CN116351471B - Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof - Google Patents
Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN116351471B CN116351471B CN202310242005.4A CN202310242005A CN116351471B CN 116351471 B CN116351471 B CN 116351471B CN 202310242005 A CN202310242005 A CN 202310242005A CN 116351471 B CN116351471 B CN 116351471B
- Authority
- CN
- China
- Prior art keywords
- prussian blue
- composite photocatalyst
- suspension
- product
- preparation
- 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
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 97
- 239000013225 prussian blue Substances 0.000 title claims abstract description 97
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 239000000725 suspension Substances 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003115 biocidal effect Effects 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 7
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 7
- 229940079593 drug Drugs 0.000 claims abstract description 6
- 239000003814 drug Substances 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 29
- 238000006731 degradation reaction Methods 0.000 abstract description 29
- 230000031700 light absorption Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 238000001782 photodegradation Methods 0.000 abstract description 3
- 239000004098 Tetracycline Substances 0.000 description 21
- 235000019364 tetracycline Nutrition 0.000 description 21
- 150000003522 tetracyclines Chemical class 0.000 description 21
- 229960002180 tetracycline Drugs 0.000 description 19
- 229930101283 tetracycline Natural products 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000012546 transfer Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 229960003405 ciprofloxacin Drugs 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- VMXUWOKSQNHOCA-LCYFTJDESA-N ranitidine Chemical compound [O-][N+](=O)/C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-LCYFTJDESA-N 0.000 description 4
- 229960000620 ranitidine Drugs 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention provides a Prussian blue/g-C 3N4 composite photocatalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4; dripping polyvinylpyrrolidone, potassium ferricyanide and a product g-C 3N4 into an HCl solution to obtain a suspension, and performing hydrothermal reaction in a stainless steel autoclave; and after the reaction is finished, cooling, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and vacuum drying to obtain the Prussian blue/g-C 3N4 composite photocatalyst. The Prussian blue/g-C 3N4 composite photocatalyst has the advantages of enlarged visible light absorption area, enhanced absorption capacity and high visible light utilization rate, and has obvious effect on photodegradation of environmental pollutants such as degradation antibiotic medicines and dyes.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a Prussian blue/g-C 3N4 composite photocatalyst, and a preparation method and application thereof.
Background
Over the last decades, with the continued development of urbanization, a large number of antibiotics have been widely used to treat human and animal infections. Tetracyclines, a typical antibiotic, have been widely used in human therapy, animal therapy and agricultural production. It has been reported that about 21 ten thousand tons of tetracycline are discharged into the aquatic ecosystem together with wastewater each year due to incomplete treatment by conventional methods. In addition, it has been found that even at nanogram levels, tetracycline in the aquatic ecosystem poses a serious threat to the environment and human health. The heterogeneous light Fenton technology is regarded as an effective method for degrading persistent organic pollutants as an advanced oxidation process due to high efficiency, good circularity, simple operation and no generation of a large amount of iron mud. However, most of the reported photo-Fenton catalysts absorb only ultraviolet rays, accounting for only about 5% of the solar spectrum, which makes it difficult to use natural solar ultraviolet rays as an energy source. In addition, some photo-Fenton catalysts exhibit high activity only at low pH values, or require expensive chemicals and time consuming synthetic processes. Therefore, developing a visible light response pH analyzer with a simple synthesis procedure and a wide operating pH is critical to facilitate the application of the photo Fenton technique.
Graphite carbonitride (g-C 3N4) is widely applied to environmental remediation and water treatment due to the characteristics of rich resources, simple preparation, unique belt structure and the like. However, its degradation performance is severely limited due to its low surface area, limited visible light utilization, and poor charge separation and transfer efficiency.
According to previous reports, it has been demonstrated that the degradation performance of g-C 3N4 can be greatly improved by expanding the light absorption range, increasing the charge separation and transfer ability, and activating the photo Fenton (-like) reaction when g-C 3N4 is coupled with a transition metal-based material. Prussian blue is a class of metal-organic frameworks with face-centered cubic cells in which ferrous (Fe II) and ferric (Fe III) ions are alternately bridged by cyano ligands (C≡N), where high spin FeHS (Fe III) is coupled to N and low spin Fe LS (Fe II) is coordinated to C. Prussian blue and its analogues are considered ideal materials for coupling with g-C 3N4 due to their low cost, low toxicity, relative stability and unique chemical composition. Although Prussian blue degradation contaminants have been reported in Fenton systems, the combination of Prussian blue with g-C 3N4 used in optical Fenton systems has been rarely studied.
Structural defect engineering has received much attention as another popular strategy for improving the photocatalytic performance of g-C 3N4, which can not only modulate the electronic structure but also increase the active sites. In particular, when defects (N, C, O, etc.) are introduced into the framework of g-C 3N4 having a larger surface area, a synergistic improvement effect of photocatalytic performance is exhibited. In addition, various forms of g-C 3N4 (including macropores, nanoplatelets, microtubes) have been widely studied, which exhibit better photocatalytic performance in the photo Fenton reaction than the conventional g-C 3N4 bulk photocatalyst. The two-dimensional ultrathin nanosheets with the porous structures not only provide more pollutant exposure, but also shorten the charge transfer distance and prolong the charge recombination time. Therefore, it is very feasible to construct porous two-dimensional ultrathin g-C 3N4 nanoplatelets with contaminant degradation defects.
According to the background, a carbon vacancy is introduced into a porous two-dimensional ultrathin g-C 3N4 nano sheet, and a high-efficiency photo Fenton catalyst with enhanced degradation performance can be constructed by combining crystalline Prussian blue nano particles. A series of Prussian blue supported and carbon vacancy g-C 3N4 (Prussian blue/porous defective g-C 3N4 nanoplatelets) hybrid catalysts were successfully synthesized by simple hydrothermal methods.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the defects existing in the prior art, the invention provides the Prussian blue/g-C 3N4 composite photocatalyst, the preparation method and the application thereof, the visible light absorption area of the Prussian blue/g-C 3N4 composite photocatalyst is enlarged, the absorption capacity is enhanced, the visible light utilization rate is high, and the Prussian blue/g-C 3N4 composite photocatalyst has obvious effect on photodegradation of environmental pollutants such as antibiotic medicines and dyes.
The technical scheme is as follows: a preparation method of Prussian blue/g-C 3N4 composite photocatalyst comprises the following steps:
Step one: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4, wherein the mass ratio of the urea to the deionized water is 1:1;
Step two: dripping polyvinylpyrrolidone, potassium ferricyanide and the product g-C 3N4 prepared in the first step into HCl solution to obtain suspension, and placing the suspension into a stainless steel autoclave for hydrothermal reaction, wherein the mass ratio of the product g-C 3N4 to the product g-C 3N4 is (50-350) to (2500-3500) to (25-28), and the mass ratio of the product g-C 3N4 to the product g-C mLHCl is (0.08-0.35).
Step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and then drying the precipitate in vacuum to obtain the Prussian blue/g-C 3N4 composite photocatalyst.
The calcination temperature in the first step is 550 ℃ and the time is 4 hours.
The concentration of the HCl solution in the second step is 0.01mol/L.
The specific procedure for the hydrothermal reaction in step two described above was to place the suspension in a stainless steel autoclave with a 50mL capacity teflon liner and to react in an oven at 80 ℃ for 20h.
And in the third step, the vacuum drying temperature is 60 ℃ and the time is 12 hours.
The Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method of the Prussian blue/g-C 3N4 composite photocatalyst is provided.
The Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method is applied to degradation of antibiotic medicines and dye pollutants.
The beneficial effects are that: the Prussian blue/g-C 3N4 composite photocatalyst and the preparation method and application thereof provided by the invention have the following beneficial effects:
1. According to the invention, due to the interfacial interaction between g-C 3N4 and Prussian blue and the synergistic effect of carbon defects, the utilization rate of the material to visible light is effectively improved, the photogenerated charge transfer efficiency is maximized, the charge transfer and conduction capacity is stronger, and the higher oxidation-reduction capacity of the material is also maintained; the visible light absorption capacity of the prepared catalyst is improved, the absorption area is enlarged, and the utilization rate of visible light is improved;
2. the composite photocatalyst prepared by the invention has obvious effect on photodegradation of environmental pollutants such as antibiotic medicines, dyes and the like;
3. The preparation method has the advantages of simplicity in operation, good repeatability, low cost, easiness in condition control and the like;
4. According to the invention, the urea is selected to prepare the g-C 3N4 at high temperature, and the Prussian blue loaded and carbon vacancy g-C 3N4 (Prussian blue/porous defective g-C 3N4 nano-sheet) hybrid catalyst is synthesized by a simple hydrothermal method, so that the catalyst is applied to degradation of environmental pollutants such as antibiotic medicines and dyes, and has good photocatalytic activity;
5. The invention provides new insight for designing a high-efficiency photoelectric Fenton catalyst for environmental remediation.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 2 is a Prussian blue/g-C 3N4 (I) composite photocatalyst Transmission Electron Microscope (TEM) diagram and an energy spectrum element distribution diagram.
FIG. 3 is an X-ray photoelectron (XPS) spectrum of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 4 is an X-ray diffraction (XRD) spectrum of Prussian blue/g-C 3N4 (I) composite photocatalyst, g-C 3N4 and Prussian blue.
FIG. 5 is a graph of photo-Fenton degradation of tetracycline for Prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II), and Prussian blue/g-C 3N4 (III).
FIG. 6 is a graph of photo-Fenton degradation of tetracycline for bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
FIG. 7 is a graph showing photo-Fenton degradation of tetracyclines with different amounts of Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 8 is a graph of photo-Fenton degradation of tetracycline at different pH conditions for Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 9 is a graph showing the degradation rate of 20 cycles of Prussian blue/g-C 3N4 (I) composite photocatalyst for degrading tetracycline.
FIG. 10 is a graph of photo-Fenton degradation of ciprofloxacin, ranitidine, methylene blue, and rhodamine B for Prussian blue/g-C 3N4 (I) composite photocatalyst.
FIG. 11 is an ultraviolet-visible diffuse reflectance absorption spectrum of bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
FIG. 12 is a graph of photocurrent and electrochemical impedance spectra of bulk g-C 3N4、g-C3N4 and Prussian blue/g-C 3N4 (I).
Detailed Description
Example 1
The embodiment provides a preparation method of Prussian blue/g-C 3N4 (I) composite photocatalyst, which comprises the following steps:
step one: 20g of urea is dissolved in 20mL of deionized water, the temperature is raised to 30 ℃, then the solution is transferred into a ceramic crucible (100 mL) with a cover, and the solution is calcined for 4 hours at 550 ℃ to obtain a product g-C 3N4;
Step two: 3g of polyvinylpyrrolidone, 26.4mg of potassium ferricyanide and 172mg of C 3N4 of the product prepared in the first step are dripped into 30mL of 0.01mol/L HCl solution to obtain a suspension, the suspension is placed into a stainless steel autoclave with a 50mL capacity Teflon lining, and the suspension is placed into an oven at 80 ℃ for hydrothermal reaction for 20 hours;
step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and vacuum drying the precipitate for 12 hours at 60 ℃ to obtain the Prussian blue/g-C 3N4 (I) composite photocatalyst.
The SEM image of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the example is shown in figure 1, and as can be seen from figure 1, the Prussian blue/g-C 3N4 (I) composite photocatalyst has a porous layered structure.
The TEM image of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in this example is shown in FIG. 2, and it can be seen from FIG. 2 that Prussian blue/g-C 3N4 (I) has a porous layered structure, prussian blue Nanoparticles (NPS) with a diameter of about 250nm are closely adhered to the porous g-C 3N4, wherein a significant and uniform Fe signal confirms successful doping and uniform distribution of Prussian blue.
The XPS spectrum of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the embodiment is shown in figure 3, and as can be seen from figure 3, prussian blue/g-C 3N4 (I) has C, N, O and Fe elements, wherein two peaks 705.1eV and 717.8eV appearing in the Fe2p spectrum correspond to Fe2p3/2 and Fe2p1/2 well, and successful loading of Prussian blue is confirmed.
The XRD spectrum of the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in the embodiment is shown in figure 4, and as can be seen from figure 4, the Prussian blue/g-C 3N4 (I) has characteristic peaks of both Prussian blue and g-C 3N4, and successful synthesis of the Prussian blue/g-C 3N4 (I) composite photocatalyst is verified.
Example 2
Example 2 differs from example 1 in that: in the second step, the mass of the g-C 3N4, the mass of the polyvinylpyrrolidone and the mass of the potassium ferricyanide are 344mg, 3g and 26.4mg respectively.
The Prussian blue/g-C 3N4 (II) composite photocatalyst is finally obtained in the embodiment.
Example 3
Example 3 differs from example 1 in that: in the second step, the mass of the g-C 3N4, the mass of the polyvinylpyrrolidone and the mass of the potassium ferricyanide are 86mg, 3g and 26.4mg respectively.
The Prussian blue/g-C 3N4 (III) composite photocatalyst is finally obtained in the embodiment.
The three composite photocatalysts of Prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II) and Prussian blue/g-C 3N4 (III) prepared in examples 1, 2 and 3 are subjected to performance test, and the process and the result are as follows:
Respectively taking 50mg of Prussian blue/g-C 3N4 (I), 50mg of Prussian blue/g-C 3N4 (II) and 50mg of Prussian blue/g-C 3N4 (III), respectively adding into 30mL of 50mg/L tetracycline solution, and continuously stirring for 30min to ensure that the suspension reaches adsorption equilibrium. 150 μ L H 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 5. As can be seen from FIG. 5, after 120min of illumination, prussian blue/g-C 3N4 (I), prussian blue/g-C 3N4 (II) and Prussian blue/g-C 3N4 (III) all reach more than 85%, wherein the photocatalytic efficiency of Prussian blue/g-C 3N4 (I) is highest.
In addition, 50mg of bulk g-C 3N4 (self-made), g-C 3N4 (self-made) and Prussian blue/g-C 3N4 (I) are respectively taken and then respectively added into 30ml of 50mg/L tetracycline solution, and the suspension is continuously stirred for 30min to reach adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 6. As can be seen from FIG. 6, after 120min of illumination, prussian blue/g-C 3N4 (I) has the highest degradation effect on tetracycline, and the degradation rate can reach about 93.3%. The single catalyst bulk-C 3N4 and g-C 3N4 have lower degradation to tetracycline, and the photocatalysis efficiency of the composite material is obviously higher than that of the single catalyst.
The preparation method of bulk g-C 3N4 (homemade) comprises the following steps: 3g of melamine is transferred into a covered ceramic crucible and calcined at 550 ℃ to obtain the product bulk-C 3N4.
G-C 3N4 (homemade) is the product obtained in step one of example 1.
In addition, specific tests are carried out on each influencing factor of Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in example 1, and the process and the result are as follows:
(1) Relation between degradation efficiency and Prussian blue/g-C 3N4 (I) addition
Prussian blue/g-C 3N4 (I) is respectively taken as 1mg, 5mg, 10mg, 25mg and 50mg, then respectively added into 30mL of 50mg/L tetracycline solution, and continuously stirred for 30min to ensure that the suspension reaches adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 7. As can be seen from FIG. 7, after 120min of illumination, the degradation effect of Prussian blue/g-C 3N4 (I) on tetracycline is positively correlated with the addition amount.
(2) Relation between visible light degradation performance and acid and alkali conditions
50Mg of Prussian blue/g-C 3N4 (I) was added to 30mL of a 50mg/L tetracycline solution, the pH was adjusted to 3 to 9, and stirring was continued for 30min to bring the suspension to adsorption equilibrium. 150. Mu. LH 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting tetracycline degradation graph is shown in FIG. 8. As can be seen from FIG. 8, after 120min of illumination, the pH value of the solution is between 3 and 9, and Prussian blue/g-C 3N4 is more than 89.6%, so that the solution has stronger degradation efficiency. When the pH of the solution is 7, the degradation efficiency can reach 98.4 percent. The Prussian blue/g-C 3N4 has good visible light degradation performance under acidic or weak alkaline conditions.
(3) Cyclic degradation of tetracycline
The result of the photocatalytic experiment for circularly degrading tetracycline by the Prussian blue/g-C 3N4 (I) composite photocatalyst prepared in example 1 is shown in FIG. 9. As can be seen from fig. 9, the photocatalyst was not significantly deactivated after 20 consecutive cycles. The stability is good, and the method has great potential value in the aspect of environmental purification.
(4) Universality of application
50Mg Prussian blue/g-C 3N4 (I) was added to 30mL of 50mg/L ciprofloxacin, ranitidine, methylene blue and rhodamine solutions, respectively, and the suspension was allowed to reach adsorption equilibrium by continuous stirring for 30 min. 150 μ L H 2O2 (30%) was then added to the suspension. Two milliliter aliquots were collected at specific time intervals and at desired intervals using a 0.45mm syringe. The concentration was assessed by taking the supernatant after centrifugation of the suspension and recording the maximum absorbance with a UV-vis spectrophotometer. The resulting degraded ciprofloxacin, ranitidine, methylene blue and rhodamine solutions are shown in the graph of fig. 10. As can be seen from FIG. 10, after 120min of illumination, the degradation efficiencies of ciprofloxacin, ranitidine, methylene blue and rhodamine can reach 59.8%, 98.4%, 99.4% and 100.0%, respectively, and the results show that Prussian blue/g-C 3N4 has good universality.
(5) Visible light absorption capacity, absorption region
The light absorption characteristics of the different samples were measured using uv-vis diffuse reflectance spectroscopy as shown in fig. 11. As can be seen from fig. 11, it is confirmed that the Prussian blue/g-C 3N4 (I) composite material has both the absorption characteristics of Prussian blue and g-C 3N4, and that Prussian blue/g-C 3N4 has a wider and stronger light absorption, which means that after loading Prussian blue, light collection is improved, the visible light absorption capacity of Prussian blue/g-C 3N4 (I) is also improved, and the absorption region is also widened.
(6) Charge transfer and conductivity capabilities
The photocurrent testing process comprises the following steps: 2.0mg of the sample was ultrasonically dispersed in 50. Mu.L of ethanol, 10. Mu.L of Nafion solution (5 wt%) and 50. Mu.L of ultra pure water to form a uniform slurry, and 20. Mu.L of the slurry was dropped to deposit on the FTO electrode. FTP electrode, platinum sheet and saturated Ag/AgCl deposited by slurry are used as working electrode, counter electrode and reference electrode. Photocurrent data was collected using a CHI660C electrochemical workstation in an analysis of photocurrent over time using a 300W Xe lamp (truncated lambda <420 nm) and Na 2SO4 (0.5M) as the light source and electrolyte.
Electrochemical impedance spectroscopy testing process: on the CHI760e workstation, a standard three-electrode system (Pt foil, ag/AgCl and working electrode, electrolyte 0.1M K 4Fe(CN)6·3H2O、0.1M K3[Fe(CN)6, 0.1M KCl mixed solution) was used, 5. Mu.L of slurry was added dropwise to the working electrode, and the electrochemical impedance spectrum was measured at an open circuit potential range of 0.01-1000 kHz.
The results of the photocurrent and electrochemical impedance spectrum tests are shown in fig. 12, and it can be seen from fig. 12 that Prussian blue/g-C 3N4 (I) loaded with Prussian blue shows the highest photocurrent response and the smallest arc radius, indicating that the synergistic effect of Prussian blue and carbon defects maximizes the photogenerated charge transfer efficiency and has the strongest charge transfer and conduction capacity.
While the embodiments of the present invention have been described in detail, those skilled in the art should not understand that the present invention is limited to the specific embodiments and applications.
Claims (7)
1. A preparation method of Prussian blue/g-C 3N4 composite photocatalyst is characterized by comprising the following steps:
Step one: dissolving urea in deionized water, heating to 30 ℃, transferring the solution into a ceramic crucible with a cover, and calcining at high temperature to obtain a product g-C 3N4, wherein the mass ratio of the urea to the deionized water is 1:1;
Step two: dripping polyvinylpyrrolidone, potassium ferricyanide and the product g-C 3N4 prepared in the first step into an HCl solution to obtain a suspension, and placing the suspension into a stainless steel autoclave for hydrothermal reaction, wherein the mass ratio of the product g-C 3N4 to the polyvinylpyrrolidone to the potassium ferricyanide is (1-7) to (50-70) to (0.5-0.56), and 1mg of the product g-C 3N4 corresponds to (0.08-0.35) mL of the HCl solution;
Step three: and (3) after the reaction of the second step is finished, cooling to room temperature, centrifuging the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for three times respectively, and then drying the precipitate in vacuum to obtain the Prussian blue/g-C 3N4 composite photocatalyst.
2. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the calcination temperature in the first step is 550 ℃ and the time is 4 hours.
3. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the concentration of the HCl solution in the second step is 0.01mol/L.
4. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: the specific process of the hydrothermal reaction in the step two is that the suspension is placed in a stainless steel autoclave with a teflon liner with a capacity of 50mL and placed in an oven at 80 ℃ for reaction for 20h.
5. The method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to claim 1, which is characterized in that: and in the third step, the vacuum drying temperature is 60 ℃ and the time is 12 hours.
6. The Prussian blue/g-C 3N4 composite photocatalyst prepared by the method for preparing the Prussian blue/g-C 3N4 composite photocatalyst according to any one of claims 1-5.
7. The application of the Prussian blue/g-C 3N4 composite photocatalyst prepared by the preparation method of the Prussian blue/g-C 3N4 composite photocatalyst in degrading antibiotic medicines and dye pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310242005.4A CN116351471B (en) | 2023-03-13 | 2023-03-13 | Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310242005.4A CN116351471B (en) | 2023-03-13 | 2023-03-13 | Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116351471A CN116351471A (en) | 2023-06-30 |
| CN116351471B true CN116351471B (en) | 2024-04-26 |
Family
ID=86934041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310242005.4A Active CN116351471B (en) | 2023-03-13 | 2023-03-13 | Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116351471B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289684A (en) * | 2015-09-29 | 2016-02-03 | 北京化工大学 | Method for preparing porous flake-like graphite phase carbon nitride on large scale, and application thereof |
| CN107381520A (en) * | 2017-08-24 | 2017-11-24 | 南昌航空大学 | A kind of band gap is adjustable and the preparation method of the class graphene carbonitride of efficient degradation of organic dye |
| CN111889127A (en) * | 2020-07-01 | 2020-11-06 | 广西大学 | In-situ growth preparation of beta-Bi2O3/g-C3N4Method for preparing nano composite photocatalyst |
| CN112138702A (en) * | 2020-10-20 | 2020-12-29 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN112194178A (en) * | 2020-10-20 | 2021-01-08 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| KR20210080874A (en) * | 2019-12-23 | 2021-07-01 | 가천대학교 산학협력단 | Porous surfur doped graphitic carbon nitride nanosheet for selective detection of silver ion and photocatalytic degradation of organic material and method of manufacturing same |
| CN115703077A (en) * | 2021-08-10 | 2023-02-17 | 中国科学院大连化学物理研究所 | PB @ MoS 2 Application of catalyst in heterogeneous Fenton-like reaction |
-
2023
- 2023-03-13 CN CN202310242005.4A patent/CN116351471B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289684A (en) * | 2015-09-29 | 2016-02-03 | 北京化工大学 | Method for preparing porous flake-like graphite phase carbon nitride on large scale, and application thereof |
| CN107381520A (en) * | 2017-08-24 | 2017-11-24 | 南昌航空大学 | A kind of band gap is adjustable and the preparation method of the class graphene carbonitride of efficient degradation of organic dye |
| KR20210080874A (en) * | 2019-12-23 | 2021-07-01 | 가천대학교 산학협력단 | Porous surfur doped graphitic carbon nitride nanosheet for selective detection of silver ion and photocatalytic degradation of organic material and method of manufacturing same |
| CN111889127A (en) * | 2020-07-01 | 2020-11-06 | 广西大学 | In-situ growth preparation of beta-Bi2O3/g-C3N4Method for preparing nano composite photocatalyst |
| CN112138702A (en) * | 2020-10-20 | 2020-12-29 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN112194178A (en) * | 2020-10-20 | 2021-01-08 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| WO2022083793A1 (en) * | 2020-10-20 | 2022-04-28 | 苏州大学 | Three-dimensional/two-dimensional ni-co bimetallic oxide/g-c3n4 nanocomposite material, and preparation method and use therefor |
| CN115703077A (en) * | 2021-08-10 | 2023-02-17 | 中国科学院大连化学物理研究所 | PB @ MoS 2 Application of catalyst in heterogeneous Fenton-like reaction |
Non-Patent Citations (6)
| Title |
|---|
| "C3N4 nanosheet-supported Prussian Blue nanoparticles as a peroxidase mimic: colorimetric enzymatic determination of lactate";Dandan Zhou et al;《Microchimica Acta 》;20191031;第186卷;全文 * |
| "g-C3N4的制备及其光催化降解诺氟沙星的机理及产物毒性研究";田倩等;《工业水处理》;20221130;第42卷;全文 * |
| "Prussian Blue decorated g-C3N4-From novel synthesis to insight study on charge transfer strategy for improving visible-light driven photo-Fenton catalytic activity";Lan Nguyen Thi et al;《Journal of Alloys and Compounds》;20220510;第916卷;全文 * |
| "The beauty of being complex: Prussian blue analogues as selective catalysts and photocatalysts in the degradation of ciprofloxacin";Sepideh G. Khasevani et al;《Journal of Catalysis》;20220630;第410卷;全文 * |
| "功能化无机二维材料用于铀和铯的吸附研究";甘泉;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20230115(第01期);全文 * |
| "普鲁士蓝对罗丹明B的光催化降解研究";程实等;《苏州科技学院学报(自然科学版)》;20091231;第26卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116351471A (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shi et al. | Onion-ring-like g-C3N4 modified with Bi3TaO7 quantum dots: A novel 0D/3D S-scheme heterojunction for enhanced photocatalytic hydrogen production under visible light irradiation | |
| Cui et al. | Bi2WO6/Nb2CTx MXene hybrid nanosheets with enhanced visible-light-driven photocatalytic activity for organic pollutants degradation | |
| Xia et al. | Novel Fe-Mn-O nanosheets/wood carbon hybrid with tunable surface properties as a superior catalyst for Fenton-like oxidation | |
| Mao et al. | Facile assembled N, S-codoped corn straw biochar loaded Bi2WO6 with the enhanced electron-rich feature for the efficient photocatalytic removal of ciprofloxacin and Cr (VI) | |
| Zhao et al. | Study on the photocatalysis mechanism of the Z-scheme cobalt oxide nanocubes/carbon nitride nanosheets heterojunction photocatalyst with high photocatalytic performances | |
| Chen et al. | Studies on the photocatalytic performance of cuprous oxide/chitosan nanocomposites activated by visible light | |
| Xie et al. | Hierarchical Bi2MoO6 microsphere photocatalysts modified with polypyrrole conjugated polymer for efficient decontamination of organic pollutants | |
| Yan et al. | In-situ synthesis of CQDs/BiOBr material via mechanical ball milling with enhanced photocatalytic performances | |
| CN105148964B (en) | A kind of three-dimensional redox graphene Mn3O4/MnCO3Nano composite material and preparation method thereof | |
| He et al. | Construction of Schottky-type Ag-loaded fiber-like carbon nitride photocatalysts for tetracycline elimination and hydrogen evolution | |
| Li et al. | A CQD/CdS/g-C3N4 photocatalyst for dye and antibiotic degradation: Dual carrier driving force and tunable electron transfer pathway | |
| CN102836702A (en) | Transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst and preparation method and application thereof | |
| CN112500579A (en) | Magnetically-recyclable cerium complex/GO/Fe3O4Ternary complex, preparation method and application | |
| Xu et al. | Bacterial cellulose flakes loaded with Bi2MoO6 nanoparticles and quantum dots for the photodegradation of antibiotic and dye pollutants | |
| CN108479772A (en) | Golden nanometer doped zinc oxide composite material and preparation method and the application in photocatalytic degradation tetracycline | |
| Liu et al. | Spatial directional separation and synergetic treatment of Cr (VI) and Rhodamine B mixed pollutants on three-layered Pd@ MIL-101/P25 photocatalyst | |
| Lei et al. | Synthesis of porous pinecone-like structure via facile carbon quantum dots modulation: A promising approach for improving the photocatalytic capability of carbon nitride | |
| Wang et al. | Photocatalytic activity of Co3O4@ C enhanced by induction of amorphous cobalt-based MOF | |
| Liao et al. | Constructing MXene-derived Z-Scheme g-C3N4/Ti3C2TX/Ag3PO4 photocatalysts with enhanced charge transfer for aquatic organic pollutants removal | |
| CN113385169A (en) | Novel piezoelectric photocatalyst capable of efficiently degrading organic pollutants, preparation method and application | |
| CN116351471B (en) | Prussian blue/g-C3N4Composite photocatalyst, preparation method and application thereof | |
| Cao et al. | Complecting the BiOCl nano-roundels based hollow microbasket induced by chitosan for dramatically enhancing photocatalytic activity | |
| Liu et al. | PI/gC 3 N 4 composite photocatalyst with enhanced activity of degrading pollutants under visible light | |
| Ding et al. | Using ZIF-8 to synthesize ZnO/C composite with enhanced photocatalytic property | |
| CN113952973A (en) | NCQDs/p-Co3O4Preparation method and application of composite photocatalyst |
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 |