CN115739118B - Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof - Google Patents
Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115739118B CN115739118B CN202211573611.6A CN202211573611A CN115739118B CN 115739118 B CN115739118 B CN 115739118B CN 202211573611 A CN202211573611 A CN 202211573611A CN 115739118 B CN115739118 B CN 115739118B
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- iron
- doped bismuth
- sulfur
- ball milling
- 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
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 62
- PQFQKWYOXSNSIP-UHFFFAOYSA-N [Bi]=O.[S] Chemical compound [Bi]=O.[S] PQFQKWYOXSNSIP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MKKCJTYKJLHFJO-UHFFFAOYSA-N [Bi].S=O Chemical compound [Bi].S=O MKKCJTYKJLHFJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004098 Tetracycline Substances 0.000 claims description 31
- 235000019364 tetracycline Nutrition 0.000 claims description 31
- 150000003522 tetracyclines Chemical class 0.000 claims description 31
- 229960002180 tetracycline Drugs 0.000 claims description 28
- 229930101283 tetracycline Natural products 0.000 claims description 28
- 230000001699 photocatalysis Effects 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000018199 S phase Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229940040944 tetracyclines Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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 an iron-doped bismuth-oxygen-sulfur photocatalyst, and a preparation method and application thereof, and belongs to the technical field of new environmental catalytic materials. The invention mainly uses Bi 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, and an iron-doped bismuth oxygen sulfur photocatalyst is prepared by adopting a high-energy ball milling method; wherein the doping amount of Fe in the Fe-doped bismuth oxide sulfur photocatalyst is 1.7-5.6%. The iron-doped bismuth oxysulfide photocatalyst obtained by the invention has higher photogenerated carrier transmission efficiency, rich reactive sites and stronger capability of activating persulfate.
Description
Technical Field
The invention belongs to the technical field of new environmental catalytic materials, and particularly relates to an iron-doped bismuth-oxygen-sulfur photocatalyst, and a preparation method and application thereof.
Background
The world's vast amount of antibiotics is continuously accumulating in the environment through the emissions of homes, hospitals, pharmaceutical companies, wastewater treatment plants, and aquaculture and livestock farms, contributing to the formation of Antibiotic Resistance Genes (ARG) and antibiotic-resistant bacteria (ARB) in the aquatic ecosystem, threatening public health. Tetracyclines (TCs) are a typical antibiotic that, due to their strong chemical stability and environmental durability, have an adverse effect on human health and the ecosystem. Moreover, the antimicrobial properties of tetracyclines make them difficult to eradicate by conventional biological wastewater treatment techniques. Therefore, there is an urgent need to develop an economical and effective antibiotic wastewater treatment method.
In recent years, advanced oxidation technology has been widely used to degrade refractory organic pollutants and mineralize them into CO 2 And H 2 O. Based on hydroxyl radicals (. OH) and sulfate radicals (SO) 4 - The prior oxidation technology is an effective method for degrading common organic pollutants, such as organic dyes, surfactants, hydrocarbons, phenols, pharmaceutical active ingredients, pesticides, and the like. However, advanced OH-based oxidation techniques degrade organic contaminants by a non-selective multi-step reaction, often requiring an acidic environment. SO based 4 - The advanced oxidation technology has more stable reaction process, less limitation conditions and faster reaction rate than the advanced oxidation technology based on OH, has rapidly progressed in recent years, and has been increasingly used in sewage treatment.
Currently, many metal ions and heterogeneous catalysts are used for SO-based 4 - Among advanced oxidation techniques, heterogeneous photocatalysts in particular have great potential for photocatalytic activation of persulfate to degrade contaminants. In addition, the catalytic activity of the photocatalyst can be obviously improved by doping transition metal into the photocatalyst, so that the aim of efficiently activating persulfate to degrade pollutants is fulfilled. However, the transition metal doping is usually prepared by a hydrothermal method or a solvothermal method, the process is long, secondary pollution can be generated, and the samples cannot be prepared in large quantities.
Disclosure of Invention
In view of the above, the present invention provides an iron doped bismuth oxysulfide photocatalyst, and a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the above purpose, the present invention proposes the following technical scheme:
an Fe-doped bismuth-oxygen-sulfur photocatalyst is prepared from Bi 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, and an iron-doped bismuth oxygen sulfur photocatalyst is prepared by adopting a high-energy ball milling method; wherein the doping amount of Fe in the Fe-doped bismuth oxide sulfur photocatalyst is 1.7-5.6%.
Further, the Bi 2 O 2 The particle size of S crystal is nano lamellar structure.
The invention also provides a preparation method of the iron-doped bismuth oxygen sulfur photocatalyst, which comprises the following steps:
bi is used as 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, and a high-energy ball milling method is adopted to prepare the Fe-doped bismuth-oxygen-sulfur photocatalyst, wherein Bi 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 The mass ratio of O is 0.5: (0.0625-0.2142).
Further, in the ball milling process, the ball milling transfer intensity was 800rpm, and the ball milling time was 20min.
Further, the ball-milled sample was stirred in water at room temperature to remove excess iron salt, which was then dried.
Still further, the stirring time was 120min.
The invention also provides application of the iron-doped bismuth oxysulfide photocatalyst in treating wastewater containing organic matters by photocatalytic activation of persulfate.
Further, the organic matter is tetracycline.
Compared with the prior art, the invention has the beneficial effects that:
1) The preparation of the iron-doped bismuth oxide sulfur photocatalyst adopts a high-energy ball milling method, and has the advantages of relatively simple and safe operation, low cost, mass preparation and the like;
2) The obtained iron-doped bismuth oxysulfide photocatalyst has higher photogenerated carrier transmission efficiency, rich reactive sites and stronger capability of activating persulfate, and is characterized in that the iron doping can change the energy band structure of the bismuth oxysulfide photocatalyst and generate new energy levels, so that the separation of the photogenerated carriers can be promoted; the surface of the ground bismuth oxysulfide photocatalyst can expose more reactive sites, so that the activation of persulfate is facilitated;
3) The obtained iron-doped bismuth oxysulfide photocatalyst shows excellent activity and stability of degrading tetracycline by photocatalytic activation of persulfate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of the iron-doped bismuth oxysulfide photocatalyst prepared by example 1-3 of the invention and a catalyst prepared by a control group;
FIG. 2 is a graph showing the effect of photocatalytic activation of persulfate to degrade tetracycline by the iron-doped bismuth oxysulfide photocatalyst prepared in examples 1-3 of the present invention and the catalyst prepared in the control group;
FIG. 3 is a TEM image of an iron-doped bismuth oxysulfide photocatalyst prepared by the method of example 2 of the present invention;
FIG. 4 is an XRD pattern of the iron-doped bismuth oxysulfide photocatalyst prepared in example 2 of the present invention before and after the photocatalytic reaction;
FIG. 5 is a graph showing the effect of the iron-doped bismuth oxysulfide photocatalyst prepared in example 2, comparative example 1 and comparative example 2 of the present invention on the degradation of tetracycline by the photocatalytic activation of persulfate.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "room temperature" as used herein is calculated as 25.+ -. 2 ℃ unless otherwise indicated.
Raw material Fe (NO) used in the present invention 3 ) 3 ·9H 2 O (analytically pure) was purchased from the national drug group;
an Fe-doped bismuth-oxygen-sulfur photocatalyst is prepared from Bi 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, and an iron-doped bismuth oxygen sulfur photocatalyst is prepared by adopting a high-energy ball milling method; wherein the doping amount of Fe in the Fe-doped bismuth oxide sulfur photocatalyst is 1.7-5.6%.
In some preferred embodiments, the Bi 2 O 2 S crystal is nano sheet structure.
The invention also provides a preparation method of the iron-doped bismuth oxygen sulfur photocatalyst, which comprises the following steps:
bi is used as 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, a high-energy ball milling method is adopted,preparing an iron-doped bismuth oxysulfide photocatalyst, wherein Bi 2 O 2 The mass of S crystal is 0.5g; fe (NO) 3 ) 3 ·9H 2 The mass of O is 0.0625-0.2142g, more preferably 0.0625g, 0.125g and 0.2142g.
In some preferred embodiments, during the ball milling process, the ball milling transfer intensity is 800rpm and the ball milling time is 20 minutes.
In some preferred embodiments, the ball milled sample is stirred in water at room temperature and dried.
In some preferred embodiments, the agitation time is 120 minutes.
The invention also provides an application of the iron-doped bismuth oxysulfide photocatalyst in activating persulfate to degrade tetracycline under simulated sunlight.
Example 1
A preparation method of an iron-doped bismuth oxygen sulfur photocatalyst comprises the following steps:
1) Weighing 0.5g of Bi 2 O 2 S crystal, 0.0625g Fe (NO) 3 ) 3 ·9H 2 Adding O into a ball milling tank, and grinding for 20min in a ball mill with the working intensity of 800rpm to obtain a ball-milled sample;
2) And adding the ball-milled sample into 250mL of water at room temperature, stirring for 120min, washing with water, and drying to obtain the iron-doped bismuth oxysulfide photocatalyst, and marking with 1.7% of Fe/BiOS.
Example 2
A preparation method of an iron-doped bismuth oxygen sulfur photocatalyst comprises the following steps:
1) Weighing 0.5g of Bi 2 O 2 S crystal, 0.125g Fe (NO) 3 ) 3 ·9H 2 Adding O into a ball milling tank, and grinding for 20min in a ball mill with the working intensity of 800rpm to obtain a ball-milled sample;
2) And adding the ball-milled sample into 250mL of water at room temperature, stirring for 120min, washing with water, and drying to obtain the iron-doped bismuth oxysulfide photocatalyst, and marking with 3.3% of Fe/BiOS.
Example 3
A preparation method of an iron-doped bismuth oxygen sulfur photocatalyst comprises the following steps:
1) Weighing 0.5g of Bi 2 O 2 S crystal, 0.2412g of Fe (NO) 3 ) 3 ·9H 2 Adding O into a ball milling tank, and grinding for 20min in a ball mill with the working intensity of 800rpm to obtain a ball-milled sample;
2) And adding the ball-milled sample into 250mL of water at room temperature, stirring for 120min, washing with water, and drying to obtain the iron-doped bismuth oxysulfide photocatalyst, and marking with 5.6% Fe/BiOS.
Control group 1
A preparation method of an iron-doped bismuth oxygen sulfur photocatalyst comprises the following steps:
Bi 2 O 2 s preparation of crystals: 1.9403g of Bi (NO 3 ) 3 ·5H 2 O was added to 60mL of deionized water and stirred well, and 0.1522g of SC (NH) 2 ) 2 Stirring was continued for 10min, then 12g of LiOH H were added 2 Slowly adding O into the mixed solution, and continuously stirring for 60min to form a brownish black mixed solution; the stirred homogeneous mixed solution was transferred to an 80mL autoclave lined with PPL. The autoclave was heated to 200℃in a forced air drying oven and maintained at this temperature for 72h. After the autoclave was cooled to room temperature, the remaining samples were collected and washed with deionized water several times. Finally, the washed sample was dried in a vacuum oven at 60℃for 12 hours. Collecting the dried sample to obtain Bi 2 O 2 S sample (labeled BiOS).
FIG. 1 is an X-ray diffraction pattern of the iron-doped bismuth oxysulfide photocatalyst prepared by example 1-3 of the invention and a catalyst prepared by a control group. As can be seen from the figure, XRD diffraction peak position of 1.7% Fe/BiOS prepared in example 1 was compared with Bi 2 O 2 S (PDF#34-1493) standard peak position corresponds to indicate Bi in the doped photocatalyst 2 O 2 S phase is not changed, and other impurities are not generated; XRD diffraction peak position of 3.3% Fe/BiOS prepared in example 2 and Bi 2 O 2 S (PDF#34-1493) standard peak position corresponds to indicate Bi in the doped photocatalyst 2 O 2 S phase is not changed, and other impurities are not generated; implementation of the embodimentsXRD diffraction peak position of 5.6% Fe/BiOS prepared in example 3 and Bi 2 O 2 S (PDF#34-1493) standard peak position corresponds to indicate Bi in the doped photocatalyst 2 O 2 The S phase is not changed, and no other impurities are generated.
Application example 1
The iron-doped bismuth oxysulfide photocatalyst prepared in the examples 1-3 and the catalyst prepared in the control group 1 are subjected to a photocatalytic activation persulfate degradation tetracycline performance test, and the specific method is as follows:
0.05g of the iron-doped bismuth oxide sulfur photocatalyst prepared in the examples 1-3 and the catalyst prepared in the control group 1 are weighed and added into 100mL of tetracycline solution with the concentration of 30mg/L, the mixture is stirred for 0.5h in a shading way, the catalyst and pollutants are uniformly mixed and reach adsorption balance, 5mL of the solution is taken into a centrifuge tube, and 1mL of methanol is added. Then, 0.03g of persulfate (potassium persulfate was used in the present experiment) was rapidly added to the beaker, while a xenon lamp (300W) was turned on to conduct a light reaction for 30 minutes, 5mL of the solution was taken into a centrifuge tube every 5 minutes, and 1mL of methanol was added. And measuring the absorbance of the tetracycline at the position of 357nm of the maximum absorption wavelength of the tetracycline by using a spectrophotometer, and analyzing the change of the tetracycline concentration according to the test result, thereby calculating the degradation effect of the photocatalyst on the tetracycline.
FIG. 2 is a graph showing the effect of photocatalytic activation of persulfate to degrade tetracycline by the iron-doped bismuth oxysulfide photocatalyst prepared in examples 1-3 of the present invention and the catalyst prepared in the control group. As can be seen from fig. 2, in the test of photocatalytic activation of persulfate to degrade tetracycline, 83% of the 1.7% fe/BiOS catalyst prepared in example 1 was degraded; in the test of photocatalytic activation of persulfate to degrade tetracycline, the 3.3% Fe/BiOS catalyst prepared in example 2, 90% of the tetracycline was degraded; in the test of photocatalytic activation of persulfate to degrade tetracycline, the 5.6% Fe/BiOS catalyst prepared in example 3, 86% of the tetracycline was degraded; while unmodified Bi 2 O 2 S in the test of degrading tetracycline by photocatalytic activation persulfate, 57% of tetracycline is degraded, thus showing that the performance of the catalysts prepared in the examples 1-3 of the invention in degrading tetracycline by photocatalytic activation persulfate is obviously higher than that of unmodified Bi 2 O 2 S。
Fig. 3 is a TEM image of the iron doped bismuth oxysulfide photocatalyst prepared by example 2 of the present invention. From the figure, the iron-doped bismuth oxygen sulfur photocatalyst prepared by the ball milling method is nano-sheet.
Fig. 4 is an XRD pattern before and after the photocatalytic reaction of the iron-doped bismuth oxysulfide photocatalyst prepared by example 2 of the present invention. From the graph, XRD of the iron-doped bismuth oxide sulfur photocatalyst before and after the photocatalytic reaction does not change obviously, which indicates that the iron-doped bismuth oxide sulfur photocatalyst has good stability.
Comparative example 1
The difference from example 2 is that the ball milling time is 10min.
The photocatalytic-activated persulfate degradation performance test was performed in the same manner as in example 2, and as a result, it was found that 84% of tetracycline was degraded.
Comparative example 2
The difference from example 2 is that the ball milling time is 40min.
The same procedure as in example 2 was followed to test the photocatalytic-activated persulfate degradation of tetracycline, and as a result, it was found that 90% of tetracycline was degraded.
FIG. 5 is a graph showing the effect of the iron-doped bismuth oxysulfide photocatalyst prepared in example 2, comparative example 1 and comparative example 2 of the present invention on the degradation of tetracycline by the photocatalytic activation of persulfate. From the graph, the effect of the iron-doped bismuth oxide sulfur photocatalyst obtained by grinding for 10min in photocatalytic reaction for 30min for degrading tetracycline through the persulfate is inferior to that of the iron-doped bismuth oxide sulfur photocatalyst obtained by grinding for 20min; the iron-doped bismuth oxysulfide photocatalyst obtained after 20min and 40min of grinding has equivalent effect of degrading tetracycline by photocatalytic activation of persulfate. However, in view of energy consumption and cost, a method for grinding for 20min to obtain the iron-doped bismuth oxysulfide photocatalyst is more suitable.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (3)
1. The preparation method of the iron-doped bismuth oxygen sulfur photocatalyst for treating tetracycline-containing wastewater by using photocatalytic activation persulfate is characterized by comprising the following steps of:
bi is used as 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 O is used as a raw material, and a high-energy ball milling method is adopted to prepare the Fe-doped bismuth-oxygen-sulfur photocatalyst, wherein Bi 2 O 2 S crystal and Fe (NO) 3 ) 3 ·9H 2 The mass ratio of O is 0.5: (0.0625-0.2142);
the doping amount of Fe in the Fe-doped bismuth oxide sulfur photocatalyst is 1.7-5.6%;
in the ball milling process, the working intensity of the ball milling is 800rpm, and the ball milling time is 20min;
the ball-milled sample was stirred in water at room temperature for 120min and dried.
2. The method according to claim 1, wherein the Bi 2 O 2 S crystal is nano sheet structure.
3. Use of the iron-doped bismuth oxysulfide photocatalyst prepared by the preparation method of claim 1 or 2 in treating tetracycline-containing wastewater by photocatalytic activation of persulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211573611.6A CN115739118B (en) | 2022-12-08 | 2022-12-08 | Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211573611.6A CN115739118B (en) | 2022-12-08 | 2022-12-08 | Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115739118A CN115739118A (en) | 2023-03-07 |
| CN115739118B true CN115739118B (en) | 2024-02-27 |
Family
ID=85344570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211573611.6A Active CN115739118B (en) | 2022-12-08 | 2022-12-08 | Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739118B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120105123A (en) * | 2011-03-15 | 2012-09-25 | 금오공과대학교 산학협력단 | TRANSITION METAL DOPED TiO2 PHOTOCATALYST'S PREPARATION METHOD |
| CN111617784A (en) * | 2020-06-23 | 2020-09-04 | 盐城工学院 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
| CN112452342A (en) * | 2020-09-15 | 2021-03-09 | 湖北省工程咨询股份有限公司 | Co-doped Bi2O2S catalyst and preparation method and application thereof |
| CN113797932A (en) * | 2021-10-13 | 2021-12-17 | 陕西科技大学 | Doped bismuth niobate titanate nanosheet and preparation method thereof |
-
2022
- 2022-12-08 CN CN202211573611.6A patent/CN115739118B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120105123A (en) * | 2011-03-15 | 2012-09-25 | 금오공과대학교 산학협력단 | TRANSITION METAL DOPED TiO2 PHOTOCATALYST'S PREPARATION METHOD |
| CN111617784A (en) * | 2020-06-23 | 2020-09-04 | 盐城工学院 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
| CN112452342A (en) * | 2020-09-15 | 2021-03-09 | 湖北省工程咨询股份有限公司 | Co-doped Bi2O2S catalyst and preparation method and application thereof |
| CN113797932A (en) * | 2021-10-13 | 2021-12-17 | 陕西科技大学 | Doped bismuth niobate titanate nanosheet and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Cobalt doped bismuth oxysulfide with abundant oxygen vacancies towards tetracycline degradation through peroxymonosulfate activation;Jie Ren et al.;《Separation and Purification Technology》;第275卷;第2页2.1，2.3节 * |
| Efficiency of Mechanochemical Ball Milling Technique in the Preparation of Fe/TiO2 Photocatalysts;Shabnam Taghipour et al.;《ChemEngineering》;第6卷(第77期);第2页2.1-2.2节，第5页第2段，第12页4节 * |
| ZnO磁性纳米材料的制备以及光催化性能的研究;秦俊鹏等;《广东化工》;第43卷(第9期);48-49 * |
| 机械力化学法改性TiO2研究;曹怀宝等;《安徽理工大学学报(自然科学版)》;第27卷(第1期);43-47 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115739118A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112337490B (en) | Mn-FeOCl material preparation and application method for catalytic degradation of malachite green in water | |
| CN107497450B (en) | A kind of compound bismuth tantalate photochemical catalyst and its preparation method and application | |
| CN107469834A (en) | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method | |
| CN113731444B (en) | Sb-SnO for degrading organic wastewater 2 /SnS 2 Nano catalyst and preparation method and application thereof | |
| CN102836702A (en) | Transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst and preparation method and application thereof | |
| CN108543542B (en) | Preparation method and application of three-dimensional porous composite photocatalyst | |
| CN110841669B (en) | Method for treating heavy metals and organic pollutants by using zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst | |
| CN115138369A (en) | Molybdenum trioxide composite material and preparation method and application thereof | |
| CN114054019B (en) | Lithium, manganese and titanium composite oxide photocatalyst, preparation method and application thereof | |
| CN114314762B (en) | Nano ZnO/pyrolusite composite particle electrode and preparation method thereof | |
| CN111632619A (en) | Copper-nitrogen co-doped titanium dioxide photocatalytic material, preparation method and application | |
| CN115739118B (en) | Iron-doped bismuth oxygen sulfur photocatalyst and preparation method and application thereof | |
| CN113578310A (en) | CdS @ ZnCr-LDHs heterojunction nano material for photocatalytic degradation of tetracycline, and preparation method and application thereof | |
| CN112517046A (en) | Universal preparation method of hierarchical-pore nitrogen-doped carbon-oxygen reduction catalyst based on double-pore-foaming agent synthesis | |
| CN108714428B (en) | Nanowire photocatalyst and preparation method and application thereof | |
| CN109499591B (en) | Preparation method and application of magnetically-recoverable photo-Fenton-like catalyst | |
| CN115463693B (en) | Ag (silver) alloy 2 O/isonicotinic acid-Bi composite photocatalyst and preparation and application thereof | |
| CN114471707B (en) | Hydrogel sphere containing catalyst, preparation method thereof and application thereof in photocatalytic treatment of organic pollutants | |
| CN115957769A (en) | MoO 2 @ CoFe LDHs photocatalyst and application thereof in degrading tetracycline with persulfate in synergy mode | |
| CN110227476B (en) | BiFeO 3 /Bi 25 FeO 40 Preparation method and application of heterostructure catalyst | |
| CN109133452A (en) | A kind of magnalium hydrotalcite load TiO2The method of photocatalysis adsorbent material processing tetracycline antibiotics waste water | |
| CN109046366A (en) | A kind of hetero-junctions micron box composite photo-catalyst and its preparation method and application | |
| CN112973671A (en) | Nano bismuth tungstate/zinc oxide heterojunction catalyst, preparation method and application thereof | |
| Priya et al. | Comparative analysis of photo degradation kinetics using linear and non-linear kinetic models | |
| CN116351424B (en) | Preparation method and application of high-moisture-resistance LDH@graphene ozonolysis catalyst |
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 |