CN114797938B - Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application - Google Patents
Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application Download PDFInfo
- Publication number
- CN114797938B CN114797938B CN202210460979.5A CN202210460979A CN114797938B CN 114797938 B CN114797938 B CN 114797938B CN 202210460979 A CN202210460979 A CN 202210460979A CN 114797938 B CN114797938 B CN 114797938B
- Authority
- CN
- China
- Prior art keywords
- stirring
- self
- heterogeneous catalyst
- temperature
- suspension
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004543 anhydrous citric acid Drugs 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000265 homogenisation Methods 0.000 claims abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 65
- 238000001354 calcination Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002957 persistent organic pollutant Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 10
- 229910001447 ferric ion Inorganic materials 0.000 claims description 8
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 7
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 42
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004021 humic acid Substances 0.000 description 4
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of water treatment, and discloses a self-assembled iron single-atom Fenton heterogeneous catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Adding absolute ethyl alcohol into deionized water, and uniformly mixing to obtain a solution A; 2) Dissolving anhydrous citric acid in the solution A, and uniformly stirring on a magnetic stirrer to obtain a suspension B; 3) Adding a ferric iron source into the suspension B prepared in the step 2, and vigorously stirring on a magnetic stirrer to obtain a suspension C; 4) And (3) adding melamine into the suspension C obtained in the step (3), and obtaining the viscous slurry D after ultrasonic homogenization. The catalyst and the preparation method thereof provided by the invention utilize the advantages of the iron metal single-atom heterogeneous catalyst, adopt low-cost synthetic materials, improve the catalytic performance of the target catalyst, and simultaneously have the advantages of higher stability of the catalyst, low metal ion leaching concentration, easy recovery after reaction and simple preparation method.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a self-assembled iron single-atom Fenton heterogeneous catalyst, a preparation method and application.
Background
Along with the high-speed development of pharmaceutical, printing and dyeing, textile, agriculture and other industries required in the era, a large amount of nondegradable organic pollutants are discharged into natural water bodies while benefiting mankind, and great harm is generated to the ecological system of the water bodies and the health of the mankind. There is a need for efficient, green, and economical water treatment technologies to address the challenges of water pollution, where advanced oxidation water treatment technologies based on monopersulfate (PMS) are of great interest. The monoperoxysulfate has the advantages of stable chemical property, safe storage and transportation and low cost, and can generate free radical attack organic pollutants with strong oxidability through activation or degrade target pollutants with higher selectivity through a non-free radical way so as to achieve the effect of purifying water. However, the homogeneous catalyst for activating the monoperoxysulfate generally has the defects of high cost, large pollution, poor performance, difficult recycling and the like, so that the heterogeneous metal catalyst is often applied to the activation of PMS, but has the problems of low metal utilization rate, large metal ion leaching concentration, few catalytic active centers, lower catalytic performance and the like. Iron is a widely existing metal element in nature, and is discharged into natural water body, so that the iron is relatively green to the biological and ecological environment. The iron metal single-atom catalyst is one of heterogeneous catalysts, and has the advantages of high metal atom utilization rate, and separated and definite catalytic active center. For noble metal catalysts such as gold, platinum and the like, the separation of metal centers enables the utilization rate of atoms to approach 100%, so that the economy of the noble metal catalysts is greatly improved.
Disclosure of Invention
The invention aims to provide a self-assembled iron single atom Fenton heterogeneous catalyst, a preparation method and application thereof, which utilize the advantages of an iron metal single atom heterogeneous catalyst, adopt a low-cost synthetic material to improve the catalytic performance of a target catalyst, and simultaneously have the advantages of higher stability of the catalyst, low leaching concentration of metal ions, and easy recovery after reaction so as to solve the defects of the existing catalyst proposed in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the self-assembled iron single-atom Fenton heterogeneous catalyst comprises the following steps:
1) Adding absolute ethyl alcohol into deionized water, and uniformly mixing to obtain a solution A;
2) Dissolving anhydrous citric acid in the solution A, and uniformly stirring on a magnetic stirrer to obtain a suspension B;
3) Adding a ferric iron source into the suspension B prepared in the step 2, and vigorously stirring on a magnetic stirrer to obtain a suspension C;
4) Adding melamine into the suspension C obtained in the step 3, and obtaining a viscous slurry D after ultrasonic homogenization;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating and stirring until the slurry D is evaporated to dryness, and grinding the slurry D into powdery solid E;
6) And (3) placing the powdery solid E obtained in the step (5) into a tubular resistance furnace, heating and calcining in a nitrogen atmosphere in a programmed way, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst.
Preferably, in the step 1, the absolute ethyl alcohol is of an analytical grade, the deionized water is prepared by a laboratory ultrapure water instrument, and the volumes of the absolute ethyl alcohol and the deionized water are as follows: absolute ethyl alcohol: deionized water = 30-60mL:30-60mL; in the step 1, the stirring tool is a glass rod, and the temperature for uniform mixing is 25-35 ℃.
Preferably, in the step 2, the anhydrous citric acid is of an analytically pure grade, and the addition mole number is 5-15mmol; in the step 2, the stirring temperature is 25-35 ℃, the stirring speed is 350-500r/min, and the stirring time is 5-15min.
Preferably, in the step 3, the ferric iron source is ferric trichloride hexahydrate, and the adding mole number of ferric ions is 0.1-0.6mmol; in the step 3, the stirring temperature is 25-35 ℃, the stirring speed is 500-700r/min, and the stirring time is 5-15min.
Preferably, in the step 4, melamine is in an analytically pure grade, and the mole number of the melamine is 30-200mmol; in the step 4, the ultrasonic frequency is 40KHz, the ultrasonic temperature is 30-60 ℃, and the ultrasonic time is 15-45min.
Preferably, in the step 5, the temperature of stirring in the water bath kettle is 70-90 ℃, the stirring speed is 500-700r/min, and the stirring time is 20-120min.
Preferably, in the step 6, the nitrogen purity for creating the nitrogen atmosphere is high-purity nitrogen (more than or equal to 99.9%), and the gas flow rate is 50-200mL/min; in the step 6, the temperature rising rate of the first stage of the tube furnace is 2.3-5 ℃/min, the temperature rises to 500-600 ℃, and the calcination time is 0.5-1.5h; in the step 6, the temperature rising rate of the second stage of the tube furnace is 2.3-5 ℃/min, the temperature rises to 700-900 ℃, and the calcination time is 2-4h.
A self-assembled iron single-atom Fenton heterogeneous catalyst is obtained by a self-assembly process in the preparation method.
The self-assembled iron single-atom Fenton heterogeneous catalyst is applied to the treatment of refractory organic pollutants in water.
Preferably, the refractory organic contaminant is at least one of bisphenol A (BPA), sulfamethoxazole (SMX), 4-chlorophenol (4-CP) and 2-chlorophenol (2-CP).
Compared with the prior art, the invention has the beneficial effects that:
1. the self-assembled iron single atom Fenton heterogeneous catalyst and the preparation method thereof provided by the invention utilize the advantages of the iron metal single atom heterogeneous catalyst, adopt low-cost synthetic materials, improve the catalytic performance of the target catalyst, and simultaneously have the advantages of higher stability of the catalyst, low metal ion leaching concentration, easy recovery after reaction and simple preparation method;
2. the catalyst can efficiently degrade organic pollutants difficult to degrade in water, greatly shortens the reaction time of degrading the organic matters by classical Fenton reaction, and improves the treatment efficiency;
3. the catalyst has good removal effect on refractory organic pollutants in water bodies of inorganic anions and natural organic matters with higher concentration;
4. the catalyst has the advantages of low iron metal ion dissolution concentration in the whole catalytic process and environmental friendliness;
5. the fixed bed flow experiment carried out by the catalyst can maintain high organic pollutant removal rate for a long time, and the catalyst has good stability;
6. the catalyst is a solid catalyst, is convenient to separate from a water body after reaction, and avoids causing secondary pollution;
7. the catalyst has the advantages of mild synthesis conditions, simple operation steps, short time consumption in the preparation process, and low cost and economy of the required synthesis raw materials.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of Fe-SAC-NC prepared in examples 1, 2, and 3;
FIG. 2 is a graph showing degradation of bisphenol A by Fe-SAC-NC prepared in example 3 and Fe-SAC-NC prepared in examples 1 and 2;
FIG. 3 is a graph showing the degradation of BPA by Fe-SAC-NC in a higher concentration water anion system prepared in example 3;
FIG. 4 is a graph showing the degradation of BPA by Fe-SAC-NC in a higher concentration humic acid system prepared in example 3;
FIG. 5 is a degradation graph of the Fe-SAC-NC prepared in example 3 with respect to BPA, SMX, 4-CP, 2-CP;
FIG. 6 is a graph showing degradation evaluation of stability of the Fe-SAC-NC prepared in example 3 and the Fe-SAC-NC prepared in example 1 against BPA in a fixed flow reactor.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-6, the present invention provides the following specific technical solutions.
The preparation method of the self-assembled iron single-atom Fenton heterogeneous catalyst comprises the following steps:
1) Adding absolute ethyl alcohol into deionized water, and uniformly mixing to obtain a solution A;
2) Dissolving anhydrous citric acid in the solution A, and uniformly stirring on a magnetic stirrer to obtain a suspension B;
3) Adding a ferric iron source into the suspension B prepared in the step 2, and vigorously stirring on a magnetic stirrer to obtain a suspension C;
4) Adding melamine into the suspension C obtained in the step 3, and obtaining a viscous slurry D after ultrasonic homogenization;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating and stirring until the slurry D is evaporated to dryness, and grinding the slurry D into powdery solid E;
6) And (3) placing the powdery solid E obtained in the step (5) into a tubular resistance furnace, heating and calcining in a nitrogen atmosphere in a programmed way, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst.
Embodiment one:
the preparation method of the self-assembled iron single-atom Fenton heterogeneous catalyst provided by the embodiment comprises the following steps:
1) Adding 50mL of absolute ethyl alcohol into 50mL of deionized water, and stirring and mixing uniformly through a glass rod at the temperature of 30 ℃ to obtain a solution A;
2) Adding 10mmol of anhydrous citric acid into the solution A, placing the solution A on a magnetic stirrer at the temperature of 30 ℃ and stirring the solution A for 10min at the rotating speed of 450r/min to obtain a suspension B;
3) Adding 0.1mmol ferric ion (Fe3+) prepared from ferric trichloride hexahydrate into the suspension B prepared in the step 2, and placing the suspension B on a magnetic stirrer for vigorous stirring at the temperature of 30 ℃ at the rotating speed of 700r/min for 10min to obtain a suspension C;
4) Adding 30mmol of melamine into the suspension C obtained in the step 3, wherein the ultrasonic frequency is 40KHz, the ultrasonic temperature is 40 ℃ and the ultrasonic time is 30min, and obtaining a viscous slurry D after the ultrasonic is uniform;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating in a water bath at 80 ℃ while magnetically stirring, wherein the magnetic stirring speed is 700r/min, heating and evaporating for 40min, and grinding to obtain powdery solid E;
6) Placing the powdery solid E obtained in the step 5 into a tubular resistance furnace, and calcining in a nitrogen atmosphere by two-stage temperature programming, wherein the first calcining stage is as follows: the temperature rising rate is 5 ℃/min, the temperature rises to 550 ℃, and the calcination time is 1h; next, a second calcination procedure is entered: the temperature rising rate is 5 ℃/min, the temperature rises to 800 ℃, and the calcination time is 2h. And after the program is finished, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst Fe-NC-SAC.
Embodiment two:
the preparation method of the self-assembled iron single-atom Fenton heterogeneous catalyst provided by the embodiment comprises the following steps:
1) Adding 50mL of absolute ethyl alcohol into 50mL of deionized water, and stirring and mixing uniformly through a glass rod at the temperature of 30 ℃ to obtain a solution A;
2) Adding 10mmol of anhydrous citric acid into the solution A, placing the solution A on a magnetic stirrer at the temperature of 30 ℃ and stirring the solution A for 10min at the rotating speed of 450r/min to obtain a suspension B;
3) Adding 0.6mmol ferric ions (Fe3+) prepared from ferric trichloride hexahydrate into the suspension B prepared in the step 2, and vigorously stirring on a magnetic stirrer at the temperature of 30 ℃ at the rotating speed of 700r/min for 10min to obtain a suspension C;
4) Adding 200mmol of melamine into the suspension C obtained in the step 3, wherein the ultrasonic frequency is 40KHz, the ultrasonic temperature is 40 ℃ and the ultrasonic time is 30min, and obtaining a viscous slurry D after the ultrasonic is uniform;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating in a water bath at 80 ℃ while magnetically stirring, wherein the magnetic stirring speed is 700r/min, heating and evaporating for 40min, and grinding to obtain powdery solid E;
6) Placing the powdery solid E obtained in the step 5 into a tubular resistance furnace, and calcining in a nitrogen atmosphere by two-stage temperature programming, wherein the first calcining stage is as follows: the temperature rising rate is 5 ℃/min, the temperature rises to 550 ℃, and the calcination time is 1h; next, a second calcination procedure is entered: the temperature rising rate is 5 ℃/min, the temperature rises to 800 ℃, and the calcination time is 2h. And after the program is finished, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst Fe-NC-SAC.
Embodiment III:
the preparation method of the self-assembled iron single-atom Fenton heterogeneous catalyst provided by the embodiment comprises the following steps:
1) Adding 50mL of absolute ethyl alcohol into 50mL of deionized water, and stirring and mixing uniformly through a glass rod at the temperature of 30 ℃ to obtain a solution A;
2) Adding 10mmol of anhydrous citric acid into the solution A, placing the solution A on a magnetic stirrer at the temperature of 30 ℃ and stirring the solution A for 10min at the rotating speed of 450r/min to obtain a suspension B;
3) Adding 0.3mmol ferric ion (Fe3+) prepared from ferric trichloride hexahydrate into the suspension B prepared in the step 2, and placing the suspension B on a magnetic stirrer for vigorous stirring at the temperature of 30 ℃ at the rotating speed of 700r/min for 10min to obtain a suspension C;
4) Adding 90mmol of melamine into the suspension C obtained in the step 3, wherein the ultrasonic frequency is 40KHz, the ultrasonic temperature is 40 ℃ and the ultrasonic time is 30min, and obtaining a viscous slurry D after the ultrasonic is uniform;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating in a water bath at 80 ℃ while magnetically stirring, wherein the magnetic stirring speed is 700r/min, heating and evaporating for 40min, and grinding to obtain powdery solid E;
6) Placing the powdery solid E obtained in the step 5 into a tubular resistance furnace, and calcining in a nitrogen atmosphere by two-stage temperature programming, wherein the first calcining stage is as follows: the temperature rising rate is 5 ℃/min, the temperature rises to 550 ℃, and the calcination time is 1h; next, a second calcination procedure is entered: the temperature rising rate is 5 ℃/min, the temperature rises to 800 ℃, and the calcination time is 2h. And after the program is finished, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst Fe-NC-SAC.
Test example 1: characterization of test examples 1, 2, 3 materials
FIG. 1 shows the X-ray powder diffraction of the self-assembled iron single-atom type Fenton heterogeneous catalyst Fe-NC-SAC prepared in examples 1, 2 and 3. The three examples do not form metal diffraction peaks of Fe, which indicates that Fe elements introduced by the iron single-atom catalyst synthesized by the three examples are isolated and uniformly dispersed, iron metal nano particles or metal oxides are not formed, and Fe exists in the catalyst in coordination with the base element of the catalyst in an isolated manner. The Fe-NC-SAC prepared in examples 1, 2 and 3 is a carbon-based catalyst, and generally, the carbon material has two diffraction peaks near 25 DEG and 43 DEG in 2 theta, corresponding to (002) and (100) crystal planes of the carbon material, respectively. In the XRD patterns of the Fe-NC-SAC prepared in the three examples, two broad diffraction peaks were shown near 24℃and 44℃in 2. Theta., which means that the catalyst forms crystalline carbon with a low graphitization degree, and since melamine was added to the synthetic precursor of the catalyst and nitrogen was introduced, the nitrogen introduced into the carbon lattice slightly distorted the crystal, resulting in a disordered structure. The (002) form of example 3 was weaker than the peaks of examples 1, 2, and the (100) form of example 3 was almost disappeared, the peak width was maximized, and therefore, the nitrogen element introduced into the crystalline carbon of example 3 was more. As the nitrogen element is doped and better coordinated with Fe, the Fe element is more stably fixed in the catalyst, so that the stability of the catalyst is improved, the loading amount of Fe metal is increased, and the catalytic activity center is increased.
Experimental example 2 application experiment
Test procedure 1: 5mg of the Fe-NC-SAC catalyst prepared in the above example 3, the Fe-NC-SAC catalyst prepared in the example 1 and the Fe-NC-SAC catalyst prepared in the example 2 are weighed and respectively added into 50mL of solution containing nondegradable organic pollutants, and the reaction system is uniformly stirred through 15min ultrasound and 15min magnetic force, the reaction is carried out at room temperature, 0.5mM monoperoxysulfate (PMS) is added to start the catalytic reaction, and the concentration of nondegradable organic pollutants in the system is sampled and measured at different reaction time points, wherein the effect of the Fe-NC-SAC prepared in the example 1 and the Fe-NC-SAC catalyst prepared in the example 2 in activating PMS Fenton-like reaction is similar to that of the example 3, and is not repeated here.
Test procedure 2: 10mg of the Fe-NC-SAC catalyst prepared in the example 3 and the Fe-NC-SAC catalyst prepared in the example 1 are weighed and evenly mixed with 5g of clean quartz sand respectively, the mixture is put into a quartz column of a fixed bed flow reactor, 23g of quartz sand is weighed and blocked at two ends of the quartz column, two liquid conveying pipelines are connected, one end of the quartz sand is bisphenol A pollutant, the other end of the quartz sand is PMS solution, after the reaction is started, the reaction is carried out at room temperature, and the concentration of refractory organic pollutants in a measuring system is sampled and measured at different reaction time points.
FIG. 2 is a graph showing degradation curves of bisphenol A (BPA) by Fe-SAC-NC prepared in example 3 and Fe-SAC-NC prepared in examples 1 and 2. Fig. 2 is a graph showing the degradation of BPA in monoperoxysulfate Fenton system by the iron monoatomic heterogeneous catalysts prepared in the various examples. In the catalyst system of example 1, the removal rate of the Fe-SAC-NC catalyzed monoperoxysulfate-degraded BPA reaches 82% at 150 s; in the Fe-SAC-NC system prepared in the examples 2 and 3, when the reaction is carried out for 150 seconds, the removal rate effect of BPA reaches 100 percent, and the reaction time for degrading organic pollutants is short compared with that of a classical Fenton system. The Fe-SAC-NC prepared in comparative example 2 and example 3 had a faster reaction rate for BPA degradation process, and the Fe-SAC-NC in example 3 catalyzed the almost complete removal of BPA at 120s reaction time. The above catalytic effect shows that the amount of melamine incorporated in the catalyst of example 3 is suitable, and the catalytic effect of the catalytic active center formed by the Fe metal element with the nitrogen element coordinated and fixed is optimal.
FIG. 3 is a graph showing the degradation of BPA by Fe-SAC-NC in a higher concentration water anion system prepared in example 3. As shown in FIG. 3, the anionic environment of 1mM of different water bodies has little influence on the catalytic degradation effect of Fe-SAC-NC prepared in example 3 on BPA. In a 1mM chloride ion (Cl-), dihydrogen phosphate ion (H2 PO 4-), nitrate ion (NO 3-), the catalytic degradation effect of Fe-SAC-NC on BPA is hardly affected compared with a Control system of Fe-SAC-NC (NO anions are added); in the carbonate ion (CO 32-) system, the removal rate of the Fe-SAC-NC to BPA is reduced to 79 percent. It can be seen that the Fe-SAC-NC prepared in example 3 can still remove BPA efficiently in most high concentration water anion environments. However, the adsorption rate of Fe-SAC-NC to BPA in the Control system is about 30%, while the adsorption rate of Fe-SAC-NC to BPA in the CO32 system is about 10%, and the catalytic degradation effect is affected by CO 32-affecting the adsorption effect of Fe-SAC-NC to BPA. The catalytic effect shows that CO 32-is adsorbed on the catalyst, occupies the active site of Fe-SAC-NC, reduces the contact between BPA and the active site, and reduces the catalytic effect.
FIG. 4 is a graph showing the degradation of BPA in a higher concentration humic acid system by Fe-SAC-NC prepared in example 3. FIG. 4 shows that the Fe-SAC-NC prepared in example 3 still has good degradation effect on BPA under the influence of high-concentration natural organic humic acid. In the environment of high-concentration humic acid, fe-SAC-NC selectively catalyzes and degrades BPA, which shows that the Fe-SAC-NC can be applied to the actual water body to selectively remove target organic pollutants such as BPA and the like.
FIG. 5 is a graph showing degradation curves of BPA, SMX, 4-CP and 2-CP by Fe-SAC-NC prepared in example 3. The reaction proceeds to about 60 seconds, and the removal rate of the Fe-SAC-NC to 4-CP, 2-CP and BPA is nearly 100%; when the reaction proceeded to 150s, the removal rate of SMX was approximately 90%. From the above-mentioned conditions of removing various organic matters, fe-SAC-NC shows good degradation effect, which indicates that the Fe-SAC-NC catalyst prepared in example 3 can treat various organic matter polluted water bodies in a targeted manner.
FIG. 6 is a graph showing degradation evaluation of stability of the Fe-SAC-NC prepared in example 3 and the Fe-SAC-NC prepared in example 1 against BPA in a fixed flow reactor. From the experimental results of the fixed bed flow reactor, the removal rate of BPA by Fe-SAC-NC prepared in example 1 was about 94% in 1h, and only 10% in 6 h. The Fe-SAC-NC catalyst prepared in example 3 had a BPA removal rate of 100% from the start of the reaction to 15 hours, a removal rate of 97% from 18 hours of the treatment failed to completely remove BPA, a reaction duration of 26 hours still had a BPA removal rate of 77.6%, and the degradation effect of Fe-SAC-NC in the fixed bed flow reactor was reduced to about 53% until 33 hours. The above results fully show the stability advantages of the Fe-SAC-NC catalyst prepared in the embodiment 3, and can be applied to the treatment of actual micro-polluted water bodies.
The catalyst, the preparation method and the application thereof provided by the invention mainly utilize the advantages of the iron metal single-atom heterogeneous catalyst, adopt low-cost synthetic materials, improve the catalytic performance of the target catalyst, and have the advantages of higher stability of the catalyst, low metal ion leaching concentration, easy recovery after reaction and simple preparation method.
It should be noted that, in the ranges of the components, the proportions and the process parameters described in the present invention, other components, proportions or values are specifically selected, so that the technical effects described in the present invention can be achieved, and therefore, the technical effects are not listed one by one.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. An application of self-assembled iron single-atom Fenton heterogeneous catalyst is characterized in that,
the self-assembled iron single-atom Fenton heterogeneous catalyst is used for treating refractory organic pollutants in water;
the refractory organic pollutant is at least one of bisphenol A (BPA), sulfamethoxazole (SMX), 4-chlorophenol (4-CP) and 2-chlorophenol (2-CP);
the self-assembled iron single-atom Fenton heterogeneous catalyst comprises the following preparation steps:
1) Adding absolute ethyl alcohol into deionized water, wherein the volumes of the absolute ethyl alcohol and deionized water are as follows: absolute ethyl alcohol: deionized water = 30-60mL:30-60mL, and uniformly mixing to obtain a solution A;
2) Dissolving anhydrous citric acid in the solution A, and uniformly stirring on a magnetic stirrer to obtain a suspension B;
3) Adding a ferric iron source into the suspension B prepared in the step 2, and vigorously stirring on a magnetic stirrer to obtain a suspension C;
4) Adding 90-200mmol of analytically pure melamine into the suspension C obtained in the step 3, and obtaining a viscous slurry D after ultrasonic homogenization;
5) Placing the slurry D obtained in the step 4 into a water bath kettle, heating and stirring until the slurry D is evaporated to dryness, and grinding the slurry D into powdery solid E; 6) Placing the powdery solid E obtained in the step 5 into a tubular resistance furnace, and performing temperature programming calcination in a nitrogen atmosphere in two stages, wherein the purity of the nitrogen is high-purity nitrogen, the purity of the nitrogen of the high-purity nitrogen is more than or equal to 99.9%, and the gas flow rate is 50-200mL/min; the first calcination stage is: the temperature rising rate is 5 ℃/min, the temperature rises to 550 ℃, and the calcination time is 1h; next, a second calcination procedure is entered: the temperature rising rate is 5 ℃/min, the temperature rises to 800 ℃, and the calcination time is 2h; and after the program is finished, naturally cooling to room temperature, and grinding to obtain the self-assembled iron single-atom Fenton heterogeneous catalyst Fe-NC-SAC.
2. The use of a self-assembled iron mono-atomic Fenton heterogeneous catalyst according to claim 1, characterized in that: in the step 1, absolute ethyl alcohol is of an analytical grade, and deionized water is prepared by a laboratory ultrapure water instrument; in the step 1, the stirring tool is a glass rod, and the temperature for uniform mixing is 25-35 ℃.
3. The use of a self-assembled iron mono-atomic Fenton heterogeneous catalyst according to claim 2, characterized in that: in the step 2, anhydrous citric acid is of an analytically pure grade, and the addition mole number is 5-15mmol; in the step 2, the stirring temperature is 25-35 ℃, the stirring speed is 350-500r/min, and the stirring time is 5-15min.
4. The use of a self-assembled iron mono-atomic Fenton heterogeneous catalyst according to claim 3, characterized in that: in the step 3, ferric iron source is ferric trichloride hexahydrate, and the adding mole number of ferric ions is 0.1-0.6mmol; in the step 3, the stirring temperature is 25-35 ℃, the stirring speed is 500-700r/min, and the stirring time is 5-15min.
5. The use of a self-assembled iron mono-atomic Fenton heterogeneous catalyst according to claim 4, characterized in that: in the step 4, the ultrasonic frequency is 40KHz, the ultrasonic temperature is 30-60 ℃, and the ultrasonic time is 15-45min.
6. The use of a self-assembled iron mono-atomic Fenton heterogeneous catalyst according to claim 5, characterized in that: in the step 5, the stirring temperature in the water bath kettle is 70-90 ℃, the stirring speed is 500-700r/min, and the stirring time is 20-120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210460979.5A CN114797938B (en) | 2022-04-28 | 2022-04-28 | Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210460979.5A CN114797938B (en) | 2022-04-28 | 2022-04-28 | Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114797938A CN114797938A (en) | 2022-07-29 |
| CN114797938B true CN114797938B (en) | 2024-02-02 |
Family
ID=82509213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210460979.5A Active CN114797938B (en) | 2022-04-28 | 2022-04-28 | Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114797938B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
| CN110102300A (en) * | 2019-06-05 | 2019-08-09 | 中北大学 | Monatomic catalyst of a kind of flexibility carbon-based supports carried metal and its preparation method and application |
| CN113019415A (en) * | 2021-03-16 | 2021-06-25 | 南京工业大学 | Preparation method of iron-based supermolecule graphite phase carbon nitride photocatalyst |
| CN113058635A (en) * | 2021-04-06 | 2021-07-02 | 南昌航空大学 | Monatomic catalyst for activating persulfate to generate pure singlet oxygen and preparation method and application thereof |
-
2022
- 2022-04-28 CN CN202210460979.5A patent/CN114797938B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636437A (en) * | 2018-05-09 | 2018-10-12 | 天津理工大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped carbon carried metal |
| CN110102300A (en) * | 2019-06-05 | 2019-08-09 | 中北大学 | Monatomic catalyst of a kind of flexibility carbon-based supports carried metal and its preparation method and application |
| CN113019415A (en) * | 2021-03-16 | 2021-06-25 | 南京工业大学 | Preparation method of iron-based supermolecule graphite phase carbon nitride photocatalyst |
| CN113058635A (en) * | 2021-04-06 | 2021-07-02 | 南昌航空大学 | Monatomic catalyst for activating persulfate to generate pure singlet oxygen and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114797938A (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zang et al. | The role of exposed facets in the Fenton-like reactivity of CeO2 nanocrystal to the Orange II | |
| Chen et al. | Catalytic performance of MgO with different exposed crystal facets towards the ozonation of 4-chlorophenol | |
| CN109772465B (en) | Preparation method of water-soluble carbon dot modified perovskite type catalytic material | |
| Gai et al. | An alternative scheme of biological removal of ammonia nitrogen from wastewater–highly dispersed Ru cluster@ mesoporous TiO2 for the catalytic wet air oxidation of low-concentration ammonia | |
| CN111359650A (en) | Preparation method, product and application of iron, nickel and palladium co-doped graphite-phase carbon nitride composite catalyst | |
| CN111517444A (en) | Method for degrading organic pollutants by boron-nitrogen co-doped carbon nanotube catalyst embedded with iron carbide | |
| CN113333007B (en) | Nitrogen-doped cobalt iron/carbon catalyst capable of efficiently activating persulfate and preparation method and application thereof | |
| CN113559912B (en) | Nitrogen-sulfur co-doped graphene supported cobalt catalyst, and preparation method and application thereof | |
| An et al. | Fe-doped g-C3N4 synthesized by supramolecular preorganization for enhanced photo-Fenton activity | |
| Liu et al. | Structural characterizations of zinc-copper silicate polymer (ZCSP) and its mechanisms of ozonation for removal of p-chloronitrobenzene in aqueous solution | |
| CN113262787A (en) | Preparation method of iron-based composite catalyst for catalytic ozonation treatment of coal chemical wastewater | |
| Yuan et al. | Enhanced photocatalytic oxidation of humic acids using Fe 3+-Zn 2+ co-doped TiO 2: The effects of ions in aqueous solutions | |
| Zhang et al. | CuO and CeO 2 assisted Fe 2 O 3/attapulgite catalyst for heterogeneous Fenton-like oxidation of methylene blue | |
| He et al. | Catalytic ozonation of NH4+-N in wastewater over composite metal oxide catalyst | |
| Zhang et al. | Novel MnCo2O4. 5@ manganese sand for efficient degradation of tetracycline through activating peroxymonosulfate: Facile synthesis, adaptable performance and long-term effectiveness | |
| Huang et al. | Multivalent iron-based magnetic porous biochar from peach gum polysaccharide as a heterogeneous Fenton catalyst for degradation of dye pollutants | |
| CN107961811B (en) | Supported catalyst for deeply degrading industrial dye wastewater and preparation method thereof | |
| CN114797938B (en) | Self-assembled iron single-atom Fenton heterogeneous catalyst, preparation method and application | |
| CN113189268A (en) | Method for degrading organic pollutants by catalytic ozone | |
| CN110586140B (en) | photo-Fenton catalyst and preparation method and application thereof | |
| CN111229281A (en) | Magnetic Fe2O3/BN composite material and preparation method and application thereof | |
| CN110302819A (en) | Bimetallic magnetic Nano porous carbon ozone catalyst and application derived from a kind of MOFs | |
| Zhang et al. | Confined catalytic with yolk-shell nanoreactor boosting the efficient removal of antibiotic by low temperature plasma-catalytic degradation: Reaction kinetics and mechanisms | |
| Zhou et al. | Heterogeneous Fenton for Removal Rhodamine-B by Iron-bearing Attapulgite Granular Catalysts | |
| Rajput et al. | Synthesis of Polyhedral Zirconia nanoparticles for the Photocatalytic Degradation of Anionic Congo Red Dye under visible light irradiation |
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 |