶解于溶液B中形成悬浊液C；步骤四、将悬浊液C在高温下搅拌蒸发至固体完全析出形成固体D；步骤五、将固体D放入马弗炉中煅烧后得到所述类芬顿催化材料。该催化材料在中性条件下对各类毒害有机污染物都具有很好的去除效果尤其是酚类污染物，并且能够实现对H 2O 2的高选择性转化。

Description

一种具有缺电子Cu中心的类芬顿催化材料及其制备方法和应用 技术领域
本发明属于材料领域，涉及一种类芬顿催化材料，尤其涉及一种具有缺电子Cu中心的类芬顿催化材料及其制备方法和应用。
背景技术
传统芬顿氧化包括均相芬顿法和非均相芬顿法，其中均相芬顿是利用Fe 2+与H 2O 2反应产生具有超强氧化能力的羟基自由基(HO·)来降解水中污染物的过程。然而，传统芬顿技术存在诸多缺陷，如严格的酸性条件(pH<3)，反应过程中铁泥的产生，以及对氧化剂极低的利用率都大大限制了传统芬顿法在实际废水处理中的应用。于是，多相相芬顿催化引起广泛关注，在多相芬顿催化研究中，一种双反应活性中心机理因其独特的优势如氧化剂利用率高，催化稳定性号等引起了研究人员极大的兴趣。然而，传统富电子Cu中心类芬顿催化剂依然存在许多不足之处阻碍其发展，如对酚类污染物的矿化度低，对分子量大的有机污染物降解效果差等。现有的涉及相关专利如下：
申请号为20110856060.7的发明公开了一种基于含铁粘土矿物负载钯催化剂的电芬顿水处理方法，该发明通过还原反应负载到含铁粘土矿物上得到把铁一体化催化剂,将钯铁一体化催化剂加入电芬顿水处理装置中催化产生经自由基,进而降解水中的有机污染物。实验表明，该催化剂可将0.5mmol/L苯甲酸钠在60分钟内去除92％，然而该装置需要用到稳定直流电源电源，消耗大量电能。另外，贵金属的使用使得该催化剂的制备成本极大，且传统类芬顿的电子转移机理必将造成贵金属的严重流失。这些缺陷严重限制了该催化剂在实际废水处理中的应用。
申请号为201611147885.3的发明公开了一种铁铜双金属负载介孔硅非均相芬顿催化材料的制备方法，用该种方法制备的介孔硅负载铁铜复合金属氧化物催化剂材料具有孔径分布广，比表面积大，金属分布比较均匀的特点。然而在降解染料废水过程中，需投加大量的氧化剂和催化剂。该实验中，在待降解染料废水中投加0.15M的H 2O 2和2g/L的催化剂反应300min后才得到62.3％的降解率。这种催化效率将大量消耗氧化剂的量，造成高额的治理成本。同时处理效果也不显著。
申请号为201510939912.X公开了一种铁一铜一铝氧化物复合催化剂的制备方法，该发明通过对介孔材料一进行修饰,获得良好纳米层,继续负载双金属组分和之后，活性组分继续保持高度分散的纳米层。然而，整个芬顿反应过程需要耗费较长时间才能污染物有效去除，整个反应仍然是遵守着经典芬顿反应的机理。且并且这种催化剂还是依靠金属单一位点的氧化还原反应实现过氧化氢的活化，体系中过氧化氢的利用率仍然很低。
申请号为CN201811311154.7公开了一种具有双反应活性中心的类芬顿催化材料的制备方法。该催化材料呈现完整的球花状介孔结构，比表面积较大，能够暴露较多的催化活性位点，使得在反应过程中H 2O 2尽可能的在富电子中心发生还原反应产生羟基自由基，新型催化材料在中性条件下对各类毒害有机污染物具有很好的去除效果,并且能够实现对H 2O 2的高选择性转化。然而该催化材料在催化降解酚类物质时矿化度很低，且在降解染料等大分子物质时催化效果也不好。
传统富电子Cu中心类芬顿催化剂依然存在对酚类污染物矿化度较低，催化大分子污染物效果差的缺陷；新近研究发现，由于酚羟基与表面铜之间形成σ-Cu-ligand作用。Cu(II)在σ-Cu(II)复合物中可以通过氧化HO-加成自由基为羟基化产物而被还原为Cu(I)，这不仅 阻止了Cu(II)氧化H2O2为HO 2·/O 2· -，而且还促进了Cu(II)/Cu(I)〔2〕的氧化还原循环。因此σ-Cu-ligand作用在酚类化合物的选择性降解和H2O2的有效利用中起着重要作用。然而要实现双反应活性中心与σ-Cu-ligand的协同作用存在几个技术难题需要解决：(1)传统富电子Cu中心类芬顿催化剂的构建会阻碍酚类物质与表面Cu的作用因此限制σ-Cu-ligand作用；(2)足够强的极化差异才能实现双反应活性中心机理，因此要选择合适的金属或金属氧化物进行负载或掺杂；(3)Cu在催化剂的晶格掺杂形式对双反应活性中心的建立起着重要作用，如何改善和提高Cu的晶格掺杂是一个难题。
发明内容
本发明提供一种具有缺电子Cu中心的类芬顿催化材料及其制备方法和应用，以克服现有技术的缺陷。
为实现上述目的，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，具有这样的特征：包括如下步骤：
步骤一、将五水合硝酸铋溶解于硝酸溶液中，并使用去离子水将溶液稀释形成溶液A；
步骤二、将柠檬酸加入到溶液A中，并用氨水调节溶液形成溶液B；
步骤三、将异丙醇铝、二水合氯化铜和葡萄糖溶解于溶液B中形成悬浊液C；
步骤四、将悬浊液C在高温下搅拌蒸发至固体完全析出形成固体D；
步骤五、将固体D放入马弗炉中煅烧后得到所述类芬顿催化材料。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，步骤一中，所述硝酸溶液的浓度为1mol/L-2mol/L，所述五水合硝酸铋与硝酸溶液之比为0.32-3.28g∶5mL。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，所述柠檬酸与所述五水合硝酸铋的添加比为0.3-0.9g∶0.32-3.28g。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，步骤二中，氨水调节溶液pH至5-9。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，步骤三中，所述异丙醇铝、二水合氯化铜和葡萄糖的添加量之比为6.0-9.0g∶0.1-0.8g∶4.0-8.0g。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，步骤四中，高温温度为100℃，搅拌速度为100-200r/min。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，还可以具有这样的特征：其中，步骤五中，马弗炉煅烧温度为400-600℃，煅烧时间为3-7h，煅烧过程中的升温速率为5-10℃/min。
由上述的制备方法制得的具有缺电子Cu中心的类芬顿催化材料，也在本发明的保护范围内，所述催化材料整体呈现蓬松的棉花状多孔形貌。根据氮气吸脱附等温线和孔径分布图可知合成的类芬顿催化剂中主要存在介孔结构，且孔径分布在7.1nm左右；所述催化材料的结构式为为(Bi,Cu)Al 2O 3，其中Cu的质量分数为3.0-9.0％，Bi 12O 15Cl 6的质量分数为5.4-50.4％；所述催化材料由于缺电子Cu中心的形成，使得在催化降解酚类污染物时可以实现双反应活性中心 与σ-Cu-ligand的协同作用。
本发明还提供上述具有缺电子Cu中心的类芬顿催化材料的应用，具有这样的特征：所述类芬顿催化材料与H 2O 2在水中联用处理降解有机污染物。
进一步，本发明提供一种具有缺电子Cu中心的类芬顿催化材料的应用，还可以具有这样的特征：其中，所述有机污染物为罗丹明B、双酚A和二氯苯酚中的任一种。
本发明公开了一种缺电子Cu中心类芬顿催化材料及其制备方法，基于γ-Cu-Al 2O 3和Bi 12O 15Cl 6两种催化剂的掺杂，通过改良的蒸发诱导自组装反应一步合成γ-Cu-Al 2O 3并负载Bi 12O 15Cl 6，利用强电负性的Bi与使催化剂形成缺电子的Cu中心。与传统的富电子铜中心催化剂不同，缺电子铜中心有利于与酚类化合物形成σ-Cu-ligand作用。这样的σ-Cu-ligand可以通过H 2O 2氧化生成HO-加合自由基，生成·OH，并通过HO-加成自由基将Cu(II)配合物中的Cu(II)同时还原成Cu(I)。值得注意的是，虽然随着反应时间的延长，由于酚类化合物的减少，σ-Cu-ligand效应逐渐减弱，但随后双反应中心在催化反应中起主导作用。通过降解模拟的双酚A和二氯苯酚废水试验，表明新型γ-Cu-Al 2O 3-Bi 12O 15Cl 6具有极高的芬顿催化效果和稳定性。
本发明的有益效果在于：
一、制备的类芬顿催化材料具有蓬松多孔的结构、比表面积较大，能够暴露出更多的有效活性位点。
二、制备出的催化材料能够在中性条件下对有机污染物，如双酚A(BPA)、罗丹明B和二氯苯酚表现出良好的催化活性和稳定性。
三、缺电子Cu中心的形成使得该催化剂极易与酚类物质形成σ-Cu-ligand作用，大大提高的酚类物质的降解速率，同时σ-Cu-ligand与双反应活性中心的协同作用使得该体系对酚类污染物的矿化度也大大提高。
四、双反应活性中心的建立也使得该催化剂能够有效利用体系中的氧化剂，因此在该体系中双氧水的利用率很高。
附图说明
图1为(Bi,Cu)Al 2O 3的扫描电镜图；
图2为(Bi,Cu)Al 2O 3中各元素分布EDS图谱；
图3为(Bi,Cu)Al 2O 3的透射电镜图；
图4为(Bi,Cu)Al 2O 3的N 2吸脱附曲线和孔径分布图谱；
图5为(Bi,Cu)Al 2O 3的X射线衍射图谱；
图6为(Bi,Cu)Al 2O 3的Bi 4f、Cu 2p和Al 2p轨道的XPS图谱；
图7为(Bi,Cu)Al 2O 3中Cu元素电子自旋共振图谱；
图8为(Bi,Cu)Al 2O 3降解双酚A各阶段的红外图谱；
图9中，A为DMPO捕获悬浮液中HO 2·/O 2·-的EPR信号图；B为DMPO捕获悬浮液中·OH的EPR信号图；
图10为不同Bi 12O 15Cl 6含量的(Bi,Cu)Al 2O 3对初始浓度为20ppm的双酚A降解去效果图；
图11为不同H 2O 2含量的(Bi,Cu)Al 2O 3对双酚A降解去效果图；
图12为(Bi,Cu)Al 2O 3在不同有机物体系下的原位拉曼图谱；
图13为(Bi,Cu)Al 2O 3与过氧化氢水溶液相互作用的机理图。
具体实施方式
以下结合具体实施例对本发明作进一步说明。
实施例1
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.32g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为5.4％。
对上述制得的催化材料进行扫描电镜以及EDS表征，由图1可知经改良的蒸发诱导自组装反应和煅烧而成的催化剂呈现棉花状非晶态结构，结构蓬松多孔，为催化反应提供大量活性位点；由图2可知，Cu、C、Bi、O、Cl、Al元素均匀的分布在体相中，表明掺入的Cu元素以及生成的Bi 12O 15Cl 6很好的分布在基体材料Al 2O 3的结构中。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
实施例2
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为10.3％。
对上述制得的催化材料进行透射电镜表征，由图3可知Bi 12O 15Cl 6纳米粒子粘附在γ-Cu-Al 2O 3表面，形成异质结构。值得注意的是，HRTEM图像清楚地表明，铜完全嵌入γ-Al 2O 3晶格中。晶面间距为0.21nm的晶格条纹对应于Cu的(111)面，而没有晶格条纹的云状结构是非晶态结构的γ-Al 2O 3。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
实施例3
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将1.28g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为29.6％。
对上述制备的催化材料进行N2吸脱附曲线和孔径分布的测试，由图4可知，(Bi,Cu)Al 2O 3的N 2吸/脱附等温线是带有H3滞回曲线的IV等温线，表明狭缝状中孔结构，第一个位于相对压力P/P0＝0.4-0.8的滞后环表明合成的样品中主要存在的是介孔；第二个较小的在相对压力P/P0＝0.8-1.0之间的滞后环，表明催化剂中存在着一小部分较大的介孔。由孔径分布图可知棉花状(Bi,Cu)Al 2O 3中的介孔孔径主要分布在7.1nm左右，且由氮气吸脱附等温线计算得到的(Bi,Cu)Al 2O 3的比表面积为240m 2/g，孔容为0.454cm 3/g。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分 数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
实施例4
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将2g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为30.3％。
对上述制备的催化材料进行X射线衍射测试，由图5可知，(Bi,Cu)Al 2O 3的X射线衍射图中没有观察到与铜相对应的衍射峰。然而掺杂Bi 12O 15Cl 6后的催化剂的XRD图谱中出现新的峰，其中大多数峰对应于Bi 12O 15C l6。2θ＝30.12°处的最强衍射峰归因于Bi 12O 15Cl 6的(413)面，表明(413)面是该晶体晶面形成的择优取向。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
实施例5
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将2.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为42.1％。
对上述制备的催化材料进行XPS表征，由图6可知，(Bi,Cu)Al 2O 3谱中74.2和75.3eV处Al 3+的两个结合能(BEs)分配分别对应Al-O-Al和Al-O-Cu。此外，测定0.64CAB中Cu的XPS，拟合所得的三个峰932.7ev、934.0ev和942.4ev分别对应于铜的还原态、氧化态和波动峰。当Bi 12O 15Cl 6掺杂到γ-Cu-Al 2O 3中后，Bi有两个特征峰Bi 4f 7/2(158.3eV)和Bi 4f 5/2(163.7eV))。另外氧空位(OVs)可以在BiOCl的煅烧过程中形成，并且随着低电荷Bi离子(Bi (3-x)+)[28，29]的产生，OVs上的局域电子会转移给Bi 3+。因此，在Bi 12O 15Cl 6的光谱中会出现结合能较低的新峰(157.3eV，162.7eV)。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
从图10中可知，所述Bi 12O 15Cl 6质量分数为9％的类芬顿催化剂在中性pH条件下对BPA的降解效果较好，30min内的去除率达到95％以上。
实施例6
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将3.28g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.3g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为50.4％。
对上述制备的催化材料进行固体EPR表征，由图7可知，Cu元素固体EPR显示出很强的伴有超精细耦合结构的信号，这是自旋为I＝3/2的Cu(II)的典型特征。(Bi,Cu)Al 2O 3样品的g因子和A值如下表所示：
样品 g// g⊥ A//(G)
γ-Cu-Al 2O 3-Bi 12O 15Cl 6 2.403 2.130 130
其中g||>g⊥>2.0023(ge)，表明催化剂表面存在的未成对电子位于Cu(II)的dx2-y2轨道上，并且g因子所在数值范围和(Bi,Cu)Al 2O 3的EPR信号形状符合处于六配位的八面体几 何结构中的Cu(II)存在形式。上述结果表明，由于Bi和Cu的电负性差异，在对Al 2O 3进行Cu的共晶格掺杂并负载Bi 12O 15Cl 6引起了催化剂表面电子的非均匀分布，并且由于Bi的电负性高于Cu，使得Cu周围电子云密度减弱产生缺电子Cu中心，相对应的产生了富电子Bi中心。
实施例7
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.6g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为10.3％。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度，结果如图10所示。
用不同反应时间(Bi,Cu)Al 2O 3的FT-IR光谱来分析催化剂的表面反应过程(图8)。新制的(Bi,Cu)Al 2O 3在3500.9和1643cm -1处的两个吸收带分别对应于O H的拉伸振动和H-O-H的混合振动。BPA的-OH和-CH 3的特征峰分别出现在3339.7和2970cm -1处。1446.8、1510和1610cm -1处的峰归因于双酚A芳香环的骨架振动，而1177到1238cm -1范围内的特征峰代表酚羟基的C-O拉伸振动。吸附BPA后，BPA的酚羟基与Cu(II)形成第一配位相。由于双酚A酚羟基的脱质子和周围环境的差异，–OH的特征峰从3339.7cm -1移动到3423cm -1。此外，BPA在吸附后的(Bi,Cu)Al 2O 3光谱中也出现了一些特征峰。随着反应时间的延长，BPA芳香环的特征峰(1446.8、1510和1610cm -1)逐渐消失。反应12h后，所有有机物的特征峰消失，(Bi,Cu)Al 2O 3(0.64CAB)的v(OH)带移回3500.3cm -1，表明BPA及其中间体完全矿化。
实施例8
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.9g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至600℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为10.3％。
为了进一步阐明催化机理，在相应样品的不同分散体中检测DMPO捕获的EPR信号(图9)。在没有H 2O 2的情况下，纯Al 2O 3和Bi 12O 15Cl 6的甲醇分散液中未检测到信号。然而，DMPO-O2· -的六个特征峰的强度为γ-Cu-Al 2O 3>(Bi,Cu)Al 2O 3。其他的峰对应于DMPO和O2· -反应产生的碳中心自由基。由于这些峰与DMPO-O2· －的特征峰重叠，很难从EPR谱中识别出来。富电子中心和O2的反应可以产生O2· -。因此，在(Bi,Cu)Al 2O 3的甲醇分散体系中，Bi 12O 15Cl 6可以作为富电子中心，将O 2还原为O2· -。由于缺电子Cu中心氧化H 2O到·OH，在γ-Cu-Al 2O 3水溶液和(Bi,Cu)Al 2O 3水溶液中观察到了DMPO-OH·的特征峰。其强度为(Bi,Cu)Al 2O 3>γ-Cu-Al 2O 3。此外，·OH攻击含碳化合物(DMPO)，生成以碳为中心的自由基加合物[45]，出现了其他六个峰。
实施例9
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.6g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至550℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为10.3％。
实施例10
本实施例提供一种具有缺电子Cu中心的类芬顿催化材料的制备方法，包括如下步骤：
(1)将0.64g五水合硝酸铋溶解在5mL硝酸溶液(2M)中，加入去离子水稀释至100mL得到溶液A；
(2)将0.6g柠檬酸溶解于步骤(1)所得的溶液A中，以100r/min的速率搅拌并用氨水 调节pH至6.5，得到溶液B；
(3)在所得步骤(2)所得的溶液B中加入8.4g异丙醇铝、0.4g二水合氯化铜和7.2g葡萄糖，以100r/min的速率搅拌12h形成溶液C；
(4)将步骤(3)所得的所得溶液C放置于电热炉上以100℃加热搅拌至水分完全蒸干得到固体D；
(5)将步骤(4)所得的固体D放入刚玉坩埚中，于马弗炉中以5℃/min的升温速率，升温至650℃进行煅烧后保温6h，得到所述缺电子Cu中心类芬顿催化材料，其中Bi 12O 15Cl 6在该体系内的质量分数为10.3％。
配置20mg/L的双酚A溶液于150mL的锥形瓶中，在锥形瓶中加入由步骤(5)制备的催化材料0.1g，放置于35℃的恒温水浴锅中搅拌30min后达到吸附平衡，然后加入0.1mL的质量分数为30％的过氧化氢溶液，每隔5min取出反应溶液1mL过0.45μm滤膜后用用高效液相色谱HPLC测定不同反应时间下的BPA的浓度。从图11中可知，所述类芬顿催化剂在中性pH条件下可以在双氧水浓度为8mmol/L时快速降解BPA，30min内的去除率达到95％以上。
实验原理为：与传统的富电子铜中心催化剂不同，如图13所示，在[(Bi,Cu)Al2O3+H 2O 2+酚类化合物]体系中，缺电子铜中心有利于与酚类化合物形成σ-Cu-ligand作用。这样的σ-Cu-ligand被H 2O 2优先氧化生成·OH和HO-加合自由基，HO-加合自由基随后将Cu(II)还原为Cu(I)。因此，σ-Cu-ligand不仅防止Cu(II)氧化H 2O 2到HO 2·/O 2· -，而且还增强了Cu(II)/Cu(I)的氧化还原循环。值得注意的是，虽然由于酚类化合物的降解，σ-Cu-ligand会随时间逐渐减少，但双反应中心仍然可以在催化后续反应中发挥重要作用。富电子Bi中心能将H 2O 2还原为·OH，降解有机物。因此，在酚类化合物的降解过程中，有三条电子转移路线可以产生·OH：(1)第一条转移路线是从σ-Cu-ligand到H 2O 2，伴随着·OH的生成和Cu(I I)的还原到Cu(I)；(2)第二条转移路线是从Cu(I)到H 2O 2，伴随着·OH的生成；(3)第三条转移路线随着·OH的生成，从富电子Bi中心向H 2O 2转移。由于σ-Cu-ligand、双反应中心的协同作用，(Bi,Cu)Al 2O 3获得了较高的催化活性和过氧化氢的利用率(η)。

Claims (10)

  1. 一种具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    包括如下步骤：
    步骤一、将五水合硝酸铋溶解于硝酸溶液中，并使用去离子水将溶液稀释形成溶液A；
    步骤二、将柠檬酸加入到溶液A中，并用氨水调节溶液形成溶液B；
    步骤三、将异丙醇铝、二水合氯化铜和葡萄糖溶解于溶液B中形成悬浊液C；
    步骤四、将悬浊液C在高温下搅拌蒸发至固体完全析出形成固体D；
    步骤五、将固体D放入马弗炉中煅烧后得到所述类芬顿催化材料。
  2. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，步骤一中，所述硝酸溶液的浓度为1mol/L-2mol/L，所述五水合硝酸铋与硝酸溶液之比为0.32-3.28g∶5mL。
  3. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，所述柠檬酸与所述五水合硝酸铋的添加比为0.3-0.9g∶0.32-3.28g。
  4. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，步骤二中，氨水调节溶液pH至5-9。
  5. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，步骤三中，所述异丙醇铝、二水合氯化铜和葡萄糖的添加量之比为6.0-9.0g∶0.1-0.8g∶4.0-8.0g。
  6. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，步骤四中，高温温度为100℃，搅拌速度为100-200r/min。
  7. 根据权利要求1所述的具有缺电子Cu中心的类芬顿催化材料的制备方法，其特征在于：
    其中，步骤五中，马弗炉煅烧温度为400-600℃，煅烧时间为3-7h，煅烧过程中的升温速率为5-10℃/min。
  8. 一种具有缺电子Cu中心的类芬顿催化材料，其特征在于：由权利要求1-7任一项所述的方法制得，所述类芬顿催化材料的结构式为(Bi,Cu)Al 2O 3，其中Cu的质量分数为3.0-9.0％，Bi 12O 15Cl 6的质量分数为5.4-50.4％。
  9. 如权利要求8所述的具有缺电子Cu中心的类芬顿催化材料的应用，其特征在于：所述类芬顿催化材料与H 2O 2在水中联用处理降解有机污染物。
  10. 根据权利要求9所述的具有缺电子Cu中心的类芬顿催化材料的应用，其特征在于：
    其中，所述有机污染物为罗丹明B、双酚A和二氯苯酚中的任一种。
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