CN113413877A - ZIF-8@ TiO2-Gd composite material and preparation method and application thereof - Google Patents

ZIF-8@ TiO2-Gd composite material and preparation method and application thereof Download PDF

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CN113413877A
CN113413877A CN202110617594.0A CN202110617594A CN113413877A CN 113413877 A CN113413877 A CN 113413877A CN 202110617594 A CN202110617594 A CN 202110617594A CN 113413877 A CN113413877 A CN 113413877A
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tio
zif
solution
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CN113413877B (en
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张晓涛
张万奇
王喜明
邵亚丽
刘哲辰
盛显良
安宇宏
胡子雏
王强
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Inner Mongolia Agricultural University
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Abstract

The invention provides ZIF-8@ TiO2The excellent property of rare earth metal is utilized to expand TiO in the-Gd composite material and the preparation method and the application thereof2The light response range greatly improves the photocatalytic degradation performance, and simultaneouslyGd-doped TiO2After being compounded with ZIF-8, the composite material improves the specific surface area of the material and introduces more reaction sites, and from two technologies of adsorption and photocatalysis, an adsorption-photocatalytic degradation material with a novel combined function of adsorption and photocatalysis is designed, so that a new idea is provided for designing a novel organic dye treatment material.

Description

ZIF-8@ TiO2-Gd composite material and preparation method and application thereof
Technical Field
The invention relates to an organic dye adsorption-photocatalysis material, in particular to a rare earth metal Gd-doped TiO2The novel adsorption-photocatalysis material is compounded with a metal organic framework material ZIF-8 and is used for photocatalytic degradation of organic dye in wastewater.
Background
With the development of industry, more and more waste water is discharged into water environment, industrial waste water contains a large amount of refractory organic pollutants, organic dyes are one of main chemical pollutants affecting water quality, and are difficult to remove from natural environment due to stable and complex structure, and can destroy local ecological environment when directly discharged into the environment, and the toxicity, carcinogenicity, mutagenicity and teratogenicity of the refractory organic pollutants can seriously threaten human health. The current society faces the situation of water resource scarcity, and a large amount of dye wastewater is discharged in factories every year, so that the toxicity in water and the required oxygen amount are increased, the water resource is seriously polluted, and the harm to the ecological environment and the human existence is great. Therefore, it is urgent to research the organic dye wastewater that can be effectively degraded.
The common treatment method for dye wastewater comprises a physical method, a chemical method, a physical-chemical method and the like. Typical methods are for example: filtration, precipitation, air flotation, high temperature deep oxidation, electrochemical methods, and the like. However, the conventional treatment methods have defects in the process of treating the organic dye wastewater to different degrees, so that the conventional treatment methods are limited in practical application, such as: some treatment methods have the treatment principle that a certain harmful substance is converted into another substance which can pollute the environment, the problem is not fundamentally solved, and the secondary pollution problem is serious.
TiO2The star molecule has the excellent properties of no toxicity, stable chemical property, low price and the like, and is a star molecule in the field of photocatalysis, so that the application of the star molecule is quite wide. For example, the organic pollutants in the sewage can be degraded, the air can be purified, and the antibacterial function in self-cleaning and medical and health can be realized. But TiO22The large forbidden band width (3.2 eV for anatase phase and 3.0 eV for rutile phase) makes it possible to utilize only UV with wavelength less than 380 nm, which is less than 5% of sunlight. Furthermore, when TiO2When excited, photogenerated carriers generated by photoexcitation are easy to recombine before being utilized, i.e. TiO2Has low quantum efficiency, which seriously restricts TiO2The practical application of (1). Therefore, how to prepare TiO with high visible light response2Photocatalysts and improvement of quantum efficiency thereof are important research subjects in the field of photocatalysis at present.
The metal organic framework Material (MOFs) is a novel porous framework material assembled by inorganic metal ions or metal ion clusters and carboxyl and amino plasma in an organic compound. Zeolite imidazolate framework materials (ZIF-8) are a subset of MOF materials, the ZnN formed by the linkage of transition metal Zn ions to N atoms in methylimidazolyl esters4A tetrahedral structural unit. The MOF material has the characteristics of large specific surface area, high porosity and the like, and also has good thermal stability and water stability. Through the specific structure and characteristics of ZIF-8, the problems of catalyst aggregation, small specific surface area and the like are reduced, and the catalyst is expected to be combined with a rare earth metal catalyst to improve the catalytic performance of the catalyst.
The invention utilizes the sol-gel method to dope the rare earth gold in the process of preparing the titanium dioxideGadolinium (Gd) to increase TiO2The gadolinium (Gd) is modified into TiO by a solvent synthesis method2Is compounded with a metal organic framework material ZIF-8 with larger specific surface area, and the excellent adsorption property of the ZIF-8 is combined with gadolinium (Gd) -modified TiO2The excellent photocatalytic degradation performance is perfectly combined to prepare the novel ZIF-8@ TiO2The (Gd) adsorbs-photocatalyst, and is applied to the photocatalytic degradation of organic dye neutral red, so that the excellent catalytic degradation effect is shown, a new treatment idea is provided for treating organic pollutants in industrial wastewater, and the application prospect is good.
Disclosure of Invention
The invention provides ZIF-8@ TiO2the-Gd composite material and the preparation method and the application thereof have the advantages of simple preparation and high degradation performance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
ZIF-8@ TiO2-Gd composite material, said material being a rare earth Gd doped TiO2And a metal-organic framework material ZIF-8 composite material, wherein the specific surface area of the composite material is 180-230m2/g, wherein Gd ions are highly dispersed in TiO2The composite material is prepared by the following steps:
(1) preparation of TiO2-Gd：
(a) Preparing a solution A: adding deionized water, glacial acetic acid and polyethylene glycol 400 into anhydrous ethanol, and adding a certain mass of Gd (NO) into the solution A3)36H2O, uniformly stirring the mixed solution, and magnetically stirring for 20-30 min;
preparing a solution B: slowly adding tetrabutyl titanate into anhydrous ethanol, stirring uniformly, and magnetically stirring for 20-30 min;
(b) slowly dripping the solution A into the solution B, stirring vigorously until the color changes from milky white to light yellow, sealing the sol in a beaker, and standing in the shade to form soft elastic solid gel;
(c) the solid gel with the sealing film removed is placed in a vacuum drying oven for drying to form yellow granular crystals, dried gel is prepared, and the dried gel is placed in a mortar for grinding to powder;
(d) placing the ground powder in a crucible, placing the crucible containing the sample in a box furnace for calcination treatment, naturally cooling and sieving;
(2) preparation of ZIF-8@ TiO2-Gd：
Adding zinc nitrate hexahydrate and 2-methylimidazole into N, N-dimethylformamide, and simultaneously adding prepared TiO2Performing ultrasonic treatment for 20-30min at room temperature to obtain mixed solution, placing the mixed solution in a stainless steel high-pressure reaction kettle, placing the mixed solution in an electric heating blowing dry box, taking out yellow solid in the reaction kettle, washing, centrifuging, drying and grinding to obtain ZIF-8@ TiO2-Gd。
In certain embodiments, the step (a) is performed in the presence of anhydrous ethanol: glacial acetic acid: the volume ratio of the polyethylene glycol 400 is 10 (2-3) to (4-6) to (0.5-1.5), preferably 10mL of absolute ethyl alcohol, 2.5 mL of deionized water, 5 mL of glacial acetic acid and 1mL of polyethylene glycol 4001, wherein the ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: (1-2), preferably 10mL of tetrabutyltitanate, 15 mL of anhydrous ethanol.
In certain embodiments, the Gd element is doped in TiO2The molar ratio of (B) is 0.1-2%.
In certain embodiments, the stirring time in step (b) is from 1 to 3 hours, and the aging time is from 18 to 30 hours; the drying temperature in the step (c) is 80-120 DEG CoC, the time is 18-36h, the sieving in the step (d) is 150-450 meshes, preferably 200 meshes, and the calcining temperature is 350-450 meshesoC, preferably 400oC。
In certain embodiments, the zinc nitrate hexahydrate: 2-methylimidazole: the mass ratio of the N, N-dimethylformamide is 450-500-100-120: 30-40, wherein 477.8 mg of zinc nitrate hexahydrate, 120 mg of 2-methylimidazole and 36mL of N, N-dimethylformamide are preferred.
In certain embodiments, the TiO is2The amount of Gd added is 0.1-0.4 g.
In some specific embodiments, in the step (2), the temperature of the electrothermal blowing drying oven is programmed to be: at 5-8oC/min is heated to 130-oC, preserving heat for 24-36h and then 0.4-0.5oThe rate of C/min was decreased to room temperature.
In certain embodiments, the washing is a DMF washing and the drying is from 50 to 70oAnd C, drying for 4-6 h in a vacuum drying oven.
In certain embodiments, the composite material is an adsorption-photocatalytic material and is used for the catalytic degradation of organic dyes.
In certain embodiments, the composite material has a degradation efficiency of greater than 93% of neutral red solution under light conditions.
TiO2Is an environment-friendly semiconductor material, has high activity and stability, is nontoxic and safe, and is widely applied to the field of modern pollution control. TiO22Heterogeneous photocatalysis has made great progress in the photocatalytic removal of aqueous and gaseous, organic and inorganic pollutants, and has received extensive attention and research as a potential environmental pollution deep purification technology. TiO22The photocatalyst can be made to enter into TiO by compounding other substances2Inside the crystal, the compounded metal ions become capture traps of photo-generated electrons so as to improve the catalytic activity of the photocatalyst. The photocatalysis technology is green and economic, has the unique advantage of solving the problem of environmental pollution by using renewable solar energy, is widely applied to the aspect of catalytically degrading organic matters in dye wastewater, avoids secondary pollution and saves cost. Modified TiO2The photocatalytic material not only has the advantages of good chemical stability, higher activity, no toxicity, no harm and the like, but also reduces the cost, expands the photocatalytic reaction under the condition of visible light, and improves the overall utilization rate of the material to the visible light.
Rare earth metals (rare earth metals), also known as rare earth elements, are a general term for 17 elements of scandium, yttrium, and lanthanides in group IIIB of the periodic table of elements. Most of rare earth elements have special electronic structures, have 4f orbitals which are not completely filled with electrons or empty 5d orbitals, and have larger atomic radius compared with Ti atoms, and due to the special electronic arrangement and larger atomic radius of the rare earth elements, the rare earth elements have the defects which are not existed in common elementsChemical nature or higher chemical activity. In TiO2The middle doped with rare earth elements is beneficial to adjusting TiO2To improve the crystal structure of TiO2The photocatalytic performance of (a).
The Metal Organic Frameworks (MOFs) are composed of Metal central ions and multifunctional Organic ligands, and are Organic-inorganic hybrid materials with unique pores and grids. Because MOFs have porosity, large specific surface area, structural and functional diversity and unsaturated metal sites, MOFs have been widely used in the fields of hydrogen storage, catalysis, drug carriers, adsorption and separation. Among them, ZIF-8 is typically represented by Zn2+The MOFs material is formed by connecting central ions and 2-methylimidazole serving as organic ligands and has a sodalite type topological structure. ZIF-8 and the composite material thereof are good adsorbents of organic dyes due to the fact that the ZIF-8 and the composite material thereof have specific surface area and good chemical stability and thermal stability. The core-shell structure material has the performance and advantages of an inner material and an outer material, and provides a new idea and a new method for synthesizing a new material. To Gd-doped TiO2Further compounding with ZIF-8 to disperse ZIF-8 in TiO2Surface formed core-shell structure material ZIF-8@ TiO2(Gd), ZIF-8 made up for TiO2Has a low specific surface area, so that the adsorptive property of the material is enhanced and the material is distributed in TiO2The rare earth metal Gd on the surface also increases the corresponding range of the material, increases the utilization rate of light, greatly improves the photocatalytic degradation performance of the material on organic dye, and is ZIF-8@ TiO2The marketing of organic dye pollutants in (Gd) treatment wastewater lays a theoretical foundation.
ZIF-8@ TiO prepared by the invention2The (Gd) material mainly comprises the following components:
1. TiO doped with rare earth metal gadolinium (Gd)2Preparation of
Selecting tetrabutyl titanate required by the test by a sol-gel method, adding the tetrabutyl titanate into absolute ethyl alcohol to prepare a solution, and selecting the rare earth metal salt Gd (NO) to be doped3)36H2O, absolute ethyl alcohol, glacial acetic acid, polyethylene glycol-400 and the likeMixing the other solution and the two solutions, stirring to form sol, aging to form wet gel, drying to form dry gel, heating and calcining to obtain the required TiO2And (3) sampling. The preparation reaction condition (rare earth metal doping amount) is changed by adopting a single-factor experiment to determine the preparation of the TiO doped with the rare earth metal gadolinium (Gd)2The best method is characterized and analyzed by applying technologies such as XRD, SEM, TEM, BET, XPS, DRS analysis and the like to know the TiO doped with rare earth metal gadolinium (Gd)2The crystal type in (1) and the microstructure of the nanostructure thereof.
2. ZIF-8@TiO2Preparation of (Gd)
Transferring metal salt zinc nitrate hexahydrate and organic ligand 2-methylimidazole required by an experiment into an organic solvent N, N-dimethylformamide according to a certain proportion by adopting a solvent synthesis method, and simultaneously adding a certain mass of prepared rare earth metal gadolinium (Gd) -doped TiO2After ultrasonic dispersion, the sample is fully dissolved and uniformly distributed, and then the solution is transferred into a reaction kettle with a polytetrafluoroethylene lining to generate ZIF-8@ TiO under the autogenous pressure2(Gd) crystals, and then carrying out subsequent treatments such as filtration, washing, drying and the like on the crystals to obtain the test sample. The ZIF-8@ TiO is known by using the techniques of XRD, SEM, TEM, BET, XPS, DRS analysis and the like2Crystal type, micro morphology, functional group, photoresponse range and the like in (Gd).
3. ZIF-8@TiO2(Gd) adsorption-photocatalytic material for adsorption-photocatalytic degradation of organic dye in water
Selecting neutral red optimal adsorption-photocatalysis conditions (neutral red initial concentration, catalyst dosage and the like) according to the properties of the organic dye neutral red subjected to adsorption-photocatalytic degradation, and using ZIF-8@ TiO2(Gd) adsorption-photocatalytic degradation material is used for carrying out adsorption-photocatalytic degradation performance research on neutral red, and ZIF-8@ TiO is measured2(Gd) compares and analyzes the maximum degradation efficiency of neutral red, tests the recycling times of the catalyst and evaluates ZIF-8@ TiO from the adsorption-catalysis efficiency and the recycling times2The (Gd) has application potential in the actual production process, and ZIF-8 and TiO are enriched2And in the treatment thereof withIndustrial application in organic pollutants.
The beneficial technical effects are as follows:
the application adopts rare earth metal Gd to TiO for the first time2Carrying out modification treatment, and further compounding with a metal organic framework material ZIF-8 to prepare a novel composite adsorption-photocatalytic material ZIF-8@ TiO with a core-shell structure and capable of carrying out adsorption-photocatalytic degradation on organic dye in industrial wastewater2(Gd), the composite adsorption-photocatalysis material expands TiO by utilizing the excellent property of rare earth metal2The photoresponse range greatly improves the photocatalytic degradation performance, and Gd-doped TiO2After the compound is compounded with ZIF-8, the specific surface area of the material is improved, and more reaction sites are introduced. From two technologies of adsorption and photocatalysis, a novel adsorption-photocatalytic degradation material with a combined function of adsorption and photocatalysis is designed, a novel thought is provided for designing a novel organic dye treatment material, and ZIF-8@ TiO is also provided2The industrial application of (Gd) in the organic dye treatment industry in the wastewater lays a certain experimental and data foundation.
Drawings
FIG. 1 Effect of Gd doping amount on photocatalytic efficiency;
FIG. 2 effect of initial concentration of neutral Red on catalytic efficiency;
FIG. 3 influence of catalyst dosage on catalytic efficiency;
FIG. 4 is a graph of catalyst cycle times;
FIG. 5 doping of different amounts of Gd element TiO2XRD pattern (a) and XRD pattern (b) of the composite material, and calcination temperature 400oC, calcining for 5 hours;
FIG. 6 ZIF-8@ TiO2EDX map of (0.3% Gd);
FIG. 7 ZIF-8@ TiO2(0.3% Gd) single element EDX-mapping plot;
FIG. 8 ZIF-8@ TiO2SEM images (a-d) and TEM images (e, f) of (0.3% Gd);
FIG. 9 TiO2（0.3%Gd）N2-suction-off of the drawing;
FIG. 10 ZIF-8@ TiO2N of (0.3% Gd)2-suction-off of the drawing;
FIG. 11 ZIF-8@ TiO2(0.3% Gd) XPS analysis;
fig. 12 materials DRS diagram (a, b) and forbidden band width diagram (c, d).
Detailed Description
Example 1 rare earth gadolinium (Gd) -doped TiO2Preparation of
1. Solution A: adding 2.5 mL deionized water, 5 mL glacial acetic acid and 1mL polyethylene glycol 400(PEG 400) into 10mL absolute ethyl alcohol, and adding a certain mass of Gd (NO) into the solution A3)36H2O, uniformly stirring the mixed solution;
and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
2. stirring the solution A and the solution B for 20-30min on a magnetic stirrer at room temperature; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; with Gd (NO)3)36H2Increasing the addition amount of O, and changing the color from milky white to light yellow; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
3. the gel with the sealing film removed was placed in a vacuum oven 100oC, drying for 24 hours to form yellow granular crystals, and preparing xerogel; the xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding;
4. placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with 200 mesh sieve after calcination, taking the lower layer powder for photocatalytic test, and treating the treated TiO2Is described as TiO2(400oC)；
5.Gd(NO3)36H2The doping amount of O is determined according to the molar ratio of Gd to Ti ions, if Gd: Ti =1%, the molar ratio of Gd to Ti ions is 1%, and Gd (NO) is determined according to the molar ratio3)36H2The mass of O; adding different substances to the solution A in sequenceAmount of Gd (NO)3)36H2Doping of O and Gd elements in TiO2The molar ratios of (A) to (B) are 0%, 0.1%, 0.3%, 0.5%, 1% and 2% in this order. For the sake of convenience, gadolinium-doped TiO2In turn denoted as TiO2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2% Gd), Gd (NO) doped3)36H2TiO of O2The calcination temperature is still 400oC。
Example 2 ZIF-8@ TiO2Preparation of (Gd)
1. 477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added2(Gd)0.2g, and performing ultrasonic treatment for 20 min at room temperature to fully dissolve and uniformly distribute the reagent;
2. mixing zinc nitrate hexahydrate, 2-methylimidazole and TiO2The mixed solution of (0.3% Gd) and DMF was placed in a 100 mL stainless steel autoclave and dried in an electrothermal blowing dry box with 5oC/min heating to 140oC. Keeping the temperature for 24 hours and then keeping the temperature for 0.4 houroThe speed of C/min is reduced to room temperature; taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing and centrifuging by using DMF (dimethyl formamide), and putting the final product at 60 DEG oDrying in a vacuum drying oven for 5 h, and grinding into powder to obtain ZIF-8@ TiO2(Gd) material.
Example 3 ZIF-8@ TiO2Catalytic degradation of organic dye by (Gd) composite adsorption-photocatalysis material
1. A BL-GHX-V type photoreaction instrument is adopted, a 550W mercury lamp is used as an ultraviolet light source, and an HP-116 type electromagnetic vibration type air pump is adopted to introduce air as an oxygen source; weighing 20mg of the adsorption-photocatalyst in the embodiment 2, adding the adsorption-photocatalyst into 100 mL of neutral red solution, and placing the solution into a photocatalytic reaction test tube; stirring for 30min in a dark environment to ensure that the sample achieves adsorption balance and avoid the influence of adsorption on the photocatalysis effect; after dark reaction for 30min, turning on a mercury lamp, taking 5 mL of reaction solution into a centrifuge tube by using a 5 mL pipette at intervals of 20 min, centrifuging (the rotation speed is 8000 rpm), taking supernatant, performing wavelength test, selecting a TU-1901 type ultraviolet-visible light photometer as a wavelength test instrument, measuring absorbance, and calculating the photocatalytic efficiency.
Example 4
TiO2Effect of doping with varying amounts of the rare earth gadolinium (Gd) on catalytic efficiency
1. Solution A: adding 2.5 mL deionized water, 5 mL glacial acetic acid and 1mL polyethylene glycol 400(PEG 400) into 10mL absolute ethyl alcohol, and adding a certain mass of Gd (NO) into the solution A3)36H2O, uniformly stirring the mixed solution;
2. and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
2. stirring the solution A and the solution B for 20-30min on a magnetic stirrer at room temperature; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; with Gd (NO)3)36H2Increasing the addition amount of O, and changing the color from milky white to light yellow; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
3. the gel with the sealing film removed was placed in a vacuum oven 100oC, drying for 24 hours to form yellow granular crystals, and preparing xerogel; the xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding;
4. placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with 200 mesh sieve after calcination, taking the lower layer powder for photocatalytic test, and treating the treated TiO2Is described as TiO2(400oC)；
5.Gd(NO3)36H2The doping amount of O is determined according to the molar ratio of Gd to Ti ions, if Gd: Ti =1%, the molar ratio of Gd to Ti ions is 1%, and Gd (NO) is determined according to the molar ratio3)36H2The mass of O; different masses of Gd (N) were added to the A solution in sequenceO3)36H2Doping of O and Gd elements in TiO2The molar ratios of (A) to (B) are 0%, 0.1%, 0.3%, 0.5%, 1% and 2% in this order. For the sake of convenience, gadolinium-doped TiO2In turn denoted as TiO2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2% Gd), Gd (NO) doped3)36H2TiO of O2The calcination temperature is still 400oC；
6. 477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added20.2g of (0.3% Gd), and performing ultrasonic treatment for 20 min at room temperature to ensure that the reagent is fully dissolved and uniformly distributed;
7. mixing TiO containing zinc nitrate hexahydrate, 2-methylimidazole and doped with different amounts of Gd2The mixed solution of DMF was placed in a 100 mL stainless steel autoclave and dried in an electric hot air drying oven at 5 deg.CoC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4 oThe speed of C/min is reduced to room temperature; taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing with DMF, and centrifuging; the final product is at 60 oDrying in a vacuum drying oven for 5 h, and grinding into powder to obtain Gd-doped ZIF-8@ TiO2(Gd) material;
8. in the photocatalysis test, a BL-GHX-V ratio Laman photochemical reaction instrument is adopted, a 550W mercury lamp is used as an ultraviolet light source, and a TU-1901 type ultraviolet-visible light photometer is used for calculating absorbance A; the catalyst is TiO2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2%Gd)、ZIF-8@TiO2(0.3% Gd); the dosage of the catalyst is 20mg, the concentration of the neutral red solution is 20 mg/L, and the volume is 100 mL; in a photochemical reaction instrument, dark reaction is firstly carried out for 30min, so that the adsorption-desorption balance of the catalyst is ensured, and the photocatalytic efficiency is prevented from being influenced by different adsorption-desorption performances of the catalyst; after dark reaction for 30min, turning on the ultraviolet lamp, sampling 5 mL every 20 min, centrifuging the solution (rotation speed 8000 rpm), measuring absorbance A, and countingCalculating the photocatalytic efficiency.
As can be seen from FIG. 1, it can be seen that in TiO2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2% Gd) in which photocatalytic efficiency increased first and then decreased, TiO2(0.3% Gd) has the highest catalytic efficiency; when the ultraviolet light irradiates for 1 h, the degradation efficiency can reach 94.53 percent, and the neutral red solution is changed from dark red to brown.
ZIF-8@TiO2(0.3% Gd) catalytic Condition and TiO2(0.3% Gd) same, but ZIF-8@ TiO2(0.3% Gd) catalytic efficiency to TiO2The (0.3% Gd) is high, the catalytic efficiency of ultraviolet irradiation for 1 h is 96.55%, and the catalytic effects of the ultraviolet irradiation and the TiO are similar, but the overall catalytic efficiency trend is ZIF-8@ TiO2(0.3% Gd) to TiO2(0.3% Gd) is high, so TiO2The (0.3 percent of Gd) and ZIF-8 are compounded to greatly improve TiO2Catalytic efficiency of (0.3% Gd); mainly due to TiO2The specific surface area of the material is improved after the (0.3% Gd) is compounded with the ZIF-8, and the analysis of the specific surface area in the table 1 shows that TiO2(0.3% Gd) has a BET specific surface area of 99.057m2/g，ZIF-8@TiO2(0.3% Gd) has a BET specific surface area of 189.14m2(ii)/g; the increase of the specific surface area solves the problem of TiO2The (0.3% Gd) reaction sites are insufficient, ZIF-8 provides a large number of reaction sites for photocatalytic reaction, and the photocatalytic efficiency is improved.
Example 5 Effect of initial concentration of neutral Red on catalytic efficiency
1. Solution A: 2.5 mL of deionized water, 5 mL of glacial acetic acid, and 1mL of polyethylene glycol 400(PEG 400) were added to 10mL of anhydrous ethanol, and 0.3% Gd (NO) was added to solution A3)36H2O (the molar ratio of elements is Gd: Ti =0.3), and uniformly stirring the mixed solution;
2. and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
2. stirring the solution A and the solution B for 20-30min on a magnetic stirrer at room temperature; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
3. the gel with the sealing film removed was placed in a vacuum oven 100oAnd C, drying for 24 hours to form yellow granular crystals, and preparing xerogel. The xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding; 4. placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with a 200-mesh sieve after calcination to obtain Gd-doped TiO2I.e. TiO2(0.3%Gd)；
5. 477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added20.2g of (0.3% Gd), and performing ultrasonic treatment for 20 min at room temperature to ensure that the reagent is fully dissolved and uniformly distributed;
6. mixing zinc nitrate hexahydrate, 2-methylimidazole and TiO2The mixed solution of (0.3% Gd) and DMF was placed in a 100 mL stainless steel autoclave and dried in an electrothermal blowing dry box with 5oC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4oThe speed of C/min is reduced to room temperature; taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing with DMF, and centrifuging; the final product is at 60 oDrying in a vacuum drying oven for 5 h, and grinding into powder to obtain Gd-doped ZIF-8@ TiO2(0.3% Gd) material;
7. in the photocatalysis test, a BL-GHX-V ratio Laman photochemical reaction instrument is adopted, a 550W mercury lamp is used as an ultraviolet light source, and a TU-1901 type ultraviolet-visible light photometer is used for calculating absorbance A; the catalyst is ZIF-8@ TiO2(0.3% Gd), the dosage of the catalyst is 20mg, the concentration of neutral red solution is 10 mg/L, 20 mg/L, 30 mg/L, 40 mg/L and 50 mg/L, and the volume is 100 mL; in a photochemical reaction instrument, dark reaction is firstly carried out for 30min, so that the adsorption-desorption balance of the catalyst is ensured, and the photocatalytic efficiency is prevented from being influenced by different adsorption-desorption performances of the catalyst; dark reaction after 30minTurning on an ultraviolet lamp, sampling 5 mL every 20 min, centrifuging the solution (the rotating speed is 8000 rpm), measuring the absorbance A, and calculating the photocatalytic efficiency;
as can be seen from FIG. 2, with the increase of the solution concentration, the catalytic efficiency is increased firstly and then reduced, and the catalytic efficiency of the neutral red solution is the highest at 20 mg/L; in the 10 mg/L neutral red solution, because a photogenerated carrier appears on the surface of the composite material, the low-concentration neutral red solution is not enough to fully utilize a reaction site, and when the concentration reaches 20 mg/L, the reaction site is fully utilized, so that the photocatalysis efficiency is improved. When the concentration of the solution is increased, the light penetration capacity is reduced, and the intermediate product occupies reaction sites, so that the photoresponse is weakened, the generation amount of photon-generated carriers is reduced, and the photocatalytic efficiency is reduced.
Example 6 Effect of catalyst amount on catalytic efficiency
1. Solution A: 2.5 mL of deionized water, 5 mL of glacial acetic acid, and 1mL of polyethylene glycol 400(PEG 400) were added to 10mL of anhydrous ethanol, and 0.3% Gd (NO) was added to solution A3)36H2O (the molar ratio of elements is Gd: Ti =0.3), and uniformly stirring the mixed solution;
and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
2. stirring the solution A and the solution B for 20-30min on a magnetic stirrer at room temperature; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
3. the gel with the sealing film removed was placed in a vacuum oven 100oAnd C, drying for 24 hours to form yellow granular crystals, and preparing xerogel. The xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding;
4. placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with 200 mesh sieve after calcination to obtain GdHetero TiO2I.e. TiO2(0.3%Gd)；
5. 477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added20.2g of (0.3% Gd), and performing ultrasonic treatment for 20 min at room temperature to ensure that the reagent is fully dissolved and uniformly distributed;
6. mixing zinc nitrate hexahydrate, 2-methylimidazole and TiO2The mixed solution of (0.3% Gd) and DMF was placed in a 100 mL stainless steel autoclave and dried in an electrothermal blowing dry box with 5oC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4oThe speed of C/min is reduced to room temperature; and (4) taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing with DMF, and centrifuging. The final product is at 60 oDrying in a vacuum drying oven for 5 h, and grinding into powder to obtain Gd-doped ZIF-8@ TiO2(0.3% Gd) material;
7. in the photocatalysis test, a BL-GHX-V ratio Laman photochemical reaction instrument is adopted, a 550W mercury lamp is used as an ultraviolet light source, and a TU-1901 type ultraviolet-visible light photometer is used for calculating absorbance A; the catalyst is ZIF-8@ TiO2(0.3% Gd), the dosage of the catalyst is 10 mg, 20mg, 30 mg, 40 mg and 50 mg, the concentration of neutral red solution is 20 mg/L, and the volume is 100 mL; in a photochemical reaction instrument, dark reaction is carried out for 30min, so that the adsorption-desorption balance of the catalyst is ensured, and the photocatalytic efficiency is prevented from being influenced by different adsorption-desorption performances of the catalyst; after dark reaction for 30min, turning on an ultraviolet lamp, sampling 5 mL every 20 min, centrifuging the solution (rotation speed 8000 rpm), measuring absorbance A, and calculating the photocatalytic efficiency according to the formula (1).
As can be seen from fig. 3, as the amount of the catalyst used increases, the photocatalytic efficiency increases, and the two are in positive correlation. This is because, as the amount of the catalyst used increases, the specific surface area and the reaction sites of the material are correspondingly increased, and under certain other conditions, as the amount of the catalyst used increases, the amount of the generated photogenerated electron-hole increases, and sufficient superoxide radicals and hydroxyl radicals are generated to participate in the degradation reaction.
Example 7 number of catalyst cycles test
1. Solution A: 2.5 mL of deionized water, 5 mL of glacial acetic acid, and 1mL of polyethylene glycol 400(PEG 400) were added to 10mL of anhydrous ethanol, and 0.3% Gd (NO) was added to solution A3)36H2O (the molar ratio of elements is Gd: Ti =0.3), and uniformly stirring the mixed solution;
and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
2. stirring the solution A and the solution B for 20-30min on a magnetic stirrer at room temperature; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
3. the gel with the sealing film removed was placed in a vacuum oven 100oC, drying for 24 hours to form yellow granular crystals, and preparing xerogel; the xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding;
4. placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with a 200-mesh sieve after calcination to obtain Gd-doped TiO2I.e. TiO2(0.3%Gd)；
5. 477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added20.2g of (0.3% Gd), and performing ultrasonic treatment for 20 min at room temperature to ensure that the reagent is fully dissolved and uniformly distributed;
6. mixing zinc nitrate hexahydrate, 2-methylimidazole and TiO2The mixed solution of (0.3% Gd) and DMF was placed in a 100 mL stainless steel autoclave and dried in an electrothermal blowing dry box with 5oC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4oThe speed of C/min is reduced to room temperature; taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing with DMF, and centrifuging; the final product is at 60 oC vacuum dryingDrying in a drying oven for 5 h, and grinding into powder to obtain Gd-doped ZIF-8@ TiO2(0.3% Gd) material;
7. in the photocatalysis test, a BL-GHX-V ratio Laman photochemical reaction instrument is adopted, a 550W mercury lamp is used as an ultraviolet light source, and a TU-1901 type ultraviolet-visible light photometer is used for calculating absorbance A; the catalyst is ZIF-8@ TiO2(0.3% Gd), the dosage of the catalyst is 20mg, the concentration of a neutral red solution is 20 mg/L, and the volume of the solution is 100 mL; from FIGS. 1, 2 and 3, ZIF-8@ TiO can be seen2After the (0.3% Gd) dark reaction is carried out for 30min, the degradation efficiency is high, in order to balance the adsorption reaction and the photocatalytic reaction in the early stage of the material and avoid one of the adsorption reaction and the photocatalytic reaction from dominating, the dark reaction is selected for 15 min, and the ultraviolet light is used for 45 min; dark reaction is carried out for 15 min; turning on an ultraviolet lamp, reacting for 45 min, taking supernate after the reaction is finished, centrifuging (the rotating speed is 8000 rpm), measuring the absorbance A, and calculating the photocatalytic efficiency; each time the bottom photocatalyst was collected, 100oC, drying for two hours and then recycling;
FIG. 4 is a graph of the number of times of catalyst recycling, and it can be seen from FIG. 4 that the catalytic efficiency can reach 81.16% after 3 times of catalyst recycling, and the fourth catalytic efficiency is reduced to 69.41%; this is because, with the use of the catalyst, a part of the catalyst is attached to the surface by the intermediate product, the catalyst becomes tan, the intermediate product occupies the active site, and the intermediate product cannot be effectively removed to affect the photocatalytic efficiency; the loss of the catalyst can be caused in the processes of centrifugation, washing and drying; wherein the influence of the intermediate products dominates.
