CN115254189A - 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
- Publication number
- CN115254189A CN115254189A CN202210768643.5A CN202210768643A CN115254189A CN 115254189 A CN115254189 A CN 115254189A CN 202210768643 A CN202210768643 A CN 202210768643A CN 115254189 A CN115254189 A CN 115254189A
- Authority
- CN
- China
- Prior art keywords
- iron tailing
- composite photocatalyst
- solution
- mof composite
- reaction kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 63
- 239000004576 sand Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 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 6
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002699 waste 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 13
- 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
- 239000011148 porous material Substances 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
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 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
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000010814 metallic waste Substances 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
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 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
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling 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
Images
Classifications
-
- 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]
-
- 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
-
- 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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/34—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates toThe method comprises the steps of preparing an iron tailing sanding catalyst, and mixing the iron tailing sanding catalyst with 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid, (CH)3COO)2Zn·2H2Mixing 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, cooling, washing the substances in the reaction kettle with an organic solvent for three times, carrying out suction filtration on the solution, and drying to obtain the iron tailing sand/MOF composite photocatalyst; according to the invention, the iron tailing sand/MOF composite photocatalyst is prepared by taking the metal-organic framework and the waste iron tailing sand as raw materials, and experimental data prove that the iron tailing sand/MOF composite photocatalyst can obviously improve the degradation rate of organic dye compared with a single iron tailing sanding catalyst.
Description
Technical Field
The invention relates to the technical field of photocatalysis, and particularly relates to an iron tailing sand/MOF composite photocatalyst as well as a preparation method and application thereof.
Background
Iron tailings are a solid waste whose discharge is also 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 living environment of human beings and destroys ecological balance. Therefore, iron tailings sand is regarded as a secondary resource to be reused by countries in the world.
In addition, the pollution of organic dyes has been a serious environmental problem, and various methods for degrading organic dyes in the environment have been sought. The technology for degrading organic pollutants by photocatalysis is a technology which can not only fully utilize solar energy, but also help people to solve the problem of organic pollutant treatment, and is considered to be one of the most promising organic dye degradation technologies. The photocatalytic material is the key to realize 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 of secondary pollution are urgent for the degradation of the organic dye.
Disclosure of Invention
The invention aims to provide an iron tailing sand/MOF composite photocatalyst, which realizes efficient degradation of organic dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing iron tailing sand/MOF composite photocatalyst comprises the steps of mixing iron tailing sand with alkaline substances, calcining, washing with boiled water, and obtaining powdery solid after ultrasonic treatment, suction filtration, drying and grinding treatment;
dissolving the powdery solid by using an acidic solution to obtain a mixed solution, then adjusting the pH value of the mixed solution to 7.5 by using an alkaline solution, then 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;
mixing the iron tailing sanding catalyst with 2,2', 6',2 '-terpyridyl-4, 4' -tricarboxylic acid, (CH)3COO)2Zn·2H2And mixing the materials, 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, cooling, washing the materials in the reaction kettle with an organic solvent for three times, carrying out suction filtration on the solution, and drying to obtain the iron tailing sand/MOF composite photocatalyst.
In a further technical scheme, the calcining treatment conditions comprise that the calcining treatment is carried out at the temperature of 740-780 ℃ for 20-40min.
In a further technical scheme, the conditions of the heating treatment of the mixed solution in the reaction kettle comprise that: the temperature is 190-210 ℃, and the time is 10-13h.
In a further technical scheme, relative to 100mg of iron tailing sanding catalyst, the dosage of the 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid is 35-40mg, and the (CH)3COO)2Zn·2H2The dosage 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 an application of the iron tailing sand/MOF composite photocatalyst in degradation of 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 proves that the iron tailing sand/MOF composite photocatalyst can obviously improve the degradation rate of organic dye compared with a single iron tailing sanding catalyst;
in addition, the raw materials for preparing the iron tailing sanding catalyst are waste iron tailing sand, so that the iron tailing sanding catalyst has a great cost advantage, and compared with an MOF photocatalyst which is high in cost and can exert a degradation effect only by meeting a certain usage amount, the amount of the MOF photocatalyst in the iron tailing sand/MOF composite photocatalyst provided by the invention is small, 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 a good application prospect in the 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 the three-dimensional pore structure of Compound 1 prepared in example 2;
FIG. 3 is a graph showing the degradation profile of the iron tailing sand/MOF composite photocatalyst on methylene orange in test example 1;
FIG. 4 is a graph showing the degradation profile of methylene orange in comparative example 1;
fig. 5 is a graph of the degradation of methylene orange by the iron tailing sanding catalyst in comparative example 2;
fig. 6 is a schematic diagram of the cyclic degradation performance of the iron tailing sand/MOF composite photocatalyst on methylene orange.
Detailed Description
The present invention will be further described with reference to the following embodiments in order to make the technical means, the technical features, the technical purposes and the functions of the present invention easy to understand.
As known to those skilled in the art, metal-organic frameworks (MOFs) are a new class of porous materials, which refer to coordination polymers with cavity structures of 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 metal-organic framework polymers such as high stability, adjustable pore size, large specific surface area, and modification of active groups in pore channels are attracting great interest of scientists.
The invention takes metal-organic framework and 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 tailings/MOF composite photocatalyst provided by the invention is further illustrated by specific examples.
Example 1: preparation of iron tailing sanding catalyst
Weighing 5.0g of NaOH and 0.3g of iron tailing sand, mixing, putting into a crucible, calcining for 30 minutes at 750 ℃ in a resistance furnace, washing with boiled water, carrying out ultrasonic treatment, carrying out suction filtration, drying and grinding to obtain a powdery solid.
Weighing 0.2g of the powdery solid, adding 4mL of nitric acid to dissolve the powdery solid to obtain a mixed solution, adjusting 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 the temperature of 200 ℃ for 12 hours, after the reaction is finished, cooling the mixed solution to room temperature, filtering out the reaction solution, drying and grinding the reaction solution to obtain the iron tailing sanding catalyst.
Example 2: preparation of MOF photocatalysts
0.1mmol (36.5 mg) of 2,2':6',2 '-terpyridine-4, 4' -tricarboxylic acid (H)3TTC) and 0.20mmol (48.5 mg) of (CH)3COO)2Zn·2H2O was mixed and put into a reaction vessel, and then 15.0ml of N, N' -Dimethylformamide (DMF) solvent and 8.0ml of deionized water were added to adjust the pH of the solution to 7.5 with nitric acid. The reaction kettle is put into an oven to be heated to 120 ℃ and kept warm for 4 days, and then the temperature is reduced to room temperature at the speed of 5 ℃/h, and colorless needle-shaped crystals are separated out. The yield was 65%.
For convenience of description, the MOF photocatalyst prepared above is represented by compound 1.
Resolution and refinement of Compound 1 was accomplished using the SHELXL-97 package. The relevant crystallographic data for compound 1 are listed in table 1.
TABLE 1 Crystal data for Compound 1
aR1＝Σ||Fo|–|Fc|)/Σ|Fo|；wR2＝[Σw(Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
In this example, an example of a microporous zinc compound [ Zn ] was obtained by hydrothermal synthesis3(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, with two separate zinc atoms in Compound 1. The Zn1 atom has four oxygen atoms participating in coordination to form a tetrahedral structure, wherein the four oxygen atoms are derived from four monodentate coordinated TTC ligands, and the Zn1 atom is not coordinated with a nitrogen atom. The Zn2 atom is respectively coordinated with two oxygen atoms and three nitrogen atoms on three TTC ligands, and the spatial configuration is a deformed triangular bipyramid. In compound 1, the oxygen atom on the fully protonated carboxylic acid ligand is monodentate. Compound 1 is a 3D tunnel complex with uncoordinated oxygen atoms extending into the tunnel, as shown in figure 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) were weighed out3TTC), 0.20mmol (48.5 mg) of (CH)3COO)2Zn·2H2Mixing O and putting into a reaction kettle;
then adding 20ml of N, N' -Dimethylformamide (DMF) and 10.0ml of deionized water, and adjusting the pH value of the solution to 7.5 by using nitric acid; and then, putting the reaction kettle into an oven, heating to 120 ℃, carrying out heat preservation treatment for 6 hours, cooling, washing the substances in the reaction kettle with DMF for three times, carrying out suction filtration on the solution, and drying to obtain the iron tailing sand/MOF composite photocatalyst.
Test example 1:
50mg of the iron tailings sand/MOF composite photocatalyst prepared in example 3 was dispersed in 100 ml of an aqueous methylene orange 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, and 5.0ml of a sample was taken every 15 minutes, followed by an analytical test using a UV-visible spectrophotometer.
As shown in FIG. 3, the iron tailings/MOF composite photocatalyst can degrade about 90% of methylene orange in 90 minutes.
Comparative example 1:
under the same test conditions as in test example 1, only 100 ml of an aqueous solution of methylene orange (10 mg/l) was taken, and the mixture was stirred in the dark for 30 minutes without adding the iron tailing sand/MOF composite photocatalyst;
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 sample every 15 minutes, and then carrying out the analytical test with a UV-visible spectrophotometer.
As shown in fig. 4, methylene orange was not substantially degraded.
Comparative example 2:
50mg of the iron tailing sanding catalyst prepared in example 1 was dispersed in 100 ml of methylene orange water 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 sample every 15 minutes, and then carrying out the analysis test with a UV-visible spectrophotometer.
As shown in fig. 5, about 50% of the methylene orange was degraded within 90 minutes.
Based on the tests, the iron tailing sanding catalyst prepared by the method has a certain photocatalytic effect and can be used for photocatalytic degradation of methylene orange; when the iron tailings sand provided by the invention is adopted
When the MOF composite photocatalyst is used, methylene orange can be degraded quickly and efficiently.
Photocatalytic cycle test:
the mixture of test example 1 after 90 minutes of degradation treatment was filtered and sieved to remove the iron tailings sand/MOF composite photocatalyst, and then dispersed again into 100 ml of a fresh aqueous methylene orange solution (10 mg/l) and stirred in the dark for 30 minutes to ensure that the adsorption-desorption equilibrium was established.
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 a UV-visible spectrophotometer.
And after 90 minutes of degradation treatment, filtering and screening the iron tailing sand/MOF composite photocatalyst again, and performing a third photocatalytic degradation test on the methylene orange by using the iron tailing sand/MOF composite photocatalyst again.
The test results are shown in fig. 6.
In FIG. 6, the abscissa represents the degradation time and the ordinate is C/C0In which C is0The concentration of the initial methylene orange is obtained, and C is the concentration of the methylene orange obtained by sampling every 15 minutes; curves in coordinate spaceFrom left to right correspond to the first, second and third tests of photocatalytic degradation of methylene orange, respectively.
Based on the test result 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.
And (4) conclusion:
in the present invention, a novel zinc compound [ Zn ] having an active site was successfully synthesized by hydrothermal synthesis3(TTC)2]nDMF (1). Compound 1 is a 3D pore complex with the uncoordinated oxygen atom extending into the pore. The experiment researches the degradation of methylene orange by the iron tailing sanding catalyst and the degradation of methylene orange by the iron tailing sand/MOF composite photocatalyst, and the experiment results show that the methylene orange can be rapidly and efficiently degraded by the iron tailing sand/MOF composite photocatalyst.
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
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 performing ultrasonic treatment, suction filtration, drying and grinding treatment to obtain powdery solid;
dissolving the powdery solid by using an acidic solution to obtain a mixed solution, then adjusting the pH value of the mixed solution to 7.5 by using an alkaline solution, then 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;
mixing the iron tailings sandPhotocatalyst and 2,2 '6', 2 '-terpyridine-4, 4' -tricarboxylic acid, (CH)3COO)2Zn·2H2And O, mixing, putting 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 5-8h, cooling, washing the substances in the reaction kettle three times by using an organic solvent, carrying out suction filtration on the solution, and drying to obtain the iron tailing sand/MOF composite photocatalyst.
2. The method as claimed in claim 1, wherein the calcination treatment conditions include calcination treatment at a temperature of 740 to 780 ℃ for 20 to 40min.
3. The method of claim 1, wherein the conditions under which the mixed liquor is heated in the reaction kettle comprise: the temperature is 190-210 ℃, and the time is 10-13h.
4. The method of claim 1, wherein the 2,2': the dosage of 6',2 '-terpyridine-4, 4' -tricarboxylic acid is 35-40mg, and the (CH)3COO) 2 Zn.2H2O in an amount of 45-50mg.
5. The iron tailing sand/MOF composite photocatalyst prepared by the method of any one of claims 1 to 4.
6. Use of the iron tailings/MOF composite photocatalyst according to claim 5 for degrading organic dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210768643.5A CN115254189B (en) | 2022-07-01 | 2022-07-01 | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210768643.5A CN115254189B (en) | 2022-07-01 | 2022-07-01 | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115254189A true CN115254189A (en) | 2022-11-01 |
| CN115254189B CN115254189B (en) | 2023-12-26 |
Family
ID=83762775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210768643.5A Active CN115254189B (en) | 2022-07-01 | 2022-07-01 | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115254189B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004090A (en) * | 2021-04-27 | 2021-06-22 | 新至农业生态科技有限公司 | Soil conditioner prepared from livestock and poultry manure and preparation method thereof |
| CN117482917A (en) * | 2023-12-19 | 2024-02-02 | 安徽建筑大学 | Phosphate removing adsorption material capable of preventing fulvic acid interference and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110033776A1 (en) * | 2009-08-10 | 2011-02-10 | Board of regents of the Nevada System of Higher Education, on Behalf of the University of | Proton exchange membranes |
| CN113649009A (en) * | 2021-08-19 | 2021-11-16 | 唐山学院 | Preparation method of NaNi3O5(OH) 2. H2O/MgNiO2 composite photocatalyst |
-
2022
- 2022-07-01 CN CN202210768643.5A patent/CN115254189B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110033776A1 (en) * | 2009-08-10 | 2011-02-10 | Board of regents of the Nevada System of Higher Education, on Behalf of the University of | Proton exchange membranes |
| CN113649009A (en) * | 2021-08-19 | 2021-11-16 | 唐山学院 | Preparation method of NaNi3O5(OH) 2. H2O/MgNiO2 composite photocatalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004090A (en) * | 2021-04-27 | 2021-06-22 | 新至农业生态科技有限公司 | Soil conditioner prepared from livestock and poultry manure and preparation method thereof |
| CN113004090B (en) * | 2021-04-27 | 2023-02-10 | 新至农业生态科技有限公司 | Soil conditioner prepared from livestock and poultry manure and preparation method thereof |
| CN117482917A (en) * | 2023-12-19 | 2024-02-02 | 安徽建筑大学 | Phosphate removing adsorption material capable of preventing fulvic acid interference and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115254189B (en) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115254189B (en) | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN106076421B (en) | A kind of MIL-53 (Fe)/g-C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| CN113000067B (en) | Bimetallic mixed ligand metal organic framework photocatalyst and preparation method thereof | |
| CN104525266B (en) | Preparation method of metal-organic framework material photocatalyst and application | |
| CN105107467A (en) | Preparation and novel application of a type of MIL-101(Cr) adsorbent modified by virtue of post translation | |
| CN111408413B (en) | Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof | |
| CN107497402B (en) | Water-stable dye adsorbent and preparation method thereof | |
| CN110787584A (en) | Application of cerium-based metal organic framework structure material in CO2Adsorption separation application of | |
| CN107739444B (en) | Based on amino functionalization of YbIIIMetal organic framework material with hexanuclear molecular structural unit and preparation method and application thereof | |
| CN112892608A (en) | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof | |
| CN108579819B (en) | Fe3O4N-doped Ni/Zn-MOFs/g-C3N4Preparation method of composite photocatalytic material | |
| CN111909383B (en) | Preparation method and application of copper-based MOF (metal organic framework) for adsorbing Congo red | |
| CN107312025A (en) | A kind of terephthalic acid (TPA) Complexes of Uranyl photochemical catalyst and preparation method thereof | |
| CN112958158B (en) | Double-ligand rare earth complex photocatalyst and preparation method and application thereof | |
| CN103447033B (en) | Method for preparing mesoporous AgGaO2 photocatalytic material | |
| CN113398914A (en) | Preparation method of visible light catalyst synthesized by one-pot hydrothermal method | |
| CN111905834A (en) | BiOBrxI1-xPreparation method of/ZIF-8 composite photocatalyst | |
| CN109806912A (en) | Can magnetic recycling Nd complex/GO/Fe3O4Ternary complex and its preparation method and application | |
| CN105056962A (en) | Preparation method of load-type rare earth double perovskite composite oxide photocatalyst and preparation method thereof | |
| CN105924459A (en) | Neodymium complex, and preparation method and application thereof | |
| CN111097386B (en) | Two-dimensional layered water-stable dye adsorbent and preparation method thereof | |
| CN115181285A (en) | Terbium coordination polymer crystal and preparation method and application thereof | |
| CN114058023B (en) | Tridentamide-modified MIL-type crystalline material and preparation method and application thereof | |
| CN104310524A (en) | Method for degrading rhodamine B and indigo organic pollutant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |