WO2018113384A1 - 一步法合成环糊精修饰的过渡金属氧化物材料的方法 - Google Patents

一步法合成环糊精修饰的过渡金属氧化物材料的方法 Download PDF

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WO2018113384A1
WO2018113384A1 PCT/CN2017/104877 CN2017104877W WO2018113384A1 WO 2018113384 A1 WO2018113384 A1 WO 2018113384A1 CN 2017104877 W CN2017104877 W CN 2017104877W WO 2018113384 A1 WO2018113384 A1 WO 2018113384A1
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cyclodextrin
salt
transition metal
modified
metal oxide
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占金华
孔令帅
孔娅
张锦文
李元培
陈玉峰
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Shandong University
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Shandong University
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Priority claimed from CN201710861568.6A external-priority patent/CN107537566B/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation

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  • the invention relates to a method for synthesizing a cyclodextrin-modified transition metal oxide material by one-step method, and belongs to the technical field of material synthesis.
  • oxide nanomaterials have been applied to many different fields, such as traditional photocatalysis, Fenton reaction, etc., and applications in new fields include photocatalytic hydrogen production and enzyme-like catalysis.
  • oxide nanomaterials have broad application prospects in biomedical fields such as medical imaging, diagnostic treatment, and mimic enzymes. The use of oxide nanoparticles has become one of the most compelling and dynamic research areas.
  • ⁇ -cyclodextrin which is represented by the second-generation supramolecules, is a cyclic oligosaccharide produced by seven D-glucopyranose units, each of which has a 1,4-glycoside The bonds are combined into a ring. Since the glycosidic linkage to the glucose unit is not free to rotate, the cyclodextrin is not a cylindrical molecule but a slightly conical ring.
  • the central cavity is hydrophobic and lipophilic, so cyclodextrin can selectively identify guest molecules and combine with some organic and inorganic guest molecules of appropriate size to form a supramolecular system, in biological probes, environmental management, Enzyme-catalyzed and other fields have been widely used, and the application prospect is huge.
  • Physiological hormones and pesticides in human life cause a certain degree of pollution to water quality. Because pesticide residues and physiological hormones are the most common pollutants in environmental water resources. Therefore, methods for removing physiological hormones and pesticides in water are facing major challenges, such as photocatalysis, physical adsorption, and biodegradation.
  • the present invention provides a method for synthesizing a cyclodextrin-modified transition metal oxide material in a one-step process, and the obtained composite material not only has catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, but also has a ring.
  • the host-guest of dextrin supramolecular is used in combination, and its excellent catalytic performance and supramolecular cooperation will play an important role in environmental pollution control.
  • a one-step method for synthesizing a cyclodextrin-modified transition metal oxide material comprises the following steps:
  • transition metal oxide salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours.
  • the solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a cyclodextrin-modified transition metal oxide material.
  • Metal oxide The mass ratio of salt to cyclodextrin is: (0.1-200): (0.1-50), the mass-to-volume ratio of transition metal oxide salt to solvent is: (0.1-10): (100-2000), unit: g /mL.
  • the transition metal oxide salt is a copper salt or an iron salt.
  • the copper salt is cuprous chloride, cuprous bromide, cuprous iodide, cuprous sulfate, cuprous carbonate or cuprous nitride.
  • the copper salt is cuprous chloride.
  • the cyclodextrin is ⁇ -cyclodextrin, ⁇ -cyclodextrin or ⁇ -cyclodextrin.
  • the cyclodextrin is ⁇ -cyclodextrin.
  • the iron salt is ferric chloride or ferrous chloride.
  • the iron salt is ferrous chloride.
  • the solvent is water or an alcohol solvent.
  • the alcohol solvent is an alcohol solvent having two or more hydroxyl groups, and more preferably, the alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1, 3 ⁇ One or more of propylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol or trimethylolpropane mixture.
  • the solvent is water.
  • the transition metal oxide salt is a copper salt
  • a one-step synthesis of a cyclodextrin-modified cuprous oxide material is prepared, and the preparation method comprises the following steps:
  • the copper salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours.
  • the brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material, copper salt and
  • the mass ratio of the cyclodextrin is: (0.1 to 10): (0.1 to 50), and the mass to volume ratio of the copper salt to the solvent is: (0.1 to 10): (100 to 2000), and the unit is g/mL.
  • the mass ratio of the copper salt to the cyclodextrin is (0.1 to 8): (0.1 to 20).
  • the mass to volume ratio of the copper salt to the solvent is: (0.1-10): (100-1000), unit: g/mL; preferably, the mass-volume ratio of the copper salt to the solvent is: (0.1-10) ): (100 to 600), unit: g / mL; most preferably, the mass ratio of copper salt to solvent is: (0.1 ⁇ 10): 200, unit: g / mL.
  • the reaction time is from 10 to 48 h, more preferably, the reaction time is from 20 to 36 h, and most preferably, the reaction time is 24 h.
  • the reaction environment is a reaction at a temperature of 40 ° C or less.
  • the reaction temperature is 20 to 40 ° C.
  • the drying is carried out in a vacuum drying oven for drying at a temperature of 50 to 70 ° C and a drying time of 10 to 16 hours.
  • a preferred technical solution of the present invention a method for synthesizing a cyclodextrin-modified cuprous oxide material in a one-step process, comprising the steps as follows:
  • the copper salt and the cyclodextrin are added to water or an alcohol solvent, and the reaction is stirred for 10 to 48 hours.
  • the brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material.
  • the mass ratio of copper salt to cyclodextrin is: (0.1 ⁇ 10): (0.1 ⁇ 50), the mass to volume ratio of copper salt to solvent is: (0.1 ⁇ 10): (100 ⁇ 1000), unit: g/ mL.
  • transition metal oxide salt is an iron salt
  • a one-step synthesis of a cyclodextrin-modified iron oxyhydroxide material is prepared, and a metal salt is doped during the preparation to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material, and the preparation method includes Proceed as follows:
  • the iron salt, the metal salt and the cyclodextrin are added to the water, and the reaction is stirred for 10 to 72 hours.
  • the yellow-brown solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide.
  • the mass ratio of the material, iron salt and cyclodextrin is: (10 ⁇ 200): (1 ⁇ 50)
  • the mass to volume ratio of iron salt to water is: (0.1 ⁇ 10): (10 ⁇ 200)
  • the metal salt is added in an amount of 0.1-10% by mass of the iron salt.
  • the metal salt is a transition metal salt or a noble metal salt
  • the transition metal salt is a carbonate, a sulfate, a nitrate, a chloride salt of copper, manganese, cobalt or nickel
  • the transition metal salt is gold, silver, Palladium or platinum salts.
  • the transition metal salt is a nitrate of copper, manganese, cobalt or nickel.
  • the salt of gold, silver, palladium or platinum is chloroauric acid, silver nitrate, palladium chloride or palladium acetate.
  • the metal salt is a transition metal salt
  • the iron salt, the transition metal salt and the cyclodextrin are added to water, the reaction is stirred, the reaction is washed, and after drying, a metal-doped cyclodextrin-modified iron oxyhydroxide material is obtained.
  • the metal salt is a noble metal salt
  • the iron salt, the noble metal salt and the cyclodextrin are added to water, the reaction is stirred, the reaction is washed, dried, and hydrogen-reduced to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material.
  • the mass ratio of the iron salt to the cyclodextrin is (10 to 100): (5 to 20).
  • the mass to volume ratio of iron salt to water is: (0.5-10): (10-100), unit: g/mL;
  • the mass to volume ratio of iron salt to water is: (0.5-10): (10-80), unit: g/mL; most preferably, the mass-volume ratio of iron salt to water is: (0.5-10) : 50, unit: g / mL.
  • the reaction time is from 10 to 36 h, more preferably, the reaction time is from 20 to 36 h, and most preferably, the reaction time is 24 h.
  • the reaction environment is a reaction at a temperature of 50 ° C or less.
  • the reaction temperature is 25 ° C.
  • the drying is carried out in an electric blast drying oven for drying at a temperature of 60 to 80 ° C and a drying time of 10 to 16 hours.
  • the metal ion is supported in the channel of the iron oxyhydroxide, and the hydroxyl group of the iron oxyhydroxide forms an H bond with the hydroxyl group of the cyclodextrin, and the bonding structure is on the one hand
  • the cyclodextrin is encapsulated on the outside of the iron oxyhydroxide to increase the stability of the iron oxyhydroxide, and on the other hand to promote the stable loading of the metal ions in the hydroxy oxidation In the channel of iron, the stability of the material is further increased, and the doping of the metal and the inclusion of the cyclodextrin synergistically improve the catalytic degradation performance of the material.
  • Precious metal doping can achieve strong interaction of metal carriers, synergistic with multiple functions, and achieve efficient combined catalysis. It can also achieve surface interaction with atoms based on cyclodextrin-modified carriers at the atomic level to achieve internal electronic surface enrichment. Collecting, thus improving the original nature.
  • the doping width of the iron oxyhydroxide can be changed by the doping of the transition metal, thereby making the optical response range adjustable, and finally achieving a better catalytic effect.
  • the doping of the transition metal of the transition metal contributes to the circulation of the ferrous iron and the ferric iron, and improves the stability of the material; the doping can also achieve efficient degradation of organic pollutants in a wide pH environment.
  • the composite material prepared by the invention not only has the catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, but also has the host-guest inclusion of cyclodextrin supramolecular, with its excellent catalytic performance and supramolecular package. Cooperation will play an important role in environmental pollution control.
  • the composite material of the invention is doped by noble metal or transition metal, and the modification of cyclodextrin greatly improves the catalytic effect of iron oxyhydroxide, and has the characteristics of catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, etc.
  • the host-guest of cyclodextrin supramolecules is used in combination, and its excellent catalytic performance and supramolecular cooperation play a very important role in the catalytic degradation of pollutants such as pesticides and physiological hormones in water.
  • the doping of the noble metal or transition metal of the composite material of the invention improves the catalytic effect of the cyclodextrin-modified iron oxyhydroxide, and the catalytic degradation effect of the iron oxyhydroxide modified by the undoped cyclodextrin is from 0 to 1.
  • Example 1 is a Fourier transform infrared spectroscopy (FTIR) spectrum of a cyclodextrin-modified cuprous oxide composite prepared in Example 1.
  • FTIR Fourier transform infrared spectroscopy
  • FIG. 2 is a comparison diagram of the degradation effect of cuprous oxide and cyclodextrin-modified cuprous oxide material on hydrogen peroxide degradation of bisphenol;
  • Example 4 is a Fourier transform infrared spectroscopy (FTIR) spectrum of a cyclodextrin-modified iron oxyhydroxide composite prepared in Example 20.
  • FTIR Fourier transform infrared spectroscopy
  • Figure 5 is a kinetic diagram of the degradation of 4-chlorophenol by hydrogen peroxide catalyzed by iron oxyhydroxide and a cyclodextrin-modified iron oxyhydroxide material.
  • Figure 6 is a comparison diagram of the effect of iron oxyhydroxide and cyclodextrin-modified iron oxyhydroxide material on the degradation of 4-chlorophenol by hydrogen peroxide;
  • Figure 7 is a graph showing the relationship of ⁇ hv ⁇ hv function of iron oxyhydroxide
  • Example 8 is an ⁇ hv ⁇ hv function of a cyclodextrin-coated composite material of iron oxyhydroxide and cobalt ions prepared in Example 22. Number relationship diagram;
  • Figure 9 is a graph showing the ⁇ hv ⁇ hv function of a composite of a cyclodextrin-coated iron oxyhydroxide and a nickel ion prepared in Example 24.
  • a one-step method for synthesizing a cyclodextrin-modified cuprous oxide material is as follows:
  • Example 2 A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous bromide was substituted for cuprous chloride.
  • Example 3 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous iodide was substituted for cuprous chloride.
  • Example 4 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous sulfate was substituted for cuprous chloride.
  • Example 5 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous carbonate was substituted for cuprous chloride.
  • Example 6 A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous nitride was substituted for cuprous chloride.
  • Example 7 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that ⁇ -cyclodextrin was substituted for ⁇ -cyclodextrin.
  • Example 8 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that ⁇ -cyclodextrin was substituted for ⁇ -cyclodextrin.
  • Example 9 A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 12 h.
  • Example 10 A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 36 h.
  • Example 11 A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 72 h.
  • Example 12 A one-step process for the synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that ethylene glycol was used instead of water.
  • Example 13 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that glycerin was used instead of water.
  • Example 14 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction temperature was 40 °C.
  • Example 15 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction temperature was 30 °C.
  • Example 15 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 400 mL.
  • Example 16 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 800 mL.
  • Example 17 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 1000 mL.
  • Example 18 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 1500 mL.
  • Example 19 A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 2000 mL.
  • the cyclodextrin-modified cuprous oxide material prepared by the invention catalyzes the degradation of bisphenol A (BPA) by hydrogen peroxide, and simultaneously compares the catalytic degradation performance with unmodified cuprous oxide.
  • BPA bisphenol A
  • the bisphenol A content in the reaction solution was measured by high performance liquid chromatography (HPLC) at different time points.
  • HPLC high performance liquid chromatography
  • the comparative degradation effect is shown in Fig. 2, and the degradation kinetics obtained is shown in Fig. 3.
  • a one-step synthesis method of metal doped cyclodextrin-modified iron oxyhydroxide material the steps are as follows:
  • Example 1 The one-step synthesis method described in Example 1 was different except that ferric chloride was used instead of ferrous chloride.
  • Example 1 The one-step synthesis method described in Example 1 is different in that cobalt nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and cobalt ions.
  • Example 1 The one-step synthesis method described in Example 1 is different in that manganese nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and manganese ions.
  • Example 1 The one-step synthesis method described in Example 1 is different in that nickel nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and nickel ions.
  • Example 1 The one-step synthesis method described in Example 1 was different in that ⁇ -cyclodextrin was substituted for ⁇ -cyclodextrin.
  • Example 1 The one-step synthesis method described in Example 1 was different in that ⁇ -cyclodextrin was substituted for ⁇ -cyclodextrin.
  • the one-step synthesis method described in Example 1 was different in that the reaction time was 12 h.
  • the one-step synthesis method described in Example 1 was different in that the reaction time was 36 h.
  • the one-step synthesis method described in Example 1 was different in that the reaction time was 72 h.
  • the one-step synthesis method described in Example 1 was different in that the amount of water added was 400 mL.
  • the one-step synthesis method described in Example 1 was different in that the amount of water added was 800 mL.
  • the one-step synthesis method described in Example 1 was different in that the amount of water added was 1000 mL.
  • the one-step synthesis method described in Example 1 was different in that the amount of water added was 1500 mL.
  • the one-step synthesis method described in Example 1 was different in that the amount of water added was 2000 mL.
  • the one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with gold chlorate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite of cyclodextrin-coated iron oxyhydroxide and gold. material.
  • the one-step synthesis method described in the first embodiment is different from: replacing silver nitrate with silver nitrate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite material of cyclodextrin-coated iron oxyhydroxide and silver. .
  • the one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with palladium acetate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite material of cyclodextrin-coated iron oxyhydroxide and palladium. .
  • the one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with platinum chloride, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite of cyclodextrin-coated iron oxyhydroxide and platinum. material.
  • the cyclodextrin-modified iron oxyhydroxide material prepared by the invention catalyzes the degradation of p-chlorophenol (4-cp) by hydrogen peroxide, and simultaneously with hydrogen peroxide, hydrogen peroxide-cyclodextrin, iron oxyhydroxide- Hydrogen peroxide and metal doped cyclodextrin-modified iron oxyhydroxide were compared for catalytic degradation performance.
  • Fig. 6 The content of p-chlorophenol in the reaction solution was measured by high performance liquid chromatography (HPLC) at different time points, and the comparative degradation effect is shown in Fig. 6.
  • the doping of the noble metal or transition metal of the composite material of the invention improves the catalytic effect of the cyclodextrin-modified iron oxyhydroxide, and after the metal doping, the ultraviolet spectrum changes, resulting in oxidation of the hydroxyl group.
  • the width of the forbidden band changes and the photocatalytic properties change.

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Abstract

一步法合成环糊精修饰的过渡金属氧化物材料的方法，包括步骤：将过渡金属氧化物盐和环糊精加入溶剂中，搅拌反应1h～72h，反应得到的固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的过渡金属氧化物材料，该复合材料不但具有催化过氧化氢，光催化等，而且还具有环糊精超分子的主客体包合作用，并以其优异的催化性能和超分子的包合作用会在环境污染治理方面起到重要作用。

Description

一步法合成环糊精修饰的过渡金属氧化物材料的方法 技术领域
本发明涉及一步法合成环糊精修饰的过渡金属氧化物材料的方法，属于材料合成技术领域。
背景技术
过去的几十年，氧化物纳米材料已经应用到很多不同领域，如传统的光催化，芬顿反应，等，在新领域的应用包括光催化产氢和类酶催化。此外，氧化物纳米材料在医学影像、诊断治疗、模拟酶等生物医学领域展现出广阔的应用前景。氧化物纳米粒子的应用成为目前最引人注目和最具活力的研究领域之一。
众所周知，作为第二代超分子代表的β-环糊精(β-CDs)是由7个D-吡喃葡萄糖单元生成的一种环状低聚糖，各葡萄糖单元均以1，4-糖苷键结合成环。由于连接葡萄糖单元的糖苷键不能自由旋转，环糊精不是圆筒状分子而是略呈锥形的圆环。其中心空腔是疏水、亲脂性的，因此环糊精可以选择性的识别客体分子，与一些尺寸相宜的有机、无机客体分子相包合，形成超分子体系，在生物探针、环境治理、类酶催化等领域得到广泛的应用，应用前景巨大。
人类生活中生理激素类、农药类等对水质造成一定程度上的污染。由于农残和生理激素是环境水资源中较为普遍的污染物。因此，去除水中生理激素类、农药类污染物方法面临重大挑战，现已应用的如光催化，物理吸附，生物降解等方法。
发明内容
针对现有技术的不足，本发明提供一步法合成环糊精修饰的过渡金属氧化物材料的方法，制得的复合材料不但具有催化过氧化氢，光催化，类酶催化等，而且还具有环糊精超分子的主客体包合作用，并且以其优异的催化性能和超分子的包合作用会在环境污染治理方面起到重要作用。
本发明是通过如下技术方案实现的：
一步法合成环糊精修饰的过渡金属氧化物材料的方法，包括步骤如下：
将过渡金属氧化物盐和环糊精加入溶剂中，搅拌反应1h～72h，反应得到的固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的过渡金属氧化物材料，过渡金属氧化物 盐与环糊精的质量比为：(0.1～200)：(0.1～50)，过渡金属氧化物盐与溶剂的质量体积比为：(0.1～10)：(100～2000)，单位：g/mL。
本发明优选的，所述的过渡金属氧化物盐为铜盐或铁盐。
本发明优选的，所述的铜盐为氯化亚铜、溴化亚铜、碘化亚铜、硫酸亚铜、碳酸亚铜或氮化亚铜。
进一步优选的，所述的铜盐为氯化亚铜。
本发明优选的，所述的环糊精为α-环糊精、β-环糊精或γ-环糊精。
进一步优选的，所述的环糊精为β-环糊精。
本发明优选的，所述的铁盐为氯化铁或氯化亚铁
进一步优选的，所述的铁盐为氯化亚铁。
本发明优选的，所述的溶剂为水或醇类溶剂。
优选的，所述的醇类溶剂为2个羟基以上的醇类溶剂，进一步优选的，所述的醇类物质选自乙二醇、二乙二醇、1,2‐丙二醇、1,3‐丙二醇、甘油、1,3‐丁二醇、1,4‐丁二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇或三羟甲基丙烷中的一种或多种的混合物。
本发明最为优选的，所述的溶剂为水。
当过渡金属氧化物盐为铜盐，制得一步法合成环糊精修饰的氧化亚铜材料，制备方法，包括步骤如下：
将铜盐和环糊精加入溶剂中，搅拌反应1h～72h，反应得到的砖红色固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的氧化亚铜材料，铜盐与环糊精的质量比为：(0.1～10)：(0.1～50)，铜盐与溶剂的质量体积比为：(0.1～10)：(100～2000)，单位：g/mL。
本发明优选的，铜盐与环糊精的质量比为：(0.1～8)：(0.1～20)。
本发明优选的，铜盐与溶剂的质量体积比为：(0.1～10)：(100～1000)，单位：g/mL；优选的，铜盐与溶剂的质量体积比为：(0.1～10)：(100～600)，单位：g/mL；最为优选的，铜盐与溶剂的质量体积比为：(0.1～10)：200，单位：g/mL。
本发明优选的，反应时间为10～48h，进一步优选的，反应时间为20～36h，最为优选的，反应时间为24h。
本发明优选的，反应环境为在小于等于40℃温度下反应，优选的，反应温度为20～40℃。
本发明优选的，所述的干燥为置于真空干燥箱中进行干燥，干燥温度为50～70℃，干燥时间10～16小时。
本发明优选的一个技术方案，一步法合成环糊精修饰的氧化亚铜材料的方法，包括步骤 如下：
将铜盐和环糊精加入水或醇类溶剂中，搅拌反应10h～48h，反应得到的砖红色固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的氧化亚铜材料，铜盐与环糊精的质量比为：(0.1～10)：(0.1～50)，铜盐与溶剂的质量体积比为：(0.1～10)：(100～1000)，单位：g/mL。
当过渡金属氧化物盐为铁盐，制得一步法合成环糊精修饰的羟基氧化铁材料，制备过程中掺杂金属盐，得到金属掺杂环糊精修饰的羟基氧化铁材料，制备方法包括步骤如下：
将铁盐、金属盐和环糊精加入水中，搅拌反应10h～72h，反应得到的黄褐色固体分别用无水乙醇、去离子水清洗，干燥后得到金属掺杂环糊精修饰的羟基氧化铁材料，铁盐与环糊精的质量比为：(10～200)：(1～50)，铁盐与水的质量体积比为：(0.1～10)：(10～200)，单位：g/mL，金属盐的加入量为铁盐质量的0.1-10％。
根据本发明优选的，金属盐为过渡金属盐或贵金属盐，过渡金属盐为铜、锰、钴或镍的碳酸盐、硫酸盐、硝酸盐、氯化盐；过渡金属盐为金、银、钯或铂的盐类。
进一步优选的，过渡金属盐为铜、锰、钴或镍的硝酸盐。
进一步优选的，金、银、钯或铂的盐类为氯金酸、硝酸银、氯化钯或醋酸钯。
当金属盐为过渡金属盐，将铁盐、过渡金属盐和环糊精加入水中，搅拌反应，反应后洗涤，干燥后得到金属掺杂环糊精修饰的羟基氧化铁材料。
当金属盐为贵金属盐，将铁盐、贵金属盐和环糊精加入水中，搅拌反应，反应后洗涤，干燥，氢气还原得到金属掺杂环糊精修饰的羟基氧化铁材料。
本发明优选的，铁盐与环糊精的质量比为：(10～100)：(5～20)。
本发明优选的，铁盐与水的质量体积比为：(0.5～10)：(10～100)，单位：g/mL；
优选的，铁盐与水的质量体积比为：(0.5～10)：(10～80)，单位：g/mL；最为优选的，铁盐与水的质量体积比为：(0.5～10)：50，单位：g/mL。
本发明优选的，反应时间为10～36h，进一步优选的，反应时间为20～36h，最为优选的，反应时间为24h。
本发明优选的，反应环境为在小于等于50℃温度下反应，优选的，反应温度为25℃。
本发明优选的，所述的干燥为置于电热鼓风干燥箱中进行干燥，干燥温度为60～80℃，干燥时间10～16小时。
本发明的金属掺杂环糊精修饰的羟基氧化铁材料，金属离子负载在羟基氧化铁的通道内，羟基氧化铁的羟基与环糊精的羟基形成H键键合，该键合结构一方面使环糊精包合在羟基氧化铁的外面，增加羟基氧化铁的稳定性，另一方面促进金属离子稳固的负载在羟基氧化 铁的通道内，进一步增加了材料的稳定性，金属的掺杂，环糊精的包合协同提高了材料的催化降解性能。贵金属掺杂可实现金属载体强相互作用，多种功能协同，实现高效的联合催化；也可以实现在单原子水平上，原子与基于环糊精改性载体的表面相互作用，实现内部电子表面富集化，从而提高原有性质。通过过渡金属的掺杂能够改变羟基氧化铁的禁带宽度，进而使光响应范围可调，最终实现更好的催化效果。在芬顿反应中，过渡金属的掺杂金属的掺杂有助于二价铁与三价铁的循环，提高材料稳定性；掺杂还可以实现在宽pH环境中高效降解有机污染物。