Example 8 ZIF-8@ TiO2Characterization of (Gd) composite adsorption-photocatalytic material XRD, SEM, TEM, BET, XPS and DRS
1. TiO doped with rare earth metal gadolinium (Gd)2Preparation of
Solution A: adding 2.5 mL deionized water, 5 mL glacial acetic acid and 1mL polyethylene glycol 400(PEG 400) into 10mL absolute ethyl alcohol, and adding a certain mass of Gd (NO) into the solution A3)36H2O, uniformly stirring the mixed solution;
and B, liquid B: slowly adding 10mL of tetrabutyl titanate into 15 mL of absolute ethyl alcohol, and uniformly stirring;
at room temperature, liquid AStirring the solution B on a magnetic stirrer for 20-30 min; violent stirring is carried out, so that different reagents are uniformly distributed and dissolved; after the solution A and the solution B are stirred, slowly dripping the solution A into the solution B, and stirring vigorously for 2 hours, wherein the vortex of the stirred solution is changed from large to small and from deep to light to generate a light yellow viscous sol; with Gd (NO)3)36H2Increasing the addition amount of O, and changing the color from milky white to light yellow; sealing the sol in a beaker, and standing for 24 hours in the shade to form soft elastic solid gel;
the gel with the sealing film removed was placed in a vacuum oven 100oC, drying for 24 hours to form yellow granular crystals, and preparing xerogel; the xerogel is put in a mortar for grinding, so that solid particles are ground into powder, and no granular feeling is generated by hand twisting and grinding;
placing the ground powder into a crucible, placing the crucible containing the sample into a box furnace for calcination treatment, and selecting the temperature to be 400 DEGoC, heating and calcining; sieving with 200 mesh sieve after calcination, taking the lower layer powder for photocatalytic test, and treating the treated TiO2Is described as TiO2(400oC)；
5Gd(NO3)36H2The doping amount of O is determined according to the molar ratio of Gd to Ti ions, if Gd: Ti =1%, the molar ratio of Gd to Ti ions is 1%, and Gd (NO) is determined according to the molar ratio3)36H2The mass of O; different masses of Gd (NO) were added to the A solution in sequence3)36H2Doping of O and Gd elements in TiO2The molar ratio of the components is 0%, 0.1%, 0.3%, 0.5%, 1% and 2% in sequence; for the sake of convenience, gadolinium-doped TiO2In turn denoted as TiO2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2% Gd), Gd (NO) doped3)36H2TiO of O2The calcination temperature is still 400oC。
Preparation of ZIF-8
Adding 477.8 mg zinc nitrate hexahydrate and 120 mg 2-methylimidazole into 36 mLN, N-Dimethylformamide (DMF), and performing ultrasonic treatment at room temperature for 20 min to fully dissolve and uniformly distribute the sample;
putting the mixed solution of zinc nitrate hexahydrate, 2-methylimidazole and DMF (dimethyl formamide) into a 100 mL stainless steel high-pressure reaction kettle, and drying in an electrothermal blowing dry box by 5 percentoC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4oCooling to room temperature at C/min, taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and inner wall, washing with DMF, centrifuging, and collecting the final product at 60 deg.CoC, drying in a vacuum drying oven for 5 hours, and grinding into powder;
3.ZIF-8@TiO2preparation of (Gd)
477.8 mg of zinc nitrate hexahydrate and 120 mg of 2-methylimidazole were added to 36mL of N, N-Dimethylformamide (DMF), and the prepared TiO was added2(Gd)0.2g, and performing ultrasonic treatment for 20 min at room temperature to fully dissolve and uniformly distribute the reagent;
mixing zinc nitrate hexahydrate, 2-methylimidazole and TiO2The mixed solution of (0.3% Gd) and DMF was placed in a 100 mL stainless steel autoclave and dried in an electrothermal blowing dry box with 5oC/min heating to 140oC, preserving the heat for 24 hours and then preserving the heat for 0.4 oThe speed of C/min is reduced to room temperature; taking out the inner container of the stainless steel high-pressure reaction kettle, scraping off yellow solids on the bottom and the inner wall, washing with DMF, and centrifuging; the final product is at 60 oDrying in a vacuum drying oven for 5 h, and grinding into powder to obtain ZIF-8@ TiO2(Gd) material for adsorption-photocatalytic degradation of organic dyes;
4. TiO prepared in this example2(400oC)、TiO2(0.1% Gd)、TiO2(0.3%Gd)、TiO2(0.5% Gd)、TiO2(1% Gd)、TiO2(2%Gd)、ZIF-8、ZIF-8@TiO2(0.3% Gd); FIG. 5 is a graph of doping of varying amounts of Gd element TiO2XRD pattern (a) and XRD pattern (b) of the composite material (calcination temperature 400)oC, calcining for 5 h); FIG. 6 is ZIF-8@ TiO2EDX map of (0.3% Gd); FIG. 7 is ZIF-8@ TiO2(0.3% Gd) single element EDX-mapping plot; FIG. 8 is ZIF-8@ TiO2SEM images (a-d) and TEM images (e, f) of (0.3% Gd); FIG. 9 is ZIF-8@ TiO2N of (0.3% Gd)2-suction and removalThe accompanying drawings; table 1 shows TiO2(0.3%Gd)、ZIF-8@TiO2(0.3% Gd) specific surface area and pore diameter value; FIG. 10 is ZIF-8@ TiO2(0.3% Gd) XPS profile; fig. 11 is a graph of material DRS (a, b) and forbidden band width (c, d); table 2 is a material forbidden bandwidth table; FIG. 12 shows TiO at different temperatures2 DRS graph (a, b) and forbidden bandwidth graph (c, d).
FIG. 5, wherein FIG. 5(a) is Gd (NO) at different molar ratios3)36H2O-doped TiO2And undoped TiO2Calcination temperature 400oC, XRD pattern of calcination time 5 h. The diffraction angles corresponding to the respective diffraction peaks in FIG. 5(a) were compared with a standard diffraction card (JCPDS No.21-1272), 400oCalcining for 5 hours under C to generate anatase TiO with single crystal form2Rutile-free and brookite TiO2And occurs. As can be seen from the graph (a), the diffraction angle (2)θ)25.21o、37.82o、47.9o、62.56oRespectively in anatase form101)、(004)、(200)、(204) A crystal face; thereby determining that the single anatase type TiO prepared by the sol-gel method is single anatase type TiO2. As can be seen from FIG. 5(a), with Gd (NO)3)36H2Increase in O doping amount, 25.21oThe diffraction peak of (2) is broadened by a sharp peak. This indicates that the doped Gd ions are on TiO2The growth of the particles is inhibited, resulting in TiO2The grain size becomes smaller, the grains are refined, and the doping of Gd ions leads to TiO2Lattice distortion occurs, causing a decrease in lattice signal, so that the diffraction peak intensity is reduced. No gadolinium compound is detected in XRD detection, no relevant diffraction peak is found, and the Gd ions are highly dispersed in TiO2In (1). FIG. 5(b) is a XRD pattern of the composite material with the ZIF-8 crystal at 7.35o、10.34o、12.68o、14.66o、16.5o、18.0oStrong diffraction peaks appear corresponding to011)、(002)、(112)、(022)、(013)、(222) Crystal face, thereby determining ZIF-8 crystal. TiO in FIG. 5(b)2Diffraction Angle (2) (0.3% Gd)θ)25.21oThe corresponding crystal face is anatase type (101) A crystal plane. In a composite material ZIF-8@ TiO2(0.3% Gd) appeared as a peak of TiO2The composite peak of (0.3% Gd) and ZIF-8 proves that the material is a composite material of the two, and the individual peak is covered due to the different intensities of the peaks.
FIGS. 6(a), (b) are ZIF-8@ TiO2The EDX diagram of the (0.3% Gd) composite material shows that the material contains five elements of oxygen, titanium, zinc, gadolinium and nitrogen.
FIG. 7 is ZIF-8@ TiO2(0.3% Gd) single element EDX map, FIG. 7(a) is O element distribution map, (b) is Ti element distribution map, (c) is Gd element distribution map, (d) is Zn element distribution map, and (e) is N element distribution map. FIGS. 7(a) and (b) show that the distribution of O and Ti elements is similar, and effective combination of Ti and O is TiO2The presence of TiO was confirmed in the XRD examination2. FIGS. 7(b) and (d) show that there is a difference in the distribution of the two elements Ti and Zn in the composite material, and there is an overlap because TiO is present in the composite material2(0.3% Gd) was not uniformly distributed, some agglomerated, and some ZIF-8 was not coated with TiO2(0.3% Gd). But coating TiO on ZIF-82(0.3% Gd) and the distribution positions of Ti and Zn elements are similar. FIG. 7(c) the distribution of Gd element is the same as that of Ti element, illustrating that Gd element is doped into TiO2Or in TiO2Surface distribution, TiO in XRD2The Gd element is doped into TiO along with the change of the grain size of Gd element2Thereby affecting the grain size and crystal structure. Gd element appears in the vicinity of Zn element, which indirectly proves that TiO2(0.3% Gd) was complexed with ZIF-8.
As shown in FIGS. 8(a) and (b), the composite material ZIF-8@ TiO2(0.3% Gd) was distributed in the form of a lamellar or massive layer, and as is clear from FIGS. 8(c) and (d), TiO2The (0.3% Gd) is agglomerated on the ZIF-8, the agglomeration in the (d) is particularly obvious, and the microspherical TiO in a large range can be clearly seen2(0.3% Gd) aggregated together. FIGS. 8(e), (f) are ZIF-8@ TiO2TEM pictures of (0.3% Gd) composites clearly show TiO2(0.3% Gd) agglomeration and ZIF-8 coating on TiO2(0.3% Gd). TiO22The agglomeration of (0.3% Gd) may occurZIF-8@TiO2In the preparation of (0.3% Gd), TiO2(0.3 percent Gd) is unevenly distributed in the inner container of the stainless steel high-pressure reaction kettle, and the uniform dispersion degree is low.
As can be seen from FIG. 9, TiO2N of (0.3% Gd)2The sorption-desorption diagram belongs to the V-curve in the IUPAC curve, there being a capillary condensed multi-layer sorption profile. In thatP/P 0At 0.5-0.9, a retained loop appears, and capillary coagulation is generated. The retention return ring belongs to H2 type, is wider, has a much steeper desorption curve than an adsorption curve, and is mostly present in materials with wider pore channels and diversified pore types. As can be seen from Table 1, TiO2(0.3% Gd) has a BET specific surface area of 99.057m2(g, BET test Total pore volumeP/P 0=0.981) 0.1846 cm3(ii)/g, average pore diameter is 7.4553 nm, average pore diameter has exceeded mesopores (2-5nm), TiO2(0.3% Gd) is among the macroporous materials.
TABLE 1 TiO2(0.3% Gd), ZIF-8@ TiO2(0.3% Gd) specific surface area and Aperture values
Sample number BET specific surface area (m)2/g) Total pore volume (cm)3/ g) Average pore diameter (nm)
TiO2(0.3%Gd) 99.057 0.1846 7.4553
ZIF-8@TiO2(0.3%Gd) 189.14 0.2031 4.2944
FIG. 10 is ZIF-8@ TiO2(0.3%Gd)N2-drawing off by suction. As can be seen from FIG. 10, ZIF-8@ TiO2(0.3%Gd)N2The adsorption-desorption curve belongs to the type IV of the IUPAC curveThere is a single layer adsorption of capillary condensation. In thatP/P 0At 0.6-0.9, a retained loop appears, and capillary coagulation is generated. The retention return ring belongs to H2 type, is wider, has a much steeper desorption curve than an adsorption curve, and is mostly present in materials with wider pore channels and diversified pore types. As can be seen from Table 1, ZIF-8@ TiO2(0.3% Gd) has a BET specific surface area of 189.14m2(g, BET test Total pore volumeP/P 0=0.989) is 0.2031cm3Per g, average pore diameter 4.2944nm, ZIF-8@ TiO2(0.3% Gd) is among the mesoporous materials.
FIG. 11(a) is ZIF-8@ TiO2(0.3% Gd) XPS analysis summary map, in the composite material detected in nitrogen, titanium, oxygen, zinc, gadolinium element. Fig. 11(b) is an XPS chart of an N element in the composite material, which is assigned to ZIF-8, and two peaks, 398.7 eV and 399.5 eV respectively, appear at the time of peak matching, corresponding to pyridine type nitrogen and pyrrole type nitrogen of the N1s peak respectively. FIG. 11(C) is XPS for oxygen in the composite material, since ZIF-8 has a molecular formula of C8H10N4Zn, so that the oxygen element is considered to be derived from TiO2The oxygen atom in (b) was subjected to peak fitting, and diffraction peaks at 529.27 eV and 531.11 eV were found. Corresponding to lattice oxygen (529.5 eV) and surface-adsorbed oxygen (531.7 eV), respectively, the diffraction peak was shifted due to the doping of Gd element. Lattice oxygen derived from TiO2The oxygen (Ti-O) in (1) is presumed to form a Ti-O-Gd bond or an oxygen vacancy, and the surface-adsorbed oxygen exists as a Ti-OH bond. FIG. 11(d) is an XPS peak-off fit plot of Ti atoms, wherein 458.01 eV and 463.7 eV respectively belong to the Ti atom Ti 2p3/2And Ti 2p1/2And a characteristic peak, wherein the characteristic peak is shifted due to the doping of Gd element, and Ti element in the material exists in a +4 valence form. FIG. 11(e) is an XPS peak-fitted chart of Zn element in the composite material, showing diffraction peaks at 1021.75 eV and 1044.8 eV, corresponding to Zn 2p, respectively2/3(1021.3 eV) and Zn 2p1/2The electron transition of the (1044.4 eV) orbital demonstrates that Zn exists in the form of +2 valence in the composite material. Due to TiO2The recombination of (0.3% Gd) causes the shift of the diffraction peak, and a red shift of about 0.4 eV occurs. FIG. 11(f) is a Gd elementXPS peak fitting chart of biotin, 139.94 eV corresponds to Gd4d orbital characteristic peak, Gd element exists in a +3 valence form, and a bond exists in a Ti-O-Gd form. No change in the chemical valence state of the element occurs during the doping and recombination processes.
TABLE 2 material forbidden bandwidth table
Figure RE-DEST_PATH_IMAGE002
XRD test shows that TiO2At 400oCalcining for 5 h to obtain crystal form of anatase type or anatase type TiO2The forbidden band width is 3.2 eV, and when ultraviolet light irradiates a photo-generated electron, the photo-generated electron can jump from a valence band to a conduction band. At this time, the light energy is converted into electron energy, so that the electrons can cross the forbidden band, and the photo-generated electrons are transferred, thereby generating photo-generated electron-hole pairs. FIGS. 12(a) and (b) are TiO2Doping with different amounts of Gd and ZIF-8@ TiO2(0.3% Gd) and TiO2(400 oC) The DRS map of (a), (b) is an enlarged view of the shaded portion in (a). Fig. 12(c) and (d) are diagrams of the forbidden band widths of the above materials, and (d) is an enlarged view of the shaded portion in (c). It can be seen from (a) that as the doping content of Gd increases, the photoresponse range increases, and the ultraviolet diffuse reflectance spectrum curve is red-shifted. The Eg data in table 2 reflects the change in the decrease in the forbidden band width, in concert with the change in the optical response range. The Eg is reduced to different degrees along with the increase of the doping amount, which shows that the doping of Gd element can cause TiO2A change in the forbidden band and a change in the photoresponse range.
The invention adopts a sol-gel method to prepare TiO2Simultaneously doping rare earth metal gadolinium (Gd) according to a certain molar mass ratio, and realizing the aim that the rare earth metal is coupled with TiO2While preparing ZIF-8 by solvent synthesis method, a certain amount of Gd modified TiO is added2Preparing ZIF-8 and rare earth metal modified TiO2Novel composite adsorption-photocatalysis material ZIF-8@ TiO2(Gd) combined with the characteristic analysis of XRD, SEM, TEM, BET, XPS, DRS and the like, and the result shows that the Gd-doped TiO2Successfully compounded with ZIF-8 to form a ZIF-8 coated TiO2(Gd) nucleusThe shell structure type material has both adsorption and photocatalytic degradation performances, and is used for photocatalytic degradation of organic dye neutral red in water. Experimental results show that the material has a good effect on photocatalytic degradation of neutral red, has certain recycling performance, and has great industrial application potential. ZIF-8@ TiO2(Gd) novel adsorption-photocatalytic Material comparison ZIF-8 and TiO2(Gd) greatly improves the adsorption performance and the photocatalytic degradation performance, simultaneously enlarges the photoresponse range of the rare earth metal, improves the utilization rate of light, and provides valuable experimental data for further large-scale photocatalytic degradation treatment of organic dye in industrial wastewater.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (10)

1. ZIF-8@ TiO2-Gd composite material, said material being a rare earth Gd doped TiO2Is a ZIF-8 composite material with a metal-organic framework material, and is characterized in that the specific surface area in the composite material is 180-230m2/g, wherein Gd ions are highly dispersed in TiO2The composite material is prepared by the following steps:
(1) preparation of TiO2-Gd：
(a) Preparing a solution A: adding deionized water, glacial acetic acid and polyethylene glycol 400 into anhydrous ethanol, and adding a certain mass of Gd (NO) into the solution A3)36H2O, uniformly stirring the mixed solution, and magnetically stirring for 20-30 min;
preparing a solution B: slowly adding tetrabutyl titanate into anhydrous ethanol, stirring uniformly, and magnetically stirring for 20-30 min;
(b) slowly dripping the solution A into the solution B, stirring vigorously until the color changes from milky white to light yellow, sealing the sol in a beaker, and standing in the shade to form soft elastic solid gel;
(c) the solid gel with the sealing film removed is placed in a vacuum drying oven for drying to form yellow granular crystals, dried gel is prepared, and the dried gel is placed in a mortar for grinding to powder;
(d) placing the ground powder in a crucible, placing the crucible containing the sample in a box furnace for calcination treatment, naturally cooling and sieving;
(2) preparation of ZIF-8@ TiO2-Gd：
Adding zinc nitrate hexahydrate and 2-methylimidazole into N, N-dimethylformamide, and simultaneously adding prepared TiO2Performing ultrasonic treatment for 20-30min at room temperature to obtain mixed solution, placing the mixed solution in a stainless steel high-pressure reaction kettle, placing the mixed solution in an electric heating blowing dry box, taking out yellow solid in the reaction kettle, washing, centrifuging, drying and grinding to obtain ZIF-8@ TiO2-Gd。
2. A ZIF-8@ TiO as set forth in claim 12-Gd composite, characterized in that the step (a) absolute ethanol: glacial acetic acid: the volume ratio of the polyethylene glycol 400 is 10 (2-3) to (4-6) to (0.5-1.5), preferably 10mL of absolute ethyl alcohol, 2.5 mL of deionized water, 5 mL of glacial acetic acid and 1mL of polyethylene glycol 4001, wherein the ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: (1-2), preferably 10mL of tetrabutyltitanate, 15 mL of anhydrous ethanol.
3. A ZIF-8@ TiO as set forth in claim 12-Gd composite, characterised in that said Gd element is doped in TiO2The molar ratio of (B) is 0.1-2%.
4. A ZIF-8@ TiO as set forth in claim 12-Gd composite material, characterised in that in step (b) the stirring time is 1-3h and the aging time is 18-30 h; the drying temperature in the step (c) is 80-120 DEG CoC, the time is 18-36h, the sieving in the step (d) is 150-450 meshes, preferably 200 meshes, and the calcining temperature is 350-450 meshesoC, preferably 400oC。
5.A ZIF-8@ TiO as set forth in claim 12-Gd composite, characterized in that the zinc nitrate hexahydrate: 2-methylimidazole: the mass ratio of the N, N-dimethylformamide is 450-500-100-120: 30-40, wherein 477.8 mg of zinc nitrate hexahydrate, 120 mg of 2-methylimidazole and 36mL of N, N-dimethylformamide are preferred.
6. A ZIF-8@ TiO as set forth in claim 12-Gd composite material, characterized in that said TiO2The amount of Gd added is 0.1-0.4 g.
7. A ZIF-8@ TiO as set forth in claim 12-Gd composite material, characterized in that in step (2) the drying oven is programmed for temperature increase in electrothermal blowing, the programmed temperature being: at 5-8oC/min heating to 130-oC, preserving heat for 24-36h and then 0.4-0.5oThe rate of C/min was decreased to room temperature.
8. A ZIF-8@ TiO as set forth in claim 12-Gd composite, characterized in that the washing is DMF washing and the drying is 50-70oAnd C, drying for 4-6 h in a vacuum drying oven.
9. A ZIF-8@ TiO as claimed in any one of claims 1 to 82-use of a Gd composite, characterized in that the composite is an adsorption-photocatalytic material and is used for the catalytic degradation of organic dyes.
10. A ZIF-8@ TiO as set forth in claim 92-use of a Gd composite characterised in that the composite has a degradation efficiency in neutral red solution of more than 93% under light conditions.
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