CN115254189B - Iron tailing sand MOF composite photocatalyst and preparation method and application thereof - Google Patents
Iron tailing sand MOF composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115254189B CN115254189B CN202210768643.5A CN202210768643A CN115254189B CN 115254189 B CN115254189 B CN 115254189B CN 202210768643 A CN202210768643 A CN 202210768643A CN 115254189 B CN115254189 B CN 115254189B
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- iron tailing
- tailing sand
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 65
- 239000004576 sand Substances 0.000 title claims abstract description 49
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 13
- 239000000975 dye Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 239000012621 metal-organic framework Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to the technical field of photocatalysis, in particular to an iron tailing sand/MOF composite photocatalyst, a preparation method and application thereof, wherein the method comprises the steps of preparing an iron tailing sand catalyst, and then mixing the iron tailing sand catalyst with 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid, (CH) 3 COO) 2 Zn·2H 2 Mixing O, putting into a reaction kettle, adding a solvent, adjusting the pH value of the solution to 7.5, then putting the reaction kettle into an oven, heating to 110-130 ℃, carrying out heat preservation treatment for 5-8 hours, after cooling, washing substances in the reaction kettle with an organic solvent for three times, carrying out suction filtration on the solution, and then drying to obtain the iron tailing sand/MOF composite photocatalyst; according to the invention, the metal-organic framework and the waste iron tailing sand are used as raw materials to prepare the iron tailing sand/MOF composite photocatalyst, and experimental data prove that compared with a single iron tailing sanding catalyst, the iron tailing sand/MOF composite photocatalyst can remarkably improve the degradation rate of organic dye.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to an iron tailing sand/MOF composite photocatalyst and a preparation method and application thereof.
Background
Iron tailings are a solid waste, and the discharge amount thereof is increasing year by year. The iron tailing sand not only occupies a large amount of land and causes huge resource waste, but also brings serious pollution and harm to the human living environment and breaks ecological balance. Therefore, iron tailings are receiving attention from countries around the world as secondary resources for reuse.
In addition, contamination of organic dyes has been a serious environmental problem, and various methods have been sought to degrade organic dyes in the environment. The technology of degrading organic pollutants by photocatalysis is a technology which can fully utilize solar energy and help people solve the difficult problem of processing the organic pollutants, and is considered as one of the most promising technology of degrading organic dyes. The photocatalytic material is the key for realizing the degradation of the organic dye, so that the design and synthesis of the catalyst material which is environment-friendly, low in price and free from secondary pollution is urgent for the degradation of the organic dye.
Disclosure of Invention
The invention aims to provide an iron tailing sand/MOF composite photocatalyst for realizing efficient degradation of organic dye.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
a method for preparing iron tailing sand/MOF composite photocatalyst comprises mixing iron tailing sand with alkaline substances, calcining, washing with boiled water, and performing ultrasonic treatment, suction filtration, drying and grinding to obtain powdery solid;
dissolving the powdery solid by using an acid solution to obtain a mixed solution, then adjusting the pH value of the mixed solution to 7.5 by using an alkaline solution, transferring the mixed solution into a reaction kettle for heating treatment, cooling to room temperature after the reaction is finished, carrying out suction filtration on the reaction solution, drying and grinding to obtain the iron tailing sanding catalyst;
the iron tailing sanding catalyst is combined with 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid, (CH) 3 COO) 2 Zn·2H 2 Mixing O, adding a solvent, adjusting the pH value of the solution to 7.5, then placing the reaction kettle into a baking oven, heating to 110-130 ℃, preserving heat for 5-8h, after cooling, washing substances in the reaction kettle with an organic solvent for three times, carrying out suction filtration on the solution, and then drying to obtain the iron tailing sand/MOF composite photocatalyst.
In a further embodiment, the calcination treatment conditions include calcination treatment at a temperature of 740-780 ℃ for 20-40min.
In a further technical scheme, the conditions for heating the mixed solution in the reaction kettle include: the temperature is 190-210 ℃ and the time is 10-13h.
In a further technical scheme, relative to 100mg of the iron tailing sanding catalyst, the dosage of the 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid is 35-40mg, the (CH) 3 COO) 2 Zn·2H 2 The amount of O is 45-50mg.
The invention also provides the iron tailing sand/MOF composite photocatalyst prepared based on the method.
The invention also provides application of the iron tailing sand/MOF composite photocatalyst in degrading organic dye.
Compared with the prior art, the invention has the following technical effects:
the inventor of the application finds that in the technical scheme provided by the invention, the iron tailing sand/MOF composite photocatalyst is prepared by taking a metal-organic framework and waste iron tailing sand as raw materials, and experimental data prove that the iron tailing sand/MOF composite photocatalyst can remarkably improve the degradation rate of organic dye compared with a single iron tailing sand polishing catalyst;
in addition, as the iron tailing sanding catalyst is prepared from waste iron tailing sand, the iron tailing sand sanding catalyst has great cost advantage, compared with the MOF photocatalyst which has high cost and can only play a role in degradation after a certain use amount is required to be met, the iron tailing sand/MOF composite photocatalyst provided by the invention has less use amount, so that the degradation cost of organic dye is obviously reduced, in other words, the iron tailing sand/MOF composite photocatalyst provided by the application has better application prospect in degradation of organic dye.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a diagram showing the coordination environment of Compound 1 prepared in example 2;
FIG. 2 is a schematic diagram of a three-dimensional pore structure of the compound 1 prepared in example 2;
FIG. 3 is a graph showing the degradation of methylene orange by the iron tailings sand/MOF composite photocatalyst of test example 1;
FIG. 4 is a graph showing the degradation of methylene orange in comparative example 1;
FIG. 5 is a graph of the degradation of methylene orange by the iron tailings sanding catalyst of comparative example 2;
FIG. 6 is a graph showing the cyclic degradation performance of the iron tailing sand/MOF composite photocatalyst on methylene orange.
Detailed Description
The invention is further described in the following with reference to specific embodiments in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
Those skilled in the art know that metal-organic frameworks (MOFs) are a new class of porous materials that refer to coordination polymers of hollow structures with regular pore sizes and shapes obtained by molecular assembly and crystal engineering methods of inorganic metal centers or clusters and organic bridging ligands. The characteristics of high stability, adjustable pore size, large specific surface area, capability of modifying active groups in pore channels and the like of the metal-organic framework polymer are attracting great interest to scientists.
The invention takes the metal-organic framework and the waste iron tailing sand as raw materials to prepare the iron tailing sand/MOF photocatalytic composite material, thereby realizing the rapid degradation of organic dye.
The iron tailing sand/MOF composite photocatalyst provided by the present invention is further described below by way of specific examples.
Example 1: preparation of iron tailing sanding catalyst
Weighing 5.0g of NaOH and 0.3g of iron tailing sand, mixing, placing into a crucible, calcining for 30 minutes at 750 ℃ in a resistance furnace, washing with boiled water, performing ultrasonic treatment, suction filtration, drying and grinding to obtain powdery solid.
Weighing 0.2g of the powdery solid, adding 4mL of nitric acid to dissolve the powdery solid to obtain a mixed solution, regulating the pH value of the mixed solution to 7.5 by using a NaOH solution, transferring the mixed solution into a reaction kettle, heating the mixed solution at 200 ℃ for 12 hours, cooling the mixed solution to room temperature after the reaction is finished, filtering out the reaction solution by pumping, drying and grinding to obtain the iron tailing sanding catalyst.
Example 2: preparation of MOF photocatalyst
0.1mmol (36.5 mg) of 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid (H) 3 TTC) and 0.20mmol (48.5 mg) of (CH 3 COO) 2 Zn·2H 2 O was mixed and placed in a reaction vessel, then 15.0ml of N, N' -Dimethylformamide (DMF) solvent, 8.0ml of deionized water was added, and the pH of the solution was adjusted to 7.5 with nitric acid. The reaction vessel was placed in an oven and heated to 120℃and incubated for 4 days, then cooled to room temperature at a rate of 5℃per hour, at which time colorless needle crystals precipitated. The yield was 65%.
For convenience of description, the MOF photocatalyst prepared as described above is represented by compound 1.
Resolution and refinement of compound 1 was accomplished using the SHELXL-97 program package. The relevant crystallographic data for compound 1 are listed in table 1.
Table 1 crystal data of compound 1
a R 1 ＝Σ||F o |–|F c |)/Σ|F o |；wR 2 ＝[Σw(F o 2 –F c 2 ) 2 /Σw(F o 2 ) 2 ] 1/2
This example shows an example of microporous zinc compound [ Zn ] obtained by hydrothermal synthesis 3 (TTC) 2 ] n ·DMF(1)
The structural units of compound 1 are two fully protonated carboxylic acid ligands TTC, three zinc atoms and one free DMF molecule.
FIG. 1 is a diagram of the coordination environment of compound 1, in which there are two independent zinc atoms in compound 1. The Zn1 atom has four oxygen atoms involved in coordination, forming a tetrahedral structure, wherein the four oxygen atoms are derived from four monodentate TTC ligands, and the Zn1 atom is not coordinated to the nitrogen atom. The Zn2 atom is coordinated with two oxygen atoms and three nitrogen atoms on three TTC ligands respectively, and the spatial configuration is a deformed triangular bipyramid. In compound 1, the oxygen atom on the fully protonated carboxylic acid ligand is a monodentate coordinate. Compound 1 is a 3D tunnel complex with non-coordinated oxygen atoms extending into the tunnel, as shown in fig. 2.
Example 3: preparation of iron tailing sand/MOF composite photocatalyst
100mg of the iron tailing sanding catalyst prepared in example 1 and 0.1mmol (36.5 mg) of 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid (H) 3 TTC), 0.20mmol (48.5 mg) (CH 3 COO) 2 Zn·2H 2 Mixing O and then placing the mixture into a reaction kettle;
then 20ml of N, N' -Dimethylformamide (DMF), 10.0ml of deionized water was added, and the pH of the solution was adjusted to 7.5 with nitric acid; and then placing the reaction kettle into an oven, heating to 120 ℃, preserving heat for 6 hours, after cooling, cleaning the materials in the reaction kettle for three times by using DMF, carrying out suction filtration on the solution, and then drying to obtain the iron tailing sand/MOF composite photocatalyst.
Test example 1:
50mg of the iron tailing sand/MOF composite photocatalyst prepared in example 3 was dispersed in 100 ml of methylene orange aqueous solution (10 mg/liter) and stirred in the dark for 30 minutes to ensure that adsorption-desorption equilibrium was established.
The photocatalytic degradation of methylene orange was carried out on a photochemical reactor equipped with a 400 watt mercury lamp, sucking 5.0ml of the sample every 15 minutes, and then carrying out the analytical test with an ultraviolet-visible spectrophotometer.
As shown in fig. 3, the iron tailing sand/MOF composite photocatalyst was able to degrade about 90% of the methylene orange in 90 minutes.
Comparative example 1:
under the same test conditions as in test example 1, only 100 ml of a methylene orange aqueous solution (10 mg/l) was taken, and the iron tailing sand/MOF composite photocatalyst was not added, and was stirred in the dark for 30 minutes;
the photocatalytic degradation of methylene orange was then carried out on a photochemical reactor equipped with a 400 watt mercury lamp, sucking 5.0ml of the sample every 15 minutes, and then carrying out the analytical test with an ultraviolet-visible spectrophotometer.
As shown in fig. 4, the methylene orange was not substantially degraded.
Comparative example 2:
50mg of the iron tailing sand light catalyst prepared in example 1 was dispersed in 100 ml of methylene orange aqueous solution (10 mg/l) and stirred in the dark for 30 minutes to ensure that the adsorption-desorption equilibrium was established.
The photocatalytic degradation of methylene orange was carried out on a photochemical reactor equipped with a 400 watt mercury lamp, sucking 5.0ml of the sample every 15 minutes, and then carrying out the analytical test with an ultraviolet-visible spectrophotometer.
As shown in fig. 5, about 50% of the methylene orange was degraded in 90 minutes.
Based on the above experiments, the iron tailing sanding catalyst prepared by the invention has a certain photocatalysis effect and can be used for photocatalytic degradation of methylene orange; when the iron tailing sand provided by the invention is adopted
And when the MOF composite photocatalyst is used, methylene orange can be rapidly and efficiently degraded.
Photocatalytic cycle test:
the mixture after the degradation treatment of test example 1 for 90 minutes was filtered to screen out the iron tailing sand/MOF composite photocatalyst, and then dispersed again into 100 ml of a new aqueous solution of methylene orange (10 mg/liter) and stirred in the dark for 30 minutes to ensure establishment of adsorption-desorption equilibrium.
A second photocatalytic degradation of methylene orange was then carried out on a photochemical reactor equipped with a 400 watt mercury lamp, sucking 5.0ml of sample every 15 minutes, and then carrying out an analytical test with an ultraviolet-visible spectrophotometer.
After the degradation treatment for 90 minutes, filtering and screening out the iron tailing sand/MOF composite photocatalyst again, and carrying out a third photocatalytic degradation methylene orange test again by using the iron tailing sand/MOF composite photocatalyst.
The test results are shown in FIG. 6.
In FIG. 6, the abscissa represents degradation time, and the ordinate is C/C 0 Wherein C is a ratio of 0 For the initial methylene orange concentration, C is the methylene orange concentration measured at 15 minute intervals; the curves in the coordinate space correspond to the first, second and third tests for photocatalytic degradation of methylene orange from left to right, respectively.
Based on the test results of fig. 6, it can be seen that the iron tailing sand/MOF composite photocatalyst provided by the invention can still show excellent catalytic performance after three cycles.
Conclusion:
in the invention, a novel zinc compound [ Zn ] with active site is successfully synthesized by a hydrothermal synthesis method 3 (TTC) 2 ] n DMF (1). Compound 1 is a 3D tunnel complex with non-coordinated oxygen atoms extending into the tunnel. The test researches the degradation of the methylene orange by the iron tailing sanding catalyst and the degradation of the methylene orange by the iron tailing sand/MOF composite photocatalyst, and the test results show that the iron tailing sand/MOF composite photocatalyst can degrade the methylene orange rapidly and efficiently.
The foregoing has outlined and described the basic principles, main features and features of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A method for preparing iron tailing sand/MOF composite photocatalyst is characterized by comprising the steps of mixing iron tailing sand with alkaline substances, calcining, washing with boiled water, and carrying out ultrasonic treatment, suction filtration, drying and grinding treatment to obtain powdery solid;
dissolving the powdery solid by using an acid solution to obtain a mixed solution, then adjusting the pH value of the mixed solution to 7.5 by using an alkaline solution, transferring the mixed solution into a reaction kettle for heating treatment, cooling to room temperature after the reaction is finished, carrying out suction filtration on the reaction solution, drying and grinding to obtain the iron tailing sanding catalyst;
the iron tailing sanding catalyst is combined with 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid, (CH) 3 COO) 2 Zn·2H 2 Mixing O, putting the mixture into a reaction kettle, adding a solvent, adjusting the pH value of the solution to 7.5, putting the reaction kettle into an oven, heating to 110-130 ℃, carrying out heat preservation treatment for 5-8 hours, after cooling, washing substances in the reaction kettle for three times by using an organic solvent, carrying out suction filtration on the solution, and then drying to obtain the iron tailing sand/MOF composite photocatalyst;
the 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid was used in an amount of 35-40mg relative to 100mg of the iron tailing sanding catalyst, the (CH) 3 COO) 2 Zn·2H 2 The amount of O is 45-50mg.
2. The method of claim 1, wherein the calcination treatment conditions include calcination treatment at a temperature of 740-780 ℃ for 20-40min.
3. The method of claim 1, wherein the conditions for heating the mixed liquor in the reaction vessel comprise: the temperature is 190-210 ℃ and the time is 10-13h.
4. An iron tailing sand/MOF composite photocatalyst prepared by the method according to any one of claims 1 to 3.
5. The use of the iron tailing sand/MOF composite photocatalyst according to claim 4 for degrading organic dyes.
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