CN110560089B - Zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst and preparation method thereof - Google Patents
Zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst and preparation method thereof Download PDFInfo
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- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 90
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- FXPNXARRBKZERZ-UHFFFAOYSA-N [Bi].[S].[Cd].[Zn] Chemical compound [Bi].[S].[Cd].[Zn] FXPNXARRBKZERZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 claims description 9
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 238000001816 cooling Methods 0.000 claims description 2
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- 238000000034 method Methods 0.000 claims 4
- 239000000975 dye Substances 0.000 claims 1
- 239000002071 nanotube Substances 0.000 abstract description 13
- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical compound [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract 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 abstract description 3
- 229940043267 rhodamine b Drugs 0.000 abstract description 3
- 150000001621 bismuth Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 7
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 6
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- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- CFVXSVUUNIZMOR-UHFFFAOYSA-N bismuth zinc cadmium(2+) sulfide Chemical compound [Cd+2].[S-2].[Zn+2].[Bi+3] CFVXSVUUNIZMOR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst and a preparation method thereof. In the zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst, the halloysite is in a nanotube structure, and zinc-cadmium-sulfur is dispersedly grown on the surface of the bismuth doped halloysite. The invention adopts a one-step solvothermal method to prepare modified bismuth doped halloysite, and the modified bismuth doped halloysite and zinc cadmium sulfur are ultrasonically compounded to form the composite photocatalyst. The zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst has good dispersibility and multiple active sites, is used for photocatalytic degradation of 10mg/L rhodamine B, shows excellent catalytic performance, and has a degradation rate of more than 85% within 60 min.
Description
Technical Field
The invention relates to a zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst and a preparation method thereof, belonging to the technical field of nano material preparation.
Background
The photocatalysis technology converts solar energy into chemical energy by utilizing unique light and electricity conversion characteristics of materials to obtain energy substances including hydrogen, hydrocarbon and the like and remove pollutants, bacteria and the like. However, the application of the existing photocatalyst is limited by the factors of low light utilization rate, high photo-generated electron recombination rate, few surface active sites and the like. The photocatalytic performance of the photocatalyst can be improved by modifying the photocatalyst, and the modification method comprises noble metal doping, semiconductor compounding, defect or heteroatom introduction, photosensitizer addition and the like.
Halloysite is a natural clay silicate mineral and has the advantages of large specific surface area, rich reserves, good thermal stability, uniform structure and the like. The halloysite has a chemical composition similar to that of kaolin and has a chemical formula of Al2Si2O5(OH)4·nH2O (n ═ 0, 2), a tubular structure formed by the spatial misfit dislocations between aluminum oxy octahedra and silicon oxy tetrahedra. The inner surface of the halloysite micron tube is Al-OH and presents electronegativity, and the outer surface is O-Si-O groups and presents electropositivity. Thus, halloysite enables the majority of metal particles or ions (Pt, Fe)3+，Ag+Etc.), metal compound (Fe)3O4CdS, CuO, etc.) and high molecular polymers (polyaniline, polythiophene, etc.) are uniformly loaded on the halloysite. Surface work of the halloysite nanotube by Siva Kumar-Krishnan et al through silver nanoparticle modificationCan be used for enzyme immobilization and biosensing [ Siva Kumar-Krishan, et al (2016). ] Surface functionalized and halloycite synthesized with silver nanoparticles for enzyme immobilization and biosensing.]. Xing, W.N. CdS-halloysite composite materials prepared by hydrothermal method are used for degrading tetracycline and have high-efficiency photocatalytic activity [ Xing, W.N. et al. (2012) ] A Preparation high photocatalytic activity of CdS/Halloycite Nanotubes (HNTs) with a hydrothermal method of Applied Surface Science 259,698-704.]. The Halloysite @ Polyaniline (HNT @ PANI) core-shell nano composite nanotube prepared by in-situ polymerization of Zhou, T.Z. and the like has high-efficiency Cr (VI) Adsorption Reduction effect [ Zhou, T.Z., et al (2017) ]effective Adsorption/Reduction of Cr (VI) Oxyanino by halogen @ Polyaniline Hybrid nanotubes of ACS Appl.Mater.Interfaces,9,6030-]. Yin, L.X. Zn prepared by hydrothermal method0.2Cd0.8The degradation of 10mg/L RhB of S microspheres within 60min is only 50% [ Yin, L.X., et al. (2019).' structuring 3D structural Zn ]0.2Cd0.8Smicrospheres for the improved visible-light-drivenphotocatalytic performance."International Journal of Hydrogen Energy,doi:10.1016]. The modification modes all use natural silicate as a carrier, halloysite is not used as a photocatalyst to participate in photocatalytic reaction, and the agglomeration phenomenon exists when single zinc-cadmium-sulfur nanocrystalline is prepared.
Disclosure of Invention
The invention aims to provide a zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst with excellent catalytic performance and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst comprises the following steps:
step 1, uniformly dispersing halloysite in a saturated aluminum trichloride solution, adding an ethylene glycol solution of bismuth nitrate pentahydrate, stirring and mixing uniformly, carrying out solvothermal reaction at 160-180 ℃, naturally cooling after the reaction is finished, centrifuging, washing, and drying to obtain bismuth-doped halloysite;
And 2, ultrasonically dispersing bismuth-doped halloysite in water, adding cadmium acetate dihydrate and zinc acetate dihydrate, ultrasonically stirring, adding thioacetamide, ultrasonically stirring for reaction, centrifuging, washing and drying to obtain the zinc-cadmium-sulfur-bismuth-doped halloysite composite photocatalyst.
Preferably, in step 1, the molar ratio of bismuth nitrate pentahydrate to halloysite is 1: 5.
preferably, in step 1, the halloysite is ultrasonically dispersed in a saturated aluminum trichloride solution and then stirred until the mixture is uniformly mixed.
Preferably, in step 1, the stirring and mixing time is 0.5h or more, and the solvothermal reaction is 24h or more.
Preferably, in the step 1, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
Preferably, in step 2, the molar ratio of the cadmium acetate dihydrate, the zinc acetate dihydrate and the thioacetamide is 1:4: 5.
Preferably, in step 2, the ratio of bismuth-doped halloysite to thioacetamide is 100mg:1 mmol.
Preferably, in the step 2, the ultrasonic stirring reaction time is more than 2 hours, the centrifugal rate is 9000r/min, and the drying temperature is 60-80 ℃.
The zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst prepared by the preparation method disclosed by the invention has a nanotube structure on the micro scale, and zinc-cadmium-sulfur is dispersedly grown on the surface of bismuth doped halloysite.
Compared with the prior art, the invention has the following advantages:
(1) preparing modified bismuth-doped halloysite by adopting a one-step solvothermal method, and ultrasonically compounding the modified bismuth-doped halloysite with zinc, cadmium and sulfur to form a composite photocatalyst; (2) the halloysite raw material is rich in resources, low in price and easy to obtain, and the pretreatment mode is simple; (3) the zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst is used for photocatalytic degradation of 10mg/L rhodamine B, shows excellent catalytic performance, and has a degradation rate of over 85% within 60 min.
Drawings
FIG. 1 is a scheme of the synthesis scheme of the preparation process of the present invention.
Fig. 2 is an optical image of unmodified halloysite nanotubes (a) and bismuth-doped halloysite (B) prepared in example 1.
Fig. 3 is a schematic representation of the doping atom pattern of the bismuth-doped halloysite prepared in example 1.
FIG. 4 is a high resolution transmission electron microscope image of undoped halloysite nanotubes (A), bismuth-doped halloysite nanotubes (B), zinc cadmium sulfur-halloysite nanocomposites (C), zinc cadmium sulfur-bismuth-doped halloysite nanocomposites (D and E), zinc cadmium sulfur nanoparticles (F).
FIG. 5 is a transmission electron microscope image of zinc cadmium sulfide-bismuth doped halloysite prepared in comparative example 1(A) and comparative example 2 (B).
Figure 6 is an XRD diffractogram of the materials prepared in example 1, example 2 and comparative example 1.
Fig. 7 is a graph of the catalytic performance of the zinc cadmium sulfide-bismuth doped halloysite prepared in example 2 and comparative example 1.
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 diagram showing the synthetic mechanism of the preparation method of the present invention, in which halloysite is dispersed in a saturated aluminum chloride solution after pretreatment; bismuth nitrate pentahydrate is dispersed in ethylene glycol. And mixing the solutions, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, taking out the solution after solvothermal reaction, and centrifugally washing and drying the solution to obtain the bismuth-doped halloysite material. And dispersing Bi-doped halloysite in deionized water, sequentially adding cadmium acetate dihydrate, zinc acetate dihydrate and thioacetamide, ultrasonically stirring, centrifuging, washing and drying to obtain the zinc-cadmium-sulfur-bismuth-doped halloysite composite material.
Example 1
Step one, mixing 1.5mmol halloysite (258g/mol) with a saturated aluminum chloride solution, performing ultrasonic dispersion for 10min, and then stirring on a magnetic stirrer for 0.5 h;
secondly, 0.3mmol of bismuth nitrate pentahydrate (the molar ratio of the bismuth nitrate pentahydrate to the halloysite is 1:5) is weighed and dispersed in 5mL of glycol solution for 10min by ultrasonic treatment;
step three, dropwise adding the solution obtained in the step two into the suspension obtained in the step one, transferring the suspension into a 100mL polytetrafluoroethylene reaction kettle, carrying out solvothermal in a drying oven at 180 ℃ for 24 hours, and then taking out;
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 modified bismuth-doped halloysite nano material.
Fig. 2 is an optical diagram of unmodified halloysite nanotubes (a) and bismuth-doped halloysite (B) prepared in example 1. As can be seen from the figure, the modified bismuth-doped halloysite changes from yellowish to grayish black, indicating that the doping is successful. FIG. 3 is a graphical representation of the doping atom pattern of the bismuth-doped halloysite prepared in example 1 in favor of the substitution of the aluminum atoms in the aluminooctahedron with bismuth atoms in a saturated aluminum chloride solution environment.
Example 2
Firstly, dispersing 100mg of bismuth-doped halloysite in 50mL of deionized water, and performing ultrasonic dispersion for more than 30 min;
secondly, quantitatively adding 0.8mmol of cadmium acetate dihydrate and 0.2mmol of zinc acetate dihydrate (the molar ratio is 8:2) into the solution obtained in the first step, and ultrasonically stirring for more than 1 hour;
step three, adding 1mmol thioacetamide into the solution obtained in the step two, and carrying out ultrasonic mechanical stirring for 2 hours;
and fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ oven for 12 hours to obtain the zinc-cadmium-sulfur-bismuth doped halloysite composite material (named ZCS/Bi-HNT-1).
Example 3
Firstly, dispersing 20mg of zinc-cadmium-sulfur-bismuth doped halloysite in 50mL of 10mg/L rhodamine B solution, and stirring for 1 hour 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 3mL of liquid is separated by 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 100mg of modified halloysite in 50mL of deionized water, and performing ultrasonic dispersion for more than 30 min;
secondly, quantitatively adding 0.8 mmol of cadmium acetate dihydrate and 0.2mmol of zinc acetate dihydrate (the molar ratio is 8:2) into the solution obtained in the first step, and ultrasonically stirring for 1 hour;
step three, adding 1mmol thioacetamide into the solution obtained in the step two, and carrying out ultrasonic mechanical stirring for 2 hours;
and fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ oven for 12 hours to obtain the zinc-cadmium-sulfur-halloysite composite material.
Comparative example 2
Firstly, dispersing 100mg of bismuth-doped halloysite in 50mL of deionized water, and performing ultrasonic dispersion for more than 30 min;
secondly, quantitatively adding 0.4mmol of cadmium acetate dihydrate and 0.1mmol of zinc acetate dihydrate (the molar ratio is 8:2) into the solution obtained in the first step, and ultrasonically stirring for more than 1 hour;
thirdly, adding 0.5mmol thioacetamide into the solution obtained in the second step, and ultrasonically and mechanically stirring for 2 hours;
And fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ oven for 12 hours to obtain the zinc-cadmium-sulfur-bismuth doped halloysite composite material (ZCS/Bi-HNT-0.5).
Comparative example 3
Firstly, dispersing 100mg of bismuth-doped halloysite in 50mL of deionized water, and performing ultrasonic dispersion for more than 30 min;
secondly, quantitatively adding 1.6mmol of cadmium acetate dihydrate and 0.4mmol of zinc acetate dihydrate (the molar ratio is 8:2) into the solution obtained in the first step, and ultrasonically stirring for more than 1 hour;
step three, adding 2mmol thioacetamide into the solution obtained in the step two, and carrying out ultrasonic mechanical stirring for 2 hours;
and fourthly, centrifugally washing the sample obtained in the third step, and drying the sample in a 60 ℃ oven for 12 hours to obtain the zinc-cadmium-sulfur-bismuth doped halloysite composite material (ZCS/Bi-HNT-2).
FIG. 4 is a high resolution transmission electron microscope image of undoped halloysite nanotubes (A), bismuth-doped halloysite nanotubes (B), zinc cadmium sulfur-halloysite nanocomposites (C), zinc cadmium sulfur-bismuth-doped halloysite nanocomposites (D and E), zinc cadmium sulfur nanoparticles (F).
FIG. 5 is a transmission electron microscope image of zinc cadmium sulfide-bismuth doped halloysite prepared in comparative example 1(A) and comparative example 2 (B). A is the composite proportion of zinc, cadmium and sulfur and bismuth doped halloysite of 0.5mmol to 100mg (ZCS/Bi-HNT-0.5), and B is the composite proportion of zinc, cadmium and sulfur and bismuth doped halloysite of 2mmol to 100mg (ZCS/Bi-HNT-2). As can be seen from the figure, there are some zinc cadmium sulfur nanoparticles that were not grown on the bismuth-doped halloysite nanotubes when the zinc cadmium sulfur input ratio was less than the optimal ratio; when the zinc-cadmium-sulfur input ratio is larger than the optimal ratio, the zinc-cadmium-sulfur nanoparticles are agglomerated.
Figure 6 is an XRD diffractogram of the materials prepared in example 1, example 2 and comparative example 1. Comparing the X-ray diffraction patterns of halloysite and bismuth-doped halloysite, the bismuth-doped halloysite diffraction peak shifts slightly to small angles at 12.2 ° 2 θ due to Bi3+Radius greater than Al3+Radius, which also confirmed the successful doping of bismuth.
Fig. 7 is a graph of the catalytic performance of the zinc cadmium sulfide-bismuth doped halloysite prepared in example 2 and comparative example 1. As can be seen from the figure, the photocatalytic effects of the zinc cadmium sulfur-halloysite and the zinc cadmium sulfur-bismuth doped halloysite composite photocatalyst are better than those of undoped halloysite within 60min, and the degradation rate of the zinc cadmium sulfur-bismuth doped halloysite is higher than that of the zinc cadmium sulfur-halloysite, so that the excellent photocatalytic activity of the zinc cadmium sulfur-bismuth doped halloysite is shown. In conclusion, the zinc-cadmium-sulfur modified halloysite has good dispersibility, and the bismuth-doped halloysite is tightly combined with the zinc-cadmium-sulfur, so that the effective specific surface area of catalytic reaction is increased, the active sites are increased, and the catalytic activity is improved.
Claims (8)
1. The preparation method of the zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst is characterized by comprising the following steps of:
Step 1, uniformly dispersing halloysite in a saturated aluminum trichloride solution, adding a glycol solution of bismuth nitrate pentahydrate, stirring and mixing uniformly, carