CN115770593A - Preparation method of carbon-doped iron oxychloride composite material - Google Patents
Preparation method of carbon-doped iron oxychloride composite material Download PDFInfo
- Publication number
- CN115770593A CN115770593A CN202211410789.9A CN202211410789A CN115770593A CN 115770593 A CN115770593 A CN 115770593A CN 202211410789 A CN202211410789 A CN 202211410789A CN 115770593 A CN115770593 A CN 115770593A
- Authority
- CN
- China
- Prior art keywords
- feocl
- carbon
- composite material
- steps
- doped iron
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- YPLPZEKZDGQOOQ-UHFFFAOYSA-M iron oxychloride Chemical compound [O][Fe]Cl YPLPZEKZDGQOOQ-UHFFFAOYSA-M 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 9
- 239000008103 glucose Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 abstract description 9
- 239000004098 Tetracycline Substances 0.000 description 23
- 229960002180 tetracycline Drugs 0.000 description 23
- 229930101283 tetracycline Natural products 0.000 description 23
- 235000019364 tetracycline Nutrition 0.000 description 23
- 150000003522 tetracyclines Chemical class 0.000 description 23
- 229910052799 carbon Inorganic materials 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 9
- 238000013032 photocatalytic reaction Methods 0.000 description 9
- 229910017112 Fe—C Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229960001031 glucose Drugs 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OSNSWKAZFASRNG-WNFIKIDCSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol;hydrate Chemical compound O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O OSNSWKAZFASRNG-WNFIKIDCSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 235000013613 poultry product Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Images
Classifications
-
- 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
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a carbon-doped iron oxychloride composite material, in particular to FeOCl crystal lattices and interlayer doping C, and the preparation method comprises the following steps: mixing and grinding FeOCl and glucose with the mass ratio of 5-6, performing a temperature rise program from room temperature to 250 ℃, keeping for 2.5h, cooling to room temperature, cleaning and drying to obtain C-FeOCl powder.
Description
Technical Field
The invention relates to a preparation method of a carbon-doped iron oxychloride composite material.
Background
With the rapid development of economy in China, the demand of people on materials is continuously improved, and particularly the demand of livestock and poultry products is increased more and more. Antibiotics, such as ciprofloxacin, tetracycline, and the like, are widely used to prevent and control a variety of pathogens in humans, livestock, and aquaculture. Compared with physical methods, chemical methods can directly remove pollutants rather than transfer of pollutants, so that a method for efficiently removing antibiotics in water bodies needs to be found. In the photo-fenton technique, visible light promotes iron circulation, so that a large amount of hydrogen peroxide is activated by ferrous iron into hydroxyl groups for complete degradation of contaminants such as antibiotics.
The catalytic ability of FeOCl materials commonly used in the photo-fenton technique is relatively insufficient.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a carbon-doped iron oxychloride composite material, and the carbon/iron oxychloride composite material prepared by the method has good photo-Fenton performance.
The technical scheme is as follows: the preparation method of the carbon/ferric oxychloride composite material comprises the following steps: mixing and grinding FeOCl and glucose in a mass ratio of 5; in the C-FeOCl composite material, C is doped in the crystal lattice and between layers of FeOCl.
Specifically, a warming procedure is performed from room temperature to 250 ℃.
Specifically, the temperature is raised to 250 ℃ at a temperature rise rate of 10 ℃/min.
Specifically, the temperature is kept at 250 ℃ for 2.5h.
Specifically, the FeOCl is prepared and synthesized by ferric chloride hexahydrate through a pyrolysis method.
Specifically, the preparation method of FeOCl comprises the following steps: and (3) performing a temperature rise program on ferric trichloride hexahydrate, keeping the temperature of 250-255 ℃ for 2.5-3 h at the temperature rise rate of 10-12 ℃/min from the room temperature to 250-255 ℃, cooling to the room temperature, cleaning and drying to obtain FeOCl powder.
