CN111085215B - alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst - Google Patents
alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst Download PDFInfo
- Publication number
- CN111085215B CN111085215B CN201911346251.4A CN201911346251A CN111085215B CN 111085215 B CN111085215 B CN 111085215B CN 201911346251 A CN201911346251 A CN 201911346251A CN 111085215 B CN111085215 B CN 111085215B
- Authority
- CN
- China
- Prior art keywords
- alpha
- temperature
- deionized water
- hours
- mil
- 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.)
- Active
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000623 carbamazepine Drugs 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- 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
- 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
- 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)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst, and preparation method and application of Cr@C porous carbon material by taking metal organic framework MIL-101 (Cr) as precursor and high-temperature roasting, wherein semiconductor material alpha-Fe 2 O 3 Introducing Cr@C porous carbon catalyst by hydrothermal synthesis method to prepare alpha-Fe 2 O 3 a/Cr@C composite photocatalyst; the porous carbon in the Cr@C material has conductivity, can rapidly transfer photogenerated electrons, inhibit the recombination of photogenerated electron-hole pairs, and enhance the photocatalytic activity; the composite photocatalyst has obvious degradation effect on carbamazepine in water under the irradiation of visible light; in addition, the alpha-Fe prepared by the invention 2 O 3 The Cr@C has good stability and service life.
Description
Technical Field
The invention relates to the technical field of preparation of new catalytic materials, in particular to an alpha-Fe 2 O 3 Preparation method of/Cr@C composite photocatalystA method of manufacturing the same.
Background
With the rapid development of science and technology, a large amount of wastewater is discharged into the environment, causing serious environmental pollution problems. Solving the environmental problem and developing green and environment-friendly technology has become urgent for human development. Photocatalytic degradation of organic pollutants in water is an emerging technology in recent years, and the photocatalytic technology has been receiving great attention by utilizing the green environmental protection technology of sunlight. In the photocatalytic degradation process, super-oxygen free radicals and hydroxyl free radicals are generated on the surface of the photocatalyst in the illumination environment, and organic pollutants in water are oxidized by the strong oxidizing property of the free radicals to form a non-toxic or less toxic product. The key technology in photocatalysis is the preparation of the photocatalyst, and the search and development of a potential efficient novel photocatalyst have become a main research trend.
Metal-organic frameworks (MOFs) are a novel class of porous materials that are crystalline materials that can be engineered to be synthesized consisting of transition metal clusters as nodes and organic ligands as frameworks. MOFs have large pore volume, high specific surface area and rich types of organic ligands, making them ideal precursors and templates for synthesizing porous materials of specific diverse porosities and pore structures. Based on the special composition and structure of MOFs, researchers have found that MOFs can be processed by high-temperature calcination and other modes to obtain porous carbon materials, besides exploring the application of different MOFs in various fields. Because MOFs are composed of metal sites and carbon-containing organic ligands, the organic ligands in MOFs can be converted into carbon materials through high-temperature calcination, and the metal sites can be converted into uniformly dispersed metal simple substances or metal oxides, so that the porous carbon composite material containing active metal sites is formed. MOFs-derived carbon materials can store and transport electrons and have good conductivity and structural stability. Semiconductor alpha-Fe 2 O 3 Has a narrow forbidden bandwidth, can be excited under visible light, and can generate photo-generated electron-hole pairs. Combining MOFs-derived carbon materials with alpha-Fe 2 O 3 The composite material can enhance the photocatalysis efficiency of the material. The carbon material has good conductivity, can effectively separate photo-generated electron-hole pairs and inhibit photo-generated electricityThe recombination of the sub-hole pairs prolongs the service life, so that the photocatalysis efficiency can be effectively improved.
Disclosure of Invention
The invention aims to provide an alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst.
In order to solve the technical problems, the invention adopts the following technical scheme:
alpha-Fe 2 O 3 Preparation method of/Cr@C composite photocatalyst comprises the steps of firstly preparing MIL-101 (Cr) catalyst, taking MIL-101 (Cr) of metal organic framework as precursor, preparing Cr@C porous carbon material by high-temperature roasting, and preparing alpha-Fe by hydrothermal method 2 O 3 A/Cr@C composite photocatalyst.
The technical scheme of the invention is further improved as follows: the method specifically comprises the following steps:
step (1): weighing 0.5-1.5 g of terephthalic acid and 1.0-3.0 g of chromium nitrate nonahydrate, adding into deionized water for dissolution, adding hydrofluoric acid, controlling the reaction temperature to be 180-220 ℃, controlling the reaction time to be 8-12 h, naturally cooling to room temperature, filtering, washing to be neutral, and drying to obtain an MIL-101 (Cr) catalyst for later use;
step (2): purifying the MIL-101 (Cr) prepared in the above manner in a vacuum drying oven, then placing the purified MIL-101 (Cr) in a tubular heating furnace, heating to 700-1100 ℃ in a nitrogen atmosphere, keeping constant temperature, and naturally cooling to room temperature to obtain Cr@C.
Step (3): respectively weigh FeCl 3 ·6H 2 Adding O and the prepared Cr@C into deionized water, uniformly stirring, transferring into a reaction kettle for crystallization, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water, and vacuum drying to obtain alpha-Fe 2 O 3 A/Cr@C composite photocatalyst.
The technical scheme of the invention is further improved as follows: the deionized water used for dissolution in the step (1) is 30mL, the hydrofluoric acid is 0.45mL, the washing solution is deionized water and absolute ethyl alcohol, the drying temperature is 100 ℃, and the drying time is 3h.
The technical scheme of the invention is further improved as follows: the purification temperature in the vacuum drying oven is 60-110 ℃, the purification time is 4-12 h, the heating rate in the heating stage in the tubular heating furnace is 5 ℃/min, and the constant temperature maintaining time in the constant temperature stage is 4-8 h.
The technical scheme of the invention is further improved as follows: weighing 0.1g Cr@C and 0.1-0.5 g FeCl respectively 3 ·6H 2 O is added into 30mL of deionized water, a polytetrafluoroethylene lining is arranged in the reaction kettle, the reaction temperature is controlled to be 120-160 ℃, and the reaction time is controlled to be 12-24 hours; the washing times of deionized water are 3 times, the vacuum drying temperature is 60-110 ℃, and the vacuum drying time is 6-12 h.
alpha-Fe 2 O 3 The application of the composite photocatalyst of/Cr@C is characterized in that: application in photocatalytic degradation of carbamazepine aqueous solution, alpha-Fe 2 O 3 The mass ratio of the Cr@C composite catalyst to carbamazepine is 3:1-7:1.
By adopting the technical scheme, the invention has the following technical progress:
in the invention, a metal organic framework MIL-101 (Cr) is used as a precursor, cr@C porous carbon material is prepared by high-temperature roasting, and then alpha-Fe is prepared by a hydrothermal method 2 O 3 A/Cr@C composite photocatalyst. The porous carbon in the Cr@C material has good conductivity, can effectively transmit electrons, inhibit the recombination of photo-generated electron-hole pairs, and enhance the catalytic activity. Under the irradiation of visible light, the organic pollutant in water is well degraded. In addition, the alpha-Fe prepared by the invention 2 O 3 The Cr@C has good stability and service life.
Drawings
FIG. 1 shows the alpha-Fe of the present invention 2 O 3 XRD pattern of Cr@C;
FIG. 2 shows the alpha-Fe of the present invention 2 O 3 SEM image of/Cr@C;
FIG. 3 is a graph showing the degradation efficiency of carbamazepine under visible light according to the present invention.
Detailed Description
The invention is further illustrated by the following examples:
alpha-Fe 2 O 3 Firstly preparing an MIL-101 (Cr) catalyst, taking a metal organic framework MIL-101 (Cr) as a precursor, preparing a Cr@C porous carbon material by high-temperature roasting, and preparing alpha-Fe by a hydrothermal method 2 O 3 A/Cr@C composite photocatalyst.
The method specifically comprises the following steps:
step (1): weighing 0.5-1.5 g of terephthalic acid and 1.0-3.0 g of chromium nitrate nonahydrate, adding into 30mL of deionized water for dissolution, adding 0.45mL of hydrofluoric acid, controlling the reaction temperature to be 180-220 ℃, controlling the reaction time to be 8-12 h, naturally cooling to room temperature, filtering, washing with deionized water and absolute ethyl alcohol to be neutral, drying at 100 ℃ for 3h, and obtaining an MIL-101 (Cr) catalyst for standby;
step (2): purifying the MIL-101 (Cr) in a vacuum drying oven at the purification temperature of 60-110 ℃ for 4-12 h, then placing the purified MIL-101 (Cr) in a tubular heating furnace, heating to 700-1100 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping the constant temperature for 4-8 h, and naturally cooling to room temperature to obtain Cr@C.
Step (3): weighing 0.1-0.5 g FeCl respectively 3 ·6H 2 Adding O and 0.1g of Cr@C prepared by the method into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to be 120-160 ℃, controlling the crystallization time to be 12-24 h, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water for 3 times, and vacuum-drying at 60-110 ℃ for 6-12 h to obtain alpha-Fe 2 O 3 A/Cr@C composite photocatalyst.
α-Fe 2 O 3 A method for evaluating the performance of a composite photocatalyst according to claim 1 to 5, comprising weighing a certain amount of the catalyst in a beaker, adding 50mL of carbamazepine solution with a concentration of 30mg/L, standing the reaction system under dark conditions for 0.5 to 4.0 hours to ensure that the adsorption-desorption balance is achieved between the catalyst and the solution, and thenAnd (3) transferring the solution to visible light for 180min, wherein the visible light is provided by a 300W xenon lamp light source, lambda is more than or equal to 420nm, taking 3mL of the solution every 30min, centrifuging, taking supernatant, and evaluating the photodegradation performance of the solution at lambda=285 nm by using an ultraviolet spectrophotometer.
α-Fe 2 O 3 Application of/Cr@C composite photocatalyst in photocatalytic degradation of carbamazepine aqueous solution and alpha-Fe 2 O 3 The mass ratio of the Cr@C composite catalyst to carbamazepine is 3:1-7:1.
Example 1
1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate are weighed, added into 30mL of deionized water for dissolution, then added with 0.45mL of hydrofluoric acid, the reaction temperature is controlled to be 180 ℃, the reaction time is 12 hours, naturally cooled to room temperature, filtered, washed to be neutral by deionized water and absolute ethyl alcohol, and dried for 3 hours at 100 ℃ to obtain the MIL-101 (Cr) catalyst. Purifying MIL-101 (Cr) prepared in the above way for 4 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) into a tubular heating furnace, heating to the temperature of 700 ℃ at 5 ℃/min in a nitrogen atmosphere, keeping the constant temperature for 6 hours, naturally cooling to the room temperature, and obtaining a carbonized sample, wherein the sample is marked as Cr@C700.
Example 2
1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate are weighed, added into 30mL of deionized water for dissolution, then added with 0.45mL of hydrofluoric acid, the reaction temperature is controlled to be 190 ℃, the reaction time is controlled to be 11 hours, naturally cooled to room temperature, filtered, washed to be neutral by deionized water and absolute ethyl alcohol, and dried for 3 hours at 100 ℃ to obtain the MIL-101 (Cr) catalyst. Purifying MIL-101 (Cr) prepared in the above way for 6 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) into a tubular heating furnace, heating to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 6 hours, naturally cooling to room temperature, and obtaining a carbonized sample, wherein the sample is marked as Cr@C800.
Example 3
1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate are weighed, added into 30mL of deionized water for dissolution, then added with 0.45mL of hydrofluoric acid, the reaction temperature is controlled to be 200 ℃, the reaction time is controlled to be 10 hours, naturally cooled to room temperature, filtered, washed to be neutral by deionized water and absolute ethyl alcohol, and dried for 3 hours at 100 ℃ to obtain the MIL-101 (Cr) catalyst. Purifying MIL-101 (Cr) prepared in the above way for 8 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) into a tubular heating furnace, heating to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 6 hours, naturally cooling to room temperature, and obtaining a carbonized sample, wherein the sample is marked as Cr@C900.
Example 4
1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate are weighed, added into 30mL of deionized water for dissolution, then added with 0.45mL of hydrofluoric acid, the reaction temperature is controlled to be 210 ℃, the reaction time is 9 hours, naturally cooled to room temperature, filtered, washed to be neutral by deionized water and absolute ethyl alcohol, and dried for 3 hours at 100 ℃ to obtain the MIL-101 (Cr) catalyst. Purifying MIL-101 (Cr) prepared in the above way for 10 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) into a tubular heating furnace, heating to 1000 ℃ at the temperature of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 6 hours, naturally cooling to room temperature, and obtaining a carbonized sample, wherein the sample is marked as Cr@C1000.
Example 5
1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate are weighed, added into 30mL of deionized water for dissolution, then added with 0.45mL of hydrofluoric acid, the reaction temperature is controlled to be 220 ℃, the reaction time is 8 hours, naturally cooled to room temperature, filtered, washed to be neutral by deionized water and absolute ethyl alcohol, and dried for 3 hours at 100 ℃ to obtain the MIL-101 (Cr) catalyst. Purifying MIL-101 (Cr) prepared in the above way for 12 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) into a tubular heating furnace, heating to 1100 ℃ at a constant temperature of 5 ℃/min in a nitrogen atmosphere for 6 hours, naturally cooling to room temperature, and obtaining a carbonized sample, wherein the sample is marked as Cr@C1100.
Example 6
Weigh 0.1g FeCl 3 ·6H 2 Adding O and 0.1g of the prepared Cr@C900 into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 12h, and naturally cooling to room temperature after crystallization is finishedCentrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60deg.C for 12 hr to obtain alpha-Fe 2 O 3 (0.1)/Cr@C900 composite photocatalyst.
Example 7
Weigh 0.2g FeCl 3 ·6H 2 Adding O and 0.1g of the prepared Cr@C900 into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 15h, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain alpha-Fe 2 O 3 (0.2)/Cr@C900 composite photocatalyst.
Example 8
Weigh 0.3g FeCl 3 ·6H 2 Adding O and 0.1g of the prepared Cr@C900 into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 18h, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain alpha-Fe 2 O 3 (0.3)/Cr@C900 composite photocatalyst.
Example 9
Weigh 0.4g FeCl 3 ·6H 2 Adding O and 0.1g of the prepared Cr@C900 into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 21h, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain alpha-Fe 2 O 3 (0.4)/Cr@C900 composite photocatalyst.
Example 10
Weigh 0.5g FeCl 3 ·6H 2 Adding O and 0.1g of the prepared Cr@C900 into 30mL of deionized water, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 24h, naturally cooling to room temperature after crystallization,centrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60deg.C for 12 hr to obtain alpha-Fe 2 O 3 (0.5)/Cr@C900 composite photocatalyst.
Example 11:
weigh 0.3g FeCl 3 ·6H 2 Adding O into 30mL of deionized water, stirring uniformly, transferring into a reaction kettle with polytetrafluoroethylene lining for crystallization, controlling the crystallization temperature to 140 ℃, controlling the crystallization time to 18h, naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain alpha-Fe 2 O 3 Photocatalyst as a blank sample.
Example 12:
photocatalytic degradation performance evaluation: will weigh 5mg of alpha-Fe 2 O 3 The (0.3)/Cr@C900 sample was placed in a 100mL beaker, then 50mL, 30mg/L carbamazepine solution was added, and the solution was first placed in the dark for 1h to ensure that the adsorption-desorption equilibrium was reached between the catalyst and the solution. Then the solution was transferred to visible light (300W xenon lamp light source, lambda: not less than 420 nm) and illuminated for 180min, 3mL of the solution was taken every 30min, centrifuged, the supernatant was taken, and the absorbance of the solution at lambda = 285nm was evaluated by ultraviolet spectrophotometer.
As can be seen from FIG. 1, the sample Cr@C900 in example 3 shows Cr 2 O 3 (JCPDS No. 38-1479). The sample pattern obtained in example 11 shows a-Fe 2 O 3 (JCPDS No. 33-0664). The sample obtained in example 8 showed significant Cr 2 O 3 And alpha-Fe 2 O 3 Characteristic diffraction peaks of (2) to illustrate alpha-Fe 2 O 3 The composite photocatalyst of/Cr@C900 was successfully prepared.
As can be seen from FIG. 2, cr@C900 has obvious small particles uniformly dispersed on the surface of the carbon material, alpha-Fe 2 O 3 alpha-Fe as uniform spherical particles 2 O 3 Larger spherical particles of alpha-Fe can be seen in the/Cr@C900 composite material 2 O 3 Attached to carbon material, illustrating alpha-Fe 2 O 3 The composite material of/Cr@C900 was successfully preparedAnd (5) preparing.
As can be seen from FIG. 3, cr@C900 has a high adsorption capacity, but its photocatalytic degradation performance is poor, as a-Fe 2 O 3 The adsorption effect is gradually reduced by adding the amount, and the photocatalytic performance is obviously improved. The sample obtained in example 8 was alpha-Fe after 180min of irradiation with visible light 2 O 3 The degradation efficiency of (0.3)/Cr@C900 to carbamazepine reaches 100%, which shows that alpha-Fe 2 O 3 the/Cr@C composite photocatalyst can effectively degrade carbamazepine.
The foregoing is merely a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (1)
1. alpha-Fe 2 O 3 The application of the composite photocatalyst of/Cr@C is characterized in that: application in photocatalytic degradation of carbamazepine aqueous solution, alpha-Fe 2 O 3 The mass ratio of the Cr@C composite catalyst to carbamazepine is 3:1-7:1;
the preparation method of the composite photocatalyst comprises the steps of firstly preparing an MIL-101 (Cr) catalyst, taking an MIL-101 (Cr) metal-organic framework as a precursor, preparing a Cr@C porous carbon material by high-temperature roasting, and preparing alpha-Fe by a hydrothermal method 2 O 3 a/Cr@C composite photocatalyst;
the method specifically comprises the following steps:
step (1): weighing 1.11g of terephthalic acid and 2.67g of chromium nitrate nonahydrate, adding into 30mL of deionized water for dissolution, adding 0.45mL of hydrofluoric acid, controlling the reaction temperature to be 200 ℃, naturally cooling to room temperature for 10 hours, filtering, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 100 ℃ for 3 hours to obtain an MIL-101 (Cr) catalyst for later use;
step (2): purifying MIL-101 (Cr) prepared in the above way for 8 hours at the temperature of 100 ℃ in a vacuum drying oven, then placing the purified MIL-101 (Cr) in a tubular heating furnace, heating to 900 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, keeping the constant temperature for 6 hours, and naturally cooling to the room temperature to obtain Cr@C900;
step (3): 0.1g of Cr@C900 and 0.3g of FeCl are weighed out respectively 3 ·6H 2 Adding O into 30mL of deionized water, uniformly stirring, transferring to a reaction kettle for crystallization, wherein the reaction kettle is internally provided with a polytetrafluoroethylene lining, and the reaction temperature is controlled to be 140 ℃ and the reaction time is controlled to be 18 hours; naturally cooling to room temperature after crystallization, centrifuging the obtained product, washing with deionized water, and vacuum drying to obtain alpha-Fe, wherein the washing times of deionized water are 3 times, the vacuum drying temperature is 60 ℃ and the vacuum drying time is 12 hours 2 O 3 (0.3)/Cr@C900 composite photocatalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911346251.4A CN111085215B (en) | 2019-12-24 | 2019-12-24 | alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911346251.4A CN111085215B (en) | 2019-12-24 | 2019-12-24 | alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111085215A CN111085215A (en) | 2020-05-01 |
| CN111085215B true CN111085215B (en) | 2023-08-15 |
Family
ID=70396753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911346251.4A Active CN111085215B (en) | 2019-12-24 | 2019-12-24 | alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111085215B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113332983B (en) * | 2021-04-29 | 2022-06-03 | 杭州师范大学 | Porous rod-like Fe21.34O32Preparation method of/C nanorod composite material |
| CN113817172B (en) * | 2021-08-11 | 2023-03-17 | 梅州绿盛林业科技有限公司 | Metal organic framework material for purifying dendrobium officinale polysaccharide compounds and purification method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908947A (en) * | 2014-04-03 | 2014-07-09 | 上海应用技术学院 | Preparation method of magnetic porous carbon/ ferric oxide nano composite material for oil-water separation |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN106076421A (en) * | 2016-06-14 | 2016-11-09 | 华东师范大学 | A kind of MIL 53 (Fe)/g C3n4the preparation method of nanometer sheet composite photocatalyst material |
| CN108435258A (en) * | 2018-02-07 | 2018-08-24 | 苏州容电环境科技有限公司 | Purify air semiconductors coupling catalyst and preparation method thereof |
| CN108751189A (en) * | 2018-07-14 | 2018-11-06 | 泉州师范学院 | The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area |
| CN110124717A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of catalyst and preparation method thereof being converted into benzaldehyde for benzyl alcohol |
| CN110124718A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of monatomic catalyst of vanadium base and preparation method thereof for benzene direct oxidation phenol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008066293A1 (en) * | 2006-11-27 | 2008-06-05 | Korea Research Institute Of Chemical Technology | A method for preparing porous organic-inorganic hybrid materials, porous organic-inorganic hybrid materials obtained by the method and catalytic uses of the materials |
-
2019
- 2019-12-24 CN CN201911346251.4A patent/CN111085215B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908947A (en) * | 2014-04-03 | 2014-07-09 | 上海应用技术学院 | Preparation method of magnetic porous carbon/ ferric oxide nano composite material for oil-water separation |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN106076421A (en) * | 2016-06-14 | 2016-11-09 | 华东师范大学 | A kind of MIL 53 (Fe)/g C3n4the preparation method of nanometer sheet composite photocatalyst material |
| CN108435258A (en) * | 2018-02-07 | 2018-08-24 | 苏州容电环境科技有限公司 | Purify air semiconductors coupling catalyst and preparation method thereof |
| CN108751189A (en) * | 2018-07-14 | 2018-11-06 | 泉州师范学院 | The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area |
| CN110124717A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of catalyst and preparation method thereof being converted into benzaldehyde for benzyl alcohol |
| CN110124718A (en) * | 2019-05-13 | 2019-08-16 | 浙江师范大学 | A kind of monatomic catalyst of vanadium base and preparation method thereof for benzene direct oxidation phenol |
Non-Patent Citations (1)
| Title |
|---|
| Quan Huo et al..Preparation of a direct Z-scheme α-Fe2O3/MIL-101(Cr) hybrid for degradation of carbamazepine under visible light irradiation.2019,第255卷117751. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111085215A (en) | 2020-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109647525B (en) | Method for photocatalytic degradation of organic pollutants by using defective metal organic framework photocatalyst | |
| CN108380233B (en) | Phosphorus-doped carbon nitride/carbon nitride homotype heterojunction photocatalyst and preparation method and application thereof | |
| CN108325555B (en) | Nitrogen self-doped graphitized carbon nitride nanosheet photocatalyst and preparation method and application thereof | |
| CN111420668B (en) | In-situ synthesis of alpha-Bi2O3/CuBi2O4Preparation method and application of heterojunction photocatalytic material | |
| CN112718009B (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
| CN108067267B (en) | Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof | |
| CN111085215B (en) | alpha-Fe 2 O 3 Preparation method and application of/Cr@C composite photocatalyst | |
| CN108620113B (en) | Preparation method of nitrogen-doped carbon-cerium composite nanosheet | |
| CN112090448A (en) | Preparation method of ZIF-8@ g-C3N4 catalyst with zeolite structure | |
| CN110624595A (en) | Calcium-indium-sulfur/titanium carbide photocatalytic composite material and preparation method thereof | |
| CN108273528A (en) | A method of preparing the high iodine oxygen bismuth photochemical catalyst of nano bar-shape | |
| CN111013664A (en) | Composite photocatalyst and preparation method thereof | |
| CN107262132A (en) | A kind of sulfur doping g C3N4The preparation method of/zinc-cadmium sulfide composite photo-catalyst | |
| CN112316969A (en) | N-doped TiO2Hollow microsphere-BiOBr photocatalytic degradation material and preparation method thereof | |
| CN112958061A (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
| CN112774718A (en) | Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof | |
| CN112316970A (en) | Preparation method and application of multi-defect graphite-phase carbon nitride photocatalyst | |
| CN113578313B (en) | Manganese-doped sillenite photocatalyst, preparation method thereof and application thereof in synchronous degradation of hexavalent chromium and organic pollutants | |
| CN114849752A (en) | Hexagonal boron nitride/flower ring-shaped graphite type carbon nitride heterojunction composite photocatalyst and preparation method and application thereof | |
| CN110639586A (en) | Flower-shaped g-C3N4/g-C3N4/BiOBr ternary heterojunction photocatalytic material and preparation method thereof | |
| CN115608388B (en) | Shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, preparation method and application thereof | |
| CN110180572B (en) | N-doped BiVO 4 -OVs/GO nano composite structured photocatalytic material and application thereof | |
| CN116212966B (en) | Indirect Z-type multicomponent bismuth-based MOF heterojunction and preparation method and application thereof | |
| CN110787817A (en) | Graphene-loaded bismuth oxyiodide photocatalyst and preparation method and application thereof | |
| CN113769735B (en) | CeO 2 /MnO 2 Composite photocatalyst and preparation method and application thereof |
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 |