CN110560027B - Silver halide-biotite composite photocatalyst and preparation method thereof - Google Patents
Silver halide-biotite composite photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN110560027B CN110560027B CN201910758939.7A CN201910758939A CN110560027B CN 110560027 B CN110560027 B CN 110560027B CN 201910758939 A CN201910758939 A CN 201910758939A CN 110560027 B CN110560027 B CN 110560027B
- Authority
- CN
- China
- Prior art keywords
- biotite
- silver halide
- preparation
- composite photocatalyst
- etched
- 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
- 229910052626 biotite Inorganic materials 0.000 title claims abstract description 69
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 31
- 239000004332 silver Substances 0.000 title claims abstract description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims 1
- -1 silver halide Chemical class 0.000 abstract description 9
- 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 abstract description 6
- 229940043267 rhodamine b Drugs 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000000224 chemical solution deposition Methods 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 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
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 2
- 229960000623 carbamazepine Drugs 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 2
- 229960001259 diclofenac Drugs 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229960005404 sulfamethoxazole Drugs 0.000 description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 2
- 229960001082 trimethoprim Drugs 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229960001482 bismuth subnitrate Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—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)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silver halide-biotite composite photocatalyst and a preparation method thereof. According to the method, the biotite is etched and stripped by an alkali etching method to obtain a porous biotite nanosheet, and then the silver halide and the biotite are subjected to chemical bath deposition compounding to obtain the silver halide-biotite composite photocatalyst. The invention adopts chemical stripping, and the etched biotite has a micropore structure under the alkaline condition, so that the specific surface area and active sites of the biotite are increased, most metal ions are retained, and the conductivity is improved. The silver halide-biotite composite photocatalyst is used for photocatalytic degradation of 10mg/L rhodamine B, shows excellent catalytic performance, and has a degradation rate of more than 85% in 90 min.
Description
Technical Field
The invention relates to a silver halide-biotite composite photocatalyst and a preparation method thereof, belonging to the technical field of nano material preparation.
Background
TiO was discovered by Fujishima and Honda in 1972 2 After the electrode can carry out photocatalytic decomposition on water under the irradiation of ultraviolet light, the photocatalytic reaction of the nano semiconductor causes extensive research.
Biotite (BIO) is a natural clay silicate mineral and has the advantages of large specific surface area, abundant reserves, good thermal stability, uniform structure and the like. The chemical formula is (Mg, Fe, Al) 3 (Al,Si) 4 O10(OH) 2 ·4H 2 O, the most common morphology of this mineral is the layered structure. Yan, t.j. et al, used for selective removal of cations in wastewater by synthesizing ultra-thin sodium iron silicate two-dimensional nanosheets [ Yan, t.j., et al (2019). "ultrarhin sodium ferric silicate 2D nanosheets:A novel and robustadsorbent for selective removal of cationic dyes in wastewater."Journal of Alloys and Compounds,784,256-265.]. Interface Modification of Attapulgite at atom-molecule level, Zhang, J, et al, for Photocatalytic Water Splitting studies, to allow Natural silicates to participate as The catalyst host in catalytic reactions [ Zhang, J., et al (2016) ] "Strong Visible Light Photocatalytic Water Splitting Based on Natural Silicate Clay Mineral: The Interface Modification of Atomic at The Atomic-Molecular level," ACS stable Chem. Eng.,4, 4601-.]. Martini-costa, et al have high efficiency in degrading diclofenac, sulfamethoxazole, trimethoprim and carbamazepine pollutants by using vermiculite photocatalysis [ Zhou, T.Z., et al (2019) ]degradation of organic contaminants diclofenac, sulfamethoxazole, trimethoprim and carbazepine by bismuth subnitrate and verticillite a pilot porous collector ". Catalysis Today, DOI:10.1016 ]. The modification modes are all that natural silicate such as biotite is used as a carrier for modification, and only simple mechanical stripping is carried out to obtain thicker biotite nanosheets.
Disclosure of Invention
The invention aims to provide a silver halide-biotite composite photocatalyst with excellent catalytic performance and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the silver halide-biotite composite photocatalyst comprises the following steps:
and 2, dispersing the alkali-etched biotite nanosheets in water, adding silver nitrate, stirring and mixing uniformly, then adding cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride, carrying out water bath reaction at 50-70 ℃, centrifuging, washing and drying after the reaction is finished, thus obtaining the silver halide-biotite composite photocatalyst.
Preferably, in step 1, the mass concentration of the biotite is 10 mg/mL.
Preferably, in step 1, the biotite is magnetically stirred in the sodium hydroxide solution for more than 2 hours, and the hydrothermal reaction is more than 24 hours.
Preferably, in the step 1, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
Preferably, in the step 2, the mass ratio of the silver nitrate to the alkali-etched biotite is 1: 1.
Preferably, in step 2, the molar concentration of the hexadecyl trimethyl ammonium bromide or chloride is 8 × 10 -3 mol/L。
Preferably, in step 2, the mixing time of the silver nitrate and the biotite is more than 0.5 h.
Preferably, in the step 2, the water bath reaction time is more than 3h, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
The silver halide-biotite composite photocatalyst prepared by the method has a nanosheet structure on the microscopic scale, and the silver halide dispersedly grows on the surface of the biotite.
Compared with the prior art, the invention has the advantages that:
(1) the layered natural silicate is stripped into a very thin biotite nanosheet by chemical stripping, so that the specific surface area and the active sites are greatly increased, and the layered natural silicate can be used as a main catalyst and an excellent carrier; (2) the biotite etched under the alkaline condition has a micropore structure, and meanwhile, most metal ions are reserved, the conductivity of the biotite is improved, and the structure is reconstructed; (3) the raw material biotite is rich in resources, low in price and easy to obtain, and the pretreatment mode is simple; (4) the silver halide-biotite composite photocatalyst is used for photocatalytic degradation of 10mg/L rhodamine B, shows excellent catalytic performance, and has a degradation rate of more than 85% in 90 min.
Drawings
FIG. 1 is a scheme of the synthesis scheme of the preparation process of the present invention.
FIG. 2 is a Zeta potential diagram of the alkali-etched biotite nanosheets prepared in example 1 in an aqueous environment.
FIG. 3 is a transmission electron microscope image of the materials prepared in example 1, example 2 and example 3.
Figure 4 is an XRD diffractogram of the materials prepared in example 1, example 2 and example 3.
Fig. 5 is a graph of the photocatalytic degradation performance of the silver chloride-biotite prepared in example 2.
Fig. 6 is a graph of the photocatalytic degradation performance of the silver bromide-biotite prepared in example 3.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
FIG. 1 is a synthesis mechanism diagram of the preparation method, wherein the biotite is dispersed in a sodium oxide solution after pretreatment, stirred and mixed, transferred to a polytetrafluoroethylene reaction kettle, subjected to solvothermal reaction, centrifuged, washed and dried to obtain the alkali-etched biotite material. And dispersing the alkali-etched biotite nanosheets in deionized water, sequentially adding silver nitrate, hexadecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide, stirring in a water bath, centrifuging, washing and drying to obtain the silver halide-biotite composite photocatalyst.
Example 1
Firstly, mixing 500mg of biotite with 50mL of 20mol/L sodium hydroxide solution, and stirring for 2 hours on a magnetic stirrer;
secondly, transferring the solution obtained in the first step into a 100mL polytetrafluoroethylene reaction kettle, performing hydrothermal treatment for 24 hours, taking out and naturally cooling;
and thirdly, centrifugally washing the sample obtained in the second step, and drying at 60 ℃ to obtain the alkali-etched biotite nanosheet.
Example 2
Firstly, dispersing 30mg of alkali-etched biotite in 50mL of deionized water, and performing ultrasonic dispersion for 30 min;
secondly, quantitatively adding 30mg of silver nitrate into the solution obtained in the first step, and stirring for 1 h;
thirdly, adding hexadecyl trimethyl ammonium chloride into the solution obtained in the second step, and stirring for 2 hours in a water bath at the temperature of 60 ℃;
and fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ drying oven for 12 hours to obtain the AgCl-biotite composite material.
Example 3
Firstly, dispersing 30mg of alkali-etched biotite in 50mL of deionized water, and performing ultrasonic dispersion for 30 min;
secondly, quantitatively adding 30mg of silver nitrate into the solution obtained in the first step, and stirring for 1 h;
thirdly, adding hexadecyl trimethyl ammonium bromide into the solution obtained in the second step, and stirring for 2 hours in a water bath at the temperature of 60 ℃;
and fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ drying oven for 12 hours to obtain the AgBr-biotite composite material.
Example 4
Firstly, dispersing 30mg of AgCl-biotite composite material in 50mL of 10mg/L rhodamine B solution, and stirring for 1h in a dark room;
secondly, placing the suspension obtained in the first step under a 300W xenon lamp (lambda is more than 420nm) for illumination, and taking 3mL of liquid at intervals of 10 minutes;
thirdly, centrifuging the liquid sample obtained in the second step for 1min at 9000r/min, and removing the catalyst;
and fourthly, detecting the centrifuged liquid obtained in the third step in an ultraviolet-visible spectrophotometer to evaluate the photocatalytic performance.
Example 5
Firstly, dispersing 30mg of AgBr-biotite composite material in 50mL of 10mg/L rhodamine B solution, and stirring for 1h in a dark room;
secondly, placing the suspension obtained in the first step under a 300W xenon lamp (lambda is more than 420nm) for illumination, and taking 3mL of liquid at intervals of 10 minutes;
thirdly, centrifuging the liquid sample obtained in the second step for 1min at 9000r/min, and removing the catalyst;
and fourthly, detecting the centrifuged liquid obtained in the third step in an ultraviolet-visible spectrophotometer to evaluate the photocatalytic performance.
Comparative example 1
Firstly, dispersing silver nitrate in 50mL of deionized water, and performing ultrasonic dispersion for 30 min;
secondly, adding hexadecyl trimethyl ammonium chloride into the solution obtained in the first step, and stirring for 2 hours in a water bath at the temperature of 80 ℃;
And thirdly, centrifugally washing the sample obtained in the second step, and drying the sample in a 60 ℃ drying oven for 12 hours to obtain AgCl.
Comparative example 2
Firstly, dispersing silver nitrate in 50mL of deionized water, and performing ultrasonic dispersion for 30 min;
secondly, adding cetyl trimethyl ammonium bromide into the solution obtained in the first step, and stirring for 2 hours in a water bath at the temperature of 80 ℃;
and thirdly, centrifugally washing the sample obtained in the second step, and drying the sample in a 60 ℃ drying oven for 12 hours to obtain AgBr.
FIG. 2 is a Zeta potential diagram of the alkali-etched biotite nanosheet prepared in example 1 in a water environment, wherein the Zeta potential is negative, which indicates that the surface of the sample is negatively charged and is beneficial to the adsorption of metal cations.
Fig. 3 is a transmission electron microscope image of the materials prepared in example 1, example 2 and example 3, a is untreated biotite flakes, B is alkali etched mesoporous biotite flakes, C is a silver chloride-biotite nanocomposite, D is a lattice line of silver chloride, E is a silver bromide-biotite nanocomposite, and F is a high resolution transmission electron microscope image of silver bromide nanoparticles. Comparing the A diagram and the B diagram, the black mica sheet after alkali etching is in a mesoporous shape, which is beneficial to the increase of active sites and the compounding of materials. It can be seen from the C and E diagrams that a layer of silver halide grows on the mesoporous black mica sheet, which shows that the black mica sheet and the silver halide are well compounded. The good crystallinity of the silver halide synthesized in the water bath can be seen from the clear lattice lines in the D and F plots.