And (3) mechanism analysis: in the invention, on one hand, glucose is used as a gas template agent, the carbon dioxide hot gas generated under the high-temperature condition expands the layers of FeOCl, the interlayer spacing of the FeOCl is expanded, the unsaturated iron active sites on the inner surface of the FeOCl are exposed, and in a Fenton system, the unsaturated iron active sites on the inner surface and the outer surface and H are simultaneously on the FeOCl 2 O 2 Coordination is carried out for adsorption and activation, so that the pollutant degradation effect is improved; on the other hand, glucose is used as a carbon source, amorphous carbon is compounded on the surface of FeOOL, and part of carbon atoms enter the interlayer of FeOOL, so that carbon points are further formed and embedded in the interlayer of FeOOL. Because the Fe-Cl bond is weak, C atoms replace Cl atoms on the outer surface and the inner surface of FeOCl to form Fe-C bonds, under the irradiation of visible light, the FeOCl, the amorphous carbon on the surface and carbon points between layers are excited by light to generate photogenerated carriers, and the Fe-C bonds on the outer surface and the inner surface greatly promote the transfer of photogenerated electrons to accelerate Fe 3+ To Fe 2+ To produce a constant supply of hydroxyl radicals for the degradation of the contaminants.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable effects:
1. the method has the advantages of simple process, easily obtained raw materials and low preparation cost, and the prepared composite material has the advantages of good chemical stability and easy separation from the solution.
2. Compared with single materials FeOCl and C, the composite material (C-FeOCl) has good visible light response performance and excellent photocatalytic performance, and can efficiently degrade antibiotics in water by using visible light.
3. The composite material (C-FeOCl) can effectively separate photon-generated carriers and promote photon-generated electrons to accelerate the circulation of iron so as to efficiently degrade antibiotics.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing a carbon doped iron oxychloride lattice composite (C-FeOCl);
FIG. 2 is an XRD pattern for C, feOCl,1C-FeOCl,2C-FeOCl and 3C-FeOCl;
FIG. 3 is a C1s spectrum of XPS of 2C-FeOCl;
FIG. 4 is a Fourier infrared spectrum (FT-IR) of C, feOCl,1C-FeOCl,2C-FeOCl and 3C-FeOCl;
FIG. 5 is an XPS survey of FeOCl and 2C-FeOCl;
FIG. 6 is a SEM image of C;
FIG. 7 is an SEM image of FeOCl;
FIG. 8 is an SEM picture of C-FeOCl;
FIG. 9 is a HRTEM image of C-FeOCl;
FIG. 10 is a Raman spectrum of C, feOCl, 2C-FeOCl;
FIG. 11 is an ultraviolet-visible diffuse reflectance spectrum (UV-vis DRS) of composite C-FeOCl, C and FeOCl;
FIG. 12 is a graph of the effect of composite C-FeOCl, C and FeOCl in removing tetracycline antibiotics.
Detailed Description
Example 1
The invention provides a preparation method of a carbon-doped ferric oxychloride lattice composite material, and figure 1 is a process flow chart of the preparation method of the carbon-doped ferric oxychloride lattice composite material (C-FeOCl); the method comprises the following steps:
step 1, preparing reddish brown iron oxychloride (marked as FeOCl) by a pyrolysis method;
the method specifically comprises the following steps: collecting 4g of ferric chloride hexahydrate in a 50mL crucible with a cover, executing a heating program, keeping the temperature of the crucible from room temperature to 250 ℃ at a heating rate of 10 ℃/min for 2.5h at 250 ℃, naturally cooling the crucible to room temperature, centrifugally cleaning the obtained reddish brown solid with water and absolute ethyl alcohol for multiple times, and finally drying the solid at 80 ℃ for 12h to obtain FeOOL powder, wherein the FeOOL powder has a nanosheet layered structure.
the method comprises the following specific steps: mixing and grinding 0.3g of FeOOL and 0.06g of glucose, placing the mixture in a 50mL crucible with a cover, wrapping the crucible with aluminum foil paper, performing a heating program from room temperature to 250 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 250 ℃ for 2.5h, naturally cooling to room temperature, centrifugally cleaning the obtained solid with water and absolute ethyl alcohol for multiple times, and finally drying at 80 ℃ for 12h to obtain 1C-FeOOL powder.
Example 2
Unlike example 1, in step 2, a glucose mass of 0.18g was used, and 2C-FeOCl powder was finally obtained.
Example 3
In step 2, a difference from example 1 was that 0.36g of glucose in mass was used to finally obtain 3C-FeOCl powder.
Example 4
And (3) performing a heating program on ferric chloride hexahydrate, keeping the temperature of 255 ℃ for 3 hours at the heating rate of 12 ℃/min from the room temperature to 255 ℃, cooling to the room temperature, cleaning and drying to obtain FeOCl powder.
FIG. 2 is an XRD pattern for C, feOCl,1C-FeOCl,2C-FeOCl and 3C-FeOCl. In the XRD pattern of C, a broad diffraction peak at 18.2 ℃ was observed, corresponding to the (002) peak of amorphous carbon. In the XRD pattern of FeOCl, typical peaks at positions 11.2, 26.1, 32.7 and 36.1 ° are assigned to the (010), (110), (120) and (021) crystal planes, respectively. Where the peak of 2 θ =11.2 ° represents the interlayer distance of FeOCl, the interlayer distance (d) calculated according to Bragg equation (2 dsin θ = λ) is 0.79nm. XRD patterns recorded on XC-FeOCl composites (X =1, 2 and 3) showed similar peaks as on FeOCl. The (010) diffraction peaks of 2C-FeOCl and 3C-FeOCl are clearly shifted from 11.2 to 7.9, and the calculated interlayer distance is increased from 0.79 to 1.10nm, which is confirmed in HRTEM of 2C-FeOCl, further demonstrating the spread of interlayer distance. A new weak peak around 22.1 ℃ appears on the XRD pattern of 2C-FeOCl, which is considered to be C (002).
The C1s spectrum of 2C-FeOCl XPS (FIG. 3) is divided into 4 peaks at 288.5, 286.1, 284.8 and 284.1eV, corresponding to O = C-O, C-C and Fe-C, respectively, indicating that the lattice Cl moiety is replaced by a C atom to generate Fe-C bonds. As shown in FIG. 4, the FT-IR spectrum of FeOCl was found to be 490cm -1 Two characteristic peaks related to Fe-O are formed,at 1630cm -1 The bending vibration of-O-H in the adsorbed water. The C samples appeared at 1200-987, 1482 and 1778-1577cm -1 The central peaks are from the stretching vibrations of C-O-C, C = C and C = O, respectively. Spectra recorded on C-FeOCl samples except at 550cm -1 A new peak is shown, and the peak is similar to that of FeOCl. The appearance of a new peak is attributed to the formation of Fe-C bonds, indicating that the C atoms enter the FeOCl lattice. The formation of Fe-C bonds may be due to the weaker Fe-Cl bonds, resulting in the replacement of the Cl atoms of the outer and inner surfaces of FeOCl by C atoms. As shown in FIG. 5, XPS measurement spectrum of 2C-FeOCl showed the presence of Fe, O, cl and C elements. In the XPS measurement spectrum of 2C-FeOCl, the signal of Cl 2p shows a weaker intensity than FeOCl, confirming that the Cl atom is partially substituted by the C atom. The above characterization results indicate that C was successfully incorporated into the crystal lattice of FeOCl.
FIGS. 6-9 are SEM, TEM and HRTEM representations of composite C-FeOCl, C and FeOCl. The shapes shown in fig. 6 and 7 show that carbon is a fish scale nanosheet, and FeOCl is a flaky nanosheet with a thickness of 100 nm. FIG. 8 shows FeOCl in C-FeOCl is exfoliated into thin nanosheets, expanding the close-packed layered structure. This is due to the thermolysis of D (+) -glucose monohydrate, the original FeOCl lamellae are supported and the interlaminar extension of FeOCl exposes rich Fe active sites and H 2 O 2 And (4) matching.
As shown in FIG. 10, in the Raman spectrum of FeOCl, 322cm -1 The bands at 390 and 535cm-1 are considered as the tensile modes of Fe-O. 708cm -1 The distinct peak at (a) belongs to the characteristic peak of FeOC. In the case of 2C-FeOCl, the FeOCl characteristic peak is blue-shifted as a whole, and it is likely that carbon dots are embedded between FeOCl layers. Furthermore, 1289cm -1 And 1584cm -1 The other two peaks are assigned to the d-band and g-band of carbon, respectively. At 217cm -1 A new peak appears due to the Fe-C bond, and the above results indicate that the carbon dots are successfully embedded between layers of FeOCl.
FIG. 11 is an ultraviolet-visible diffuse reflectance spectrum (UV-vis DRS) of composite C-FeOCl, C and FeOCl. It can be seen that pure FeOCl responds relatively weakly to visible light. Compared with pure FeOCl, the visible light optical response of the C-FeOCl composite material is greatly enhanced. The introduction of carbon can greatly improve the visible light response of the C-FeOCl composite material.
The effect of the composite materials prepared in examples 1 to 3 (labeled as 1C-FeOCl,2C-FeOCl and 3C-FeOCl, respectively) on the degradation of tetracycline by photo-Fenton under visible light was compared:
taking 3 groups of 100mL tetracycline solutions with the initial concentration of 100mg/L, respectively placing the 3 groups of solutions into beakers for carrying out photocatalytic reaction, respectively adding the same amount of the composite materials (1C-FeOCl, 2C-FeOCl and 3C-FeOCl) prepared in the embodiments 1-3 into each group of tetracycline solutions, respectively, wherein the concentration of the composite materials is 0.1g/L, carrying out dark reaction for 30min through magnetic stirring to achieve adsorption and desorption balance, then placing the solutions under a visible light source of the photocatalytic reaction, adding a certain amount of hydrogen peroxide, continuing the magnetic stirring for 15min, taking supernate, passing through a 0.22 mu m water system film, and then determining the content of tetracycline in the solution under the wavelength of 357nm through an ultraviolet visible spectrophotometer.
Comparative example 1
100mL of tetracycline solution with the initial concentration of 100mg/L is taken and put into a beaker for carrying out photocatalytic reaction, equal FeOCl with the concentration of 0.1g/L is added into each group of tetracycline solution, dark reaction is carried out for 30min by magnetic stirring to achieve adsorption and desorption balance, then the tetracycline solution is placed under a visible light source of the photocatalytic reaction, a certain amount of hydrogen peroxide is added, after the magnetic stirring is continued for 15min, the supernatant is taken to pass through a 0.22 mu m water system film, and then the content of tetracycline in the solution is measured by an ultraviolet-visible spectrophotometer at the wavelength of 357 nm.
Comparative example 2
Taking 100mL of tetracycline solution with the initial concentration of 100mg/L, putting the tetracycline solution into a beaker for carrying out photocatalytic reaction, opening a visible light source, continuing magnetic stirring for 15min, taking supernatant, passing through a 0.22 mu m water system film, and measuring the content of tetracycline in the solution by an ultraviolet visible spectrophotometer at a wavelength of 357 nm.
Comparative example 3
100mL of tetracycline solution with the initial concentration of 100mg/L is taken and put into a beaker for carrying out photocatalytic reaction, the same amount of C with the concentration of 0.1g/L is added into each group of tetracycline solution, dark reaction is carried out for 30min by magnetic stirring to achieve adsorption-desorption balance, then the tetracycline solution is placed under a visible light source of the photocatalytic reaction, a certain amount of hydrogen peroxide is added, after the magnetic stirring is continued for 15min, the supernatant is taken to pass through a 0.22 mu m water system film, and then the content of tetracycline in the solution is measured by an ultraviolet-visible spectrophotometer at the wavelength of 357 nm.
Comparative example 4
100mL of tetracycline solution with the initial concentration of 100mg/L is taken and put into a beaker for carrying out photocatalytic reaction, the same amount of physically mixed C-FeOCl with the concentration of 0.1g/L is added into each group of tetracycline solution, dark reaction is carried out for 30min by magnetic stirring to achieve adsorption and desorption balance, then the tetracycline solution is placed under a visible light source of the photocatalytic reaction, a certain amount of hydrogen peroxide is added, magnetic stirring is continued for 15min, the supernatant is taken, passes through a 0.22 mu m water system membrane, and then the tetracycline content in the solution is measured by an ultraviolet visible spectrophotometer at the wavelength of 357 nm.
Table 1 shows the results of the composite materials obtained in examples 1 to 3 for removing tetracycline from water
| Catalyst and process for producing the same | Removal rate of |
| Photocatalyst of example 1 (1C-FeOCl) | 70％ |
| Photocatalyst of example 2 (2C-FeOCl) | 85％ |
| Photocatalyst of example 3 (3C-FeOCl) | 78％ |
| Comparison ofExample 1 | 50％ |
| Comparative example 2 | 3％ |
| Comparative example 3 | 6％ |
| Comparative example 4 | 62％ |
As can be seen from Table 1, the C-FeOCl composite material obtained in example 2 has the best tetracycline removal capacity, which is improved by 15% and 7% compared with examples 1 and 3, respectively. The catalyst of example 1 was due to too little glucose, resulting in insufficient hot gas flow to allow the inter-layer spacing of FeOCl to expand, leaving the unsaturated iron active sites on the inner surface exposed. In the case of the 3C-FeOCl catalyst, too much carbon source causes the unsaturated activated sites on the inner and outer surfaces to be masked, resulting in a decrease in the performance of activating hydrogen peroxide.
FIG. 12 is a graph of the effect of composite C-FeOCl, C and FeOCl in removing tetracycline antibiotics. The degradation of 2C-FeOCl to tetracycline can reach 85% within 15min, and the degradation is improved by 2.2 times compared with FeOCl, because the introduction of C enhances the absorption capability of visible light on one hand, and on the other hand, after C enters FeOCl crystal lattice, fe-C bond is formed between C and FeOCl, which is beneficial to the migration of photo-generated electrons to promote Fe 3+ So that there is an active and constant Fe 2+ And the water reacts with hydrogen peroxide to generate hydroxyl to degrade pollutants. The introduction of carbon in the composite material can improve the separation of photon-generated carriers, promote the iron circulation and greatly improve the photo-Fenton catalytic performance of the composite material.
Claims (6)
1. A preparation method of a carbon-doped iron oxychloride composite material is characterized by comprising the following steps: mixing and grinding FeOCl and glucose in a mass ratio of 5; in the C-FeOCl composite material, C is doped between layers and in crystal lattices of FeOCl.
2. The method for preparing a carbon-doped iron oxychloride composite material as claimed in claim 1, wherein the method comprises the following steps: a warming procedure was performed from room temperature to 250 ℃.
3. The method for preparing a carbon-doped iron oxychloride composite material as claimed in claim 1, wherein the method comprises the following steps: the temperature is raised to 250 ℃ at a heating rate of 10 ℃/min.
4. The method for preparing a carbon-doped iron oxychloride composite material as claimed in claim 1, wherein the method comprises the following steps: the temperature is kept at 250 ℃ for 2.5h.
5. The method for preparing a carbon-doped iron oxychloride composite material as claimed in claim 1, wherein the method comprises the following steps: the FeOCl is prepared and synthesized by ferric trichloride hexahydrate through a pyrolysis method.
6. The method for preparing a carbon-doped iron oxychloride composite material as claimed in claim 5, wherein the method comprises the following steps: the preparation method of the FeOCl comprises the following steps: and (3) performing a temperature rise program on ferric trichloride hexahydrate, keeping the temperature of 250-255 ℃ for 2.5-3 h at the temperature rise rate of 10-12 ℃/min from the room temperature to 250-255 ℃, cooling to the room temperature, cleaning and drying to obtain FeOCl powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211410789.9A CN115770593A (en) | 2022-11-11 | 2022-11-11 | Preparation method of carbon-doped iron oxychloride composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211410789.9A CN115770593A (en) | 2022-11-11 | 2022-11-11 | Preparation method of carbon-doped iron oxychloride composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115770593A true CN115770593A (en) | 2023-03-10 |
Family
ID=85388895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211410789.9A Pending CN115770593A (en) | 2022-11-11 | 2022-11-11 | Preparation method of carbon-doped iron oxychloride composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115770593A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150375302A1 (en) * | 2013-02-27 | 2015-12-31 | University Of Calcutta | Metal nanoparticles and methods for their preparation and use |
| CN107720928A (en) * | 2017-11-09 | 2018-02-23 | 哈尔滨工业大学 | A kind of method that FeOCl catalytic ozonation removes Organic substance in water |
| CN109999853A (en) * | 2019-04-18 | 2019-07-12 | 河南师范大学 | A kind of high activity BiOCl/Bi24O31Cl10The preparation method of composite photocatalyst material |
| CN112337490A (en) * | 2020-11-10 | 2021-02-09 | 安徽舜禹水务股份有限公司 | Preparation of Mn-FeOCl material and application method of Mn-FeOCl material in catalytic degradation of malachite green in water |
| CN113786849A (en) * | 2021-09-29 | 2021-12-14 | 上海电力大学 | FeOCl/GQDs composite transition metal catalyst, and preparation method and application thereof |
| CN113941343A (en) * | 2021-11-08 | 2022-01-18 | 武汉纺织大学 | Sludge-based composite catalyst and preparation method and application thereof |
-
2022
- 2022-11-11 CN CN202211410789.9A patent/CN115770593A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150375302A1 (en) * | 2013-02-27 | 2015-12-31 | University Of Calcutta | Metal nanoparticles and methods for their preparation and use |
| CN107720928A (en) * | 2017-11-09 | 2018-02-23 | 哈尔滨工业大学 | A kind of method that FeOCl catalytic ozonation removes Organic substance in water |
| CN109999853A (en) * | 2019-04-18 | 2019-07-12 | 河南师范大学 | A kind of high activity BiOCl/Bi24O31Cl10The preparation method of composite photocatalyst material |
| CN112337490A (en) * | 2020-11-10 | 2021-02-09 | 安徽舜禹水务股份有限公司 | Preparation of Mn-FeOCl material and application method of Mn-FeOCl material in catalytic degradation of malachite green in water |
| CN113786849A (en) * | 2021-09-29 | 2021-12-14 | 上海电力大学 | FeOCl/GQDs composite transition metal catalyst, and preparation method and application thereof |
| CN113941343A (en) * | 2021-11-08 | 2022-01-18 | 武汉纺织大学 | Sludge-based composite catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANGUO SUN ET AL.: "Enhanced photocatalytic activity induced by sp3 to sp2 transition of carbon dopants in BiOCl crystals", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 221, pages 468 * |
| JUN ZHANG ET AL.: "Carbon nanodot-modified FeOCl for photo-assisted Fenton reaction featuring synergistic in-situ H2O2 production and activation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 266, pages 2 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Enhanced photocatalytic activity of g-C3N4 2D nanosheets through thermal exfoliation using dicyandiamide as precursor | |
| Zaeni et al. | In situ nitrogen functionalization of biochar via one-pot synthesis for catalytic peroxymonosulfate activation: characteristics and performance studies | |
| Yu et al. | Co/N co-doped carbonized wood sponge with 3D porous framework for efficient peroxymonosulfate activation: Performance and internal mechanism | |
| Naeem et al. | Synthesis and characterization of graphene oxide sheets integrated with gold nanoparticles and their applications to adsorptive removal and catalytic reduction of water contaminants | |
| Kan et al. | Preparation and characterization of activated carbons from waste tea by H3PO4 activation in different atmospheres for oxytetracycline removal | |
| Li et al. | Tuning and thermal exfoliation graphene-like carbon nitride nanosheets for superior photocatalytic activity | |
| Saputra et al. | Egg-shaped core/shell α-Mn2O3@ α-MnO2 as heterogeneous catalysts for decomposition of phenolics in aqueous solutions | |
| CN108543544B (en) | Honeycomb homoheterojunction carbon nitride composite material, preparation method thereof and application thereof in catalytic treatment of waste gas | |
| Tan et al. | Equilibrium and kinetic studies on basic dye adsorption by oil palm fibre activated carbon | |
| Danish et al. | Characterization of Acacia mangium wood based activated carbons prepared in the presence of basic activating agents | |
| Chen et al. | Preparation of porous carbon-based material from corn straw via mixed alkali and its application for removal of dye | |
| CN109012724B (en) | CoMoO4/g-C3N4Composite photocatalyst and preparation method and application thereof | |
| Ji et al. | Immobilized Ag 3 PO 4/GO on 3D nickel foam and its photocatalytic degradation of norfloxacin antibiotic under visible light | |
| Wang et al. | Photocatalytic degradation of rhodamin B and diclofenac sodium on hollow hierarchical microspheres of BiOBr modified with sepiolite and polyvinyl pyrrolidone (PVP) | |
| Zhang et al. | Degradation of methylene blue by a heterogeneous Fenton reaction catalyzed by FeCo2O4-NC nanocomposites derived by ZIFs | |
| CN114409917A (en) | Moisture-resistant iron-based metal organic framework material with catalytic ozonolysis capability and preparation method and application thereof | |
| Saadati et al. | Insight into the adsorption and photocatalytic properties of in-situ synthesized g-C3N4/SnS2 nanocomposite | |
| Bo et al. | Interior engineering of seaweed-derived N-doped versatile carbonaceous beads with Co x O y for universal organic pollutant degradation | |
| Ren et al. | Facilely synthesized porous 3D coral-like Fe-based N-doped carbon composite as effective Fenton catalyst in methylene blue degradation | |
| Wu et al. | MoS2 and g-C3N4 nanosheet co-modified Bi2WO6 ternary heterostructure catalysts coupling with H2O2 for improved visible photocatalytic activity | |
| Lu et al. | The collaborative incentive effect in adsorption-photocatalysis: A special perspective on phosphorus recovery and reuse | |
| Maged et al. | Efficient photocatalytic reduction of p-nitrophenol under visible light irradiation based on Ag NPs loaded brown 2D g-C3N4/g-C3N4 QDs nanocomposite | |
| Ren et al. | The study on adsorption behavior of 2, 4-DCP in solution by biomass carbon modified with CTAB-KOH | |
| CN115770593A (en) | Preparation method of carbon-doped iron oxychloride composite material | |
| Chen et al. | Controllable conversion of Prussian blue@ yeast bio-template into 3D cage-like magnetic Fe 3 O 4@ N-doped carbon absorbent and its cohesive regeneration by persulfate activation |
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 |