本发明所用原料及设备均为现有技术。
本发明的优点如下：
1、本发明制得的复合材料不但具有催化过氧化氢，光催化，类酶催化等，而且还具有环糊精超分子的主客体包合作用，以其优异的催化性能和超分子的包合作用会在环境污染治理方面起到重要作用。
2、本发明的复合材料通过贵金属或过渡金属的掺杂，环糊精的修饰大大提高了羟基氧化铁的催化作用，不但具有催化过氧化氢，光催化，类酶催化等特点，而且还具有环糊精超分子的主客体包合作用，并且以其优异的催化性能和超分子的包合作用在催化降解水中农药类、生理激素类等污染物起着非常重要的作用。
3、本发明的复合材料贵金属或过渡金属的掺杂，提高了环糊精修饰的羟基氧化铁的催化作用，比不掺杂的环糊精修饰的羟基氧化铁催化降解效果实现从0到1的突破；同时金属掺杂以后，紫外光谱发生改变，导致羟基氧化铁禁带宽度改变，光催化性能进而改变。
附图说明
图1是实施例1制备的环糊精修饰的氧化亚铜复合材料的傅里叶转换红外光谱(FTIR)图谱。采用德国Bruker ALPHA-T傅里叶转换红外光谱仪，检测器:RT-DLATGS。
图2为氧化亚铜与环糊精修饰的氧化亚铜材料催化过氧化氢降解双酚降解效果对比图；
图3氧化亚铜与环糊精修饰的氧化亚铜材料催化过氧化氢降解双酚降解动力学图。
图4是实施例20制备的环糊精修饰的羟基氧化铁复合材料的傅里叶转换红外光谱(FTIR)图谱。采用德国Bruker ALPHA-T傅里叶转换红外光谱仪，检测器:RT-DLATGS。
图5为羟基氧化铁与环糊精修饰的羟基氧化铁材料催化过氧化氢降解4-氯苯酚动力学图。
图6为羟基氧化铁与环糊精修饰的羟基氧化铁材料催化过氧化氢降解4-氯苯酚效果对比图；
图7为羟基氧化铁的αhv∝hv函数关系图；
图8为实施例22制得的环糊精包覆羟基氧化铁和钴离子的复合材料的αhv∝hv函 数关系图；
图9为实施例24制得的环糊精包覆羟基氧化铁和镍离子的复合材料的αhv∝hv函数关系图。
具体实施方式
下面通过具体实施例对本发明做进一步说明，但不限于此。
以下实施例所用原料均为市够产品，分析纯。
实施例1
一步法合成环糊精修饰的氧化亚铜材料的方法，步骤如下：
首先称取0.1-10克的氯化亚铜和0.1-50克β-环糊精置于锥形瓶中，倒入200mL的水，室温溶解，搅拌，反应24h，将制备的砖红色固体分别用无水乙醇、去离子水清洗，干燥即可得到环糊精修饰的氧化亚铜材料。
实施例2：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：溴化亚铜代替氯化亚铜。
实施例3：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：碘化亚铜代替氯化亚铜。
实施例4：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：硫酸亚铜代替氯化亚铜。
实施例5：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：碳酸亚铜代替氯化亚铜。
实施例6：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：氮化亚铜代替氯化亚铜。
实施例7：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：α-环糊精代替β-环糊精。
实施例8：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：γ-环糊精代替β-环糊精。
实施例9：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：反应时间为12h。
实施例10：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：反应时间为36h。
实施例11：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：反应时间为72h。
实施例12：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：用乙二醇代替水。
实施例13：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：用甘油代替水。
实施例14：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：反应温度为40℃。
实施例15：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：反应温度为30℃。
实施例15：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：水的加入量为400mL。
实施例16：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：水的加入量为800mL。
实施例17：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：水的加入量为1000mL。
实施例18：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：水的加入量为1500mL。
实施例19：如实施例1所述一步法合成环糊精修饰的氧化亚铜材料的方法，所不同的是：水的加入量为2000mL。
实验例1：催化降解
将本发明制得的环糊精修饰的氧化亚铜材料催化过氧化氢降解双酚A(BPA)，同时与未经修饰的氧化亚铜进行催化降解性能对比。
实验仪器：高效液相色谱(HPLC)，型号ELITE P1201,仪器装配二极管阵列检测器和C18反相柱(5μm，4.6mm*150mm)，流动相为甲醇/水(70：30，v/v)流速1mL/min柱温40℃，BPA检测波长278nm。
实验配方：浓度为0.01g/L的Cu2O以及Cu2O@β-CD，30mM H2O2，10ppm双酚A，室温下搅拌。
取不同时间点用高效液相色谱(HPLC)测试反应液中的双酚A含量，对比降解效果如图2所示，得到的降解动力学图如图3所示。
通过图3进行动力学分析，得出Cu2O@β-CD表观速率常数(Kobs)为0.0064min-1，明显高于Cu2O降解双酚A的数值(kobs＝0.0036min-1)。
实施例20
金属掺杂环糊精修饰的羟基氧化铁材料的一步合成方法，步骤如下：
称取10～100克的氯化亚铁、5～20克β-环糊精置、硝酸铜于锥形瓶中，倒入250mL的水，超声溶解，25℃水浴搅拌，反应时间30h，反应得到的固体分别用无水乙醇、去离子水清洗，干燥即可得到金属掺杂环糊精修饰的羟基氧化铁材料，即为环糊精包覆羟基氧化铁和铜离子的复合材料。
实施例21：
同实施例1所述的一步合成方法，所不同的是：用氯化铁代替氯化亚铁。
实施例22：
同实施例1所述的一步合成方法，所不同的是：用硝酸钴代替硝酸铜，得到环糊精包覆羟基氧化铁和钴离子的复合材料。
实施例23：
同实施例1所述的一步合成方法，所不同的是：用硝酸锰代替硝酸铜，得到环糊精包覆羟基氧化铁和锰离子的复合材料。
实施例24：
同实施例1所述的一步合成方法，所不同的是：用硝酸镍代替硝酸铜，得到环糊精包覆羟基氧化铁和镍离子的复合材料。
实施例25：
同实施例1所述的一步合成方法，所不同的是：α-环糊精代替β-环糊精。
实施例26：
同实施例1所述的一步合成方法，所不同的是：γ-环糊精代替β-环糊精。
实施例27：
同实施例1所述的一步合成方法，所不同的是：反应时间为12h。
实施例28：
同实施例1所述的一步合成方法，所不同的是：反应时间为36h。
实施例29：
同实施例1所述的一步合成方法，所不同的是：反应时间为72h。
实施例30：
同实施例1所述的一步合成方法，所不同的是：水的加入量为400mL。
实施例31：
同实施例1所述的一步合成方法，所不同的是：水的加入量为800mL。
实施例32：
同实施例1所述的一步合成方法，所不同的是：水的加入量为1000mL。
实施例33：
同实施例1所述的一步合成方法，所不同的是：水的加入量为1500mL。
实施例34：
同实施例1所述的一步合成方法，所不同的是：水的加入量为2000mL。
实施例35：
同实施例1所述的一步合成方法，所不同的是：用氯酸金代替硝酸钴，搅拌反应后，洗涤，干燥，然后进行氢气还原，得到环糊精包覆羟基氧化铁和金的复合材料。
实施例36：
同实施例1所述的一步合成方法，所不同的是：用硝酸银代替硝酸钴，搅拌反应后，洗涤，干燥，然后进行氢气还原，得到环糊精包覆羟基氧化铁和银的复合材料。
实施例37：
同实施例1所述的一步合成方法，所不同的是：用醋酸钯代替硝酸钴，搅拌反应后，洗涤，干燥，然后进行氢气还原，得到环糊精包覆羟基氧化铁和钯的复合材料。
实施例38：
同实施例1所述的一步合成方法，所不同的是：用氯化铂代替硝酸钴，搅拌反应后，洗涤，干燥，然后进行氢气还原，得到环糊精包覆羟基氧化铁和铂的复合材料。
实验例2：催化降解
1、将本发明制得的环糊精修饰的羟基氧化铁材料催化过氧化氢降解对氯苯酚(4-cp)，同时与过氧化氢、过氧化氢-环糊精、羟基氧化铁-过氧化氢、金属掺杂环糊精修饰的羟基氧化铁分别进行催化降解性能对比。
实验仪器：高效液相色谱(HPLC)，型号ELITE P1201,仪器装配二极管阵列检测器和C18反相柱(5μm，4.6mm*150mm)，流动相为甲醇/水(70：30，v/v)流速1mL/min柱温30℃，4-CP检测波长280nm。
实验配方：浓度为0.1g/L的FeOOH以及FeOOH@β-CD，20mM H2O2，100ppm对氯苯酚,100ppmβ-CD，室温下搅拌。
取不同时间点用高效液相色谱(HPLC)测试反应液中的对氯苯酚含量，对比降解效果如图6所示。通过图6进行动力学分析，得出FeOOH@β-CD表观速率常数(Kobs)为0.0064min-1，明显高于FeOOH降解4-氯苯酚的数值(kobs＝0.0036min-1)。
从图7-9对比来看，本发明的复合材料贵金属或过渡金属的掺杂，提高了环糊精修饰的羟基氧化铁的催化作用，同时金属掺杂以后，紫外光谱发生改变，导致羟基氧化铁禁带宽度改变，光催化性能进而改变。

Claims (20)

  1. 一步法合成环糊精修饰的过渡金属氧化物材料的方法，包括步骤如下：
    将过渡金属氧化物盐和环糊精加入溶剂中，搅拌反应1h～72h，反应得到的固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的过渡金属氧化物材料，过渡金属氧化物盐与环糊精的质量比为：(0.1～200)：(0.1～50)，过渡金属氧化物盐与溶剂的质量体积比为：(0.1～10)：(100～2000)，单位：g/mL。
  2. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，所述的过渡金属氧化物盐为铜盐或铁盐。
  3. 根据权利要求2所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，所述的铜盐为氯化亚铜、溴化亚铜、碘化亚铜、硫酸亚铜、碳酸亚铜或氮化亚铜；所述的铜盐为氯化亚铜。
  4. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，所述的环糊精为α-环糊精、β-环糊精或γ-环糊精；优选的，所述的环糊精为β-环糊精。
  5. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，所述的铁盐为氯化铁或氯化亚铁；优选的，所述的铁盐为氯化亚铁。
  6. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，所述的溶剂为水或醇类溶剂；优选的，所述的醇类溶剂为2个羟基以上的醇类溶剂，进一步优选的，所述的醇类物质选自乙二醇、二乙二醇、1,2‐丙二醇、1,3‐丙二醇、甘油、1,3‐丁二醇、1,4‐丁二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇或三羟甲基丙烷中的一种或多种的混合物；所述的溶剂为水。
  7. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，当过渡金属氧化物盐为铜盐，制得一步法合成环糊精修饰的氧化亚铜材料，制备方法，包括步骤如下：
    将铜盐和环糊精加入溶剂中，搅拌反应1h～72h，反应得到的砖红色固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的氧化亚铜材料，铜盐与环糊精的质量比为：(0.1～10)：(0.1～50)，铜盐与溶剂的质量体积比为：(0.1～10)：(100～2000)，单位：g/mL。
  8. 根据权利要求7所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，铜盐与环糊精的质量比为：(0.1～8)：(0.1～20)。
  9. 根据权利要求7所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特 征在于，铜盐与溶剂的质量体积比为：(0.1～10)：(100～1000)，单位：g/mL；
  10. 根据权利要求9所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，铜盐与溶剂的质量体积比为：(0.1～10)：(100～600)，单位：g/mL；最为优选的，铜盐与溶剂的质量体积比为：(0.1～10)：200，单位：g/mL。
  11. 根据权利要求7所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，反应时间为10～48h，进一步优选的，反应时间为20～36h，最为优选的，反应时间为24h。
  12. 根据权利要求7所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，反应环境为在小于等于40℃温度下反应，优选的，反应温度为20～40℃；所述的干燥为置于真空干燥箱中进行干燥，干燥温度为50～70℃，干燥时间10～16小时。
  13. 一步法合成环糊精修饰的氧化亚铜材料的方法，包括步骤如下：
    将铜盐和环糊精加入水或醇类溶剂中，搅拌反应10h～48h，反应得到的砖红色固体分别用无水乙醇、去离子水清洗，干燥后得到环糊精修饰的氧化亚铜材料，铜盐与环糊精的质量比为：(0.1～10)：(0.1～50)，铜盐与溶剂的质量体积比为：(0.1～10)：(100～1000)，单位：g/mL。
  14. 根据权利要求1所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，当过渡金属氧化物盐为铁盐，制得一步法合成环糊精修饰的羟基氧化铁材料，制备过程中掺杂金属盐，得到金属掺杂环糊精修饰的羟基氧化铁材料，制备方法包括步骤如下：
    将铁盐、金属盐和环糊精加入水中，搅拌反应10h～72h，反应得到的黄褐色固体分别用无水乙醇、去离子水清洗，干燥后得到金属掺杂环糊精修饰的羟基氧化铁材料，铁盐与环糊精的质量比为：(10～200)：(1～50)，铁盐与水的质量体积比为：(0.1～10)：(10～200)，单位：g/mL，金属盐的加入量为铁盐质量的0.1-10％。
  15. 根据权利要求14所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，金属盐为过渡金属盐或贵金属盐，过渡金属盐为铜、锰、钴或镍的碳酸盐、硫酸盐、硝酸盐、氯化盐；过渡金属盐为金、银、钯或铂的盐类。
  16. 根据权利要求14所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，，其特征在于，过渡金属盐为铜、锰、钴或镍的硝酸盐。
  17. 根据权利要求16所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，金、银、钯或铂的盐类为氯金酸、硝酸银、氯化钯或醋酸钯；
    当金属盐为过渡金属盐，将铁盐、过渡金属盐和环糊精加入水中，搅拌反应，反应后洗涤，干燥后得到金属掺杂环糊精修饰的羟基氧化铁材料；
    当金属盐为贵金属盐，将铁盐、贵金属盐和环糊精加入水中，搅拌反应，反应后洗涤，干燥，氢气还原得到金属掺杂环糊精修饰的羟基氧化铁材料。
  18. 根据权利要求14所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，铁盐与环糊精的质量比为：(10～100)：(5～20)。
  19. 根据权利要求14所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，铁盐与水的质量体积比为：(0.5～10)：(10～100)，单位：g/mL；
    优选的，铁盐与水的质量体积比为：(0.5～10)：(10～80)，单位：g/mL；最为优选的，铁盐与水的质量体积比为：(0.5～10)：50，单位：g/mL；反应时间为10～36h，进一步优选的，反应时间为20～36h，最为优选的，反应时间为24h。
  20. 根据权利要求14所述的一步法合成环糊精修饰的过渡金属氧化物材料的方法，其特征在于，反应环境为在小于等于50℃温度下反应，优选的，反应温度为25℃；所述的干燥为置于电热鼓风干燥箱中进行干燥，干燥温度为60～80℃，干燥时间10～16小时。
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