Figure 4 is an XRD diffractogram of the materials prepared in example 1, example 2 and example 3.
Fig. 5 is a graph of the photocatalytic degradation performance of the silver chloride-biotite prepared in example 2. As can be seen from the figure, the degradation rate of 10mg/L rhodamine B for degrading 50mL by 30mg of silver chloride-biotite catalyst within 90min reaches more than 95%.
Fig. 6 is a graph of the photocatalytic degradation performance of the silver bromide-biotite prepared in example 3. As can be seen from the figure, the degradation rate of 10mg/L rhodamine B for degrading 50mL by 30mg of silver bromide-biotite catalyst within 90min reaches more than 85%. In conclusion, the silver halide has good dispersibility on the biotite, and the biotite is tightly combined with the silver halide, so that the effective specific surface area of catalytic reaction is increased, the active sites are increased, and the catalytic activity is improved.
Claims (9)
1. The preparation method of the silver halide-biotite composite photocatalyst is characterized by comprising the following steps:
step 1, stirring and dispersing biotite in 16-20 mol/L sodium hydroxide solution, carrying out hydrothermal reaction at 160-180 ℃, naturally cooling, centrifuging, washing and drying after the reaction is finished, so as to obtain alkali-etched biotite nanosheets, wherein the magnetic stirring time of the biotite in the sodium hydroxide solution is more than 2 hours, and the hydrothermal reaction is more than 24 hours;
And 2, dispersing the alkali-etched biotite nanosheets in water, adding silver nitrate, stirring and mixing uniformly, then adding cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride, carrying out water bath reaction at 50-70 ℃, centrifuging, washing and drying after the reaction is finished, thus obtaining the silver halide-biotite composite photocatalyst.
2. The method according to claim 1, wherein the mass concentration of biotite in step 1 is 10 mg/mL.
3. The preparation method according to claim 1, wherein in the step 1, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
4. The preparation method according to claim 1, wherein in the step 2, the mass ratio of the silver nitrate to the alkali-etched biotite is 1: 1.
5. The method according to claim 1, wherein the molar concentration of cetyltrimethylammonium bromide or chloride in step 2 is 8 x 10 -3 mol/L。
6. The method according to claim 1, wherein in step 2, the silver nitrate is mixed with the biotite for 0.5h or more.
7. The preparation method according to claim 1, wherein in the step 2, the water bath reaction time is more than 3h, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
8. The silver halide-biotite composite photocatalyst prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the silver halide-biotite composite photocatalyst according to claim 8 in photocatalytic degradation of organic dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910758939.7A CN110560027B (en) | 2019-08-16 | 2019-08-16 | Silver halide-biotite composite photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910758939.7A CN110560027B (en) | 2019-08-16 | 2019-08-16 | Silver halide-biotite composite photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110560027A CN110560027A (en) | 2019-12-13 |
| CN110560027B true CN110560027B (en) | 2022-08-12 |
Family
ID=68775661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910758939.7A Active CN110560027B (en) | 2019-08-16 | 2019-08-16 | Silver halide-biotite composite photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110560027B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689839A (en) * | 2015-02-02 | 2015-06-10 | 河西学院 | Preparation method for Ag-AgCl/attapulgite nano compound photocatalyst |
| CN109422270A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Mesoporousization bentonite and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060293430A1 (en) * | 2005-06-20 | 2006-12-28 | Eastman Kodak Company | Exfoliated clay nanocomposites |
-
2019
- 2019-08-16 CN CN201910758939.7A patent/CN110560027B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689839A (en) * | 2015-02-02 | 2015-06-10 | 河西学院 | Preparation method for Ag-AgCl/attapulgite nano compound photocatalyst |
| CN109422270A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Mesoporousization bentonite and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| AgBr/TiO2(001)纳米片可见光光催化剂的制备;张旺喜等;《湖北工业大学学报》;20140430;第29卷(第2期);摘要、第1.1.2节和第2.1.1节 * |
| Highly efficient removal of organic dyes by novel as-synthesized AgBr/montmorillonite composite;LÜ Jianchang et al.;《Journal of Wuhan University of Technology-Mater. Sci. Ed.》;20190228;第34卷(第1期);摘要和第2.1节 * |
| 硅藻土及复合材料孔结构和表面特性与调湿性能研究;胡志波;《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》;20180215(第2期);第4.1节、第4.2.3节、第4.3节、表 2.1和表 4.1 * |
| 碘化银/硅藻土光催化剂的制备及可见光催化性能研究;龚久炎等;《无机盐工业》;20180131;第50卷(第1期);摘要和试验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110560027A (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Iron–copper bimetallic nanoparticles supported on hollow mesoporous silica spheres: an effective heterogeneous Fenton catalyst for orange II degradation | |
| US10486138B2 (en) | Method for hydrothermal synthesis of three dimensional Bi4MoO9/TiO2 nanostructure heterojunction | |
| CN111604077B (en) | g-C for degrading ammonia nitrogen3N4/Gr/TiO2Z-system photocatalytic material and preparation method and application thereof | |
| CN112028038B (en) | Preparation method and application of alkalized carbon nitride nanotube | |
| Li et al. | Facile synthesis of spiny mesoporous titania tubes with enhanced photocatalytic activity | |
| Yang et al. | Construction of a rod-like Bi 2 O 4 modified porous gC 3 N 4 nanosheets heterojunction photocatalyst for the degradation of tetracycline | |
| CN111974385A (en) | Photocatalytic material for efficiently removing high-concentration nitrate through photocatalysis, and preparation method and application thereof | |
| CN113649075B (en) | Balsam pear-like NaNbO 3 Preparation method of @ ZIF-8 piezoelectric-photocatalyst | |
| CN1891335A (en) | Method for preparing nano titanium dioxide photocatalyst and its product | |
| CN110124693A (en) | The composite metal ion doped deficiency semiconductor light-catalyst preparation method of graphene | |
| CN108636436A (en) | Effectively construct the preparation method of Z-type ternary heterojunction photochemical catalyst | |
| CN101817552B (en) | Titanium dioxide micron tube material and preparation method thereof | |
| CN106582718B (en) | A kind of preparation method of graphene-sulfur antimony micron bar composite photo-catalyst | |
| CN110560027B (en) | Silver halide-biotite composite photocatalyst and preparation method thereof | |
| CN108855056B (en) | Double-layer core-shell structure palladium catalyst and preparation method and application thereof | |
| Sufian | Development of the g-C3N4/BiVO4 microflower photocatalyst for photocatalytic degradation of amoxicillin and hydrogen production | |
| Chen et al. | Fabrication of Pt/TiO2 nanocomposites in alginate and their applications to the degradation of phenol and methylene blue in aqueous solutions | |
| CN115703077A (en) | PB @ MoS 2 Application of catalyst in heterogeneous Fenton-like reaction | |
| CN106082201B (en) | The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load | |
| CN100496726C (en) | Hydrotalcite like structural catalyst with mica as matrix and preparation method | |
| CN101696109B (en) | Method for preparing mesoporous titanium dioxide microspheres | |
| CN112892557B (en) | SiO (silicon dioxide) 2 @CdS@SiO 2 Preparation method and application of core-shell photocatalyst | |
| Wang et al. | Constructing flower-like MoS2/ZnIn2S4 microspheres for efficient visible light-driven photocatalytic removal of hexavalent chromium | |
| Badiei et al. | Study of electrochemical behavior and adsorption mechanism of [Co (en) 2Cl2]+ on mesoporous modified carbon paste electrode | |
| CN113479897B (en) | Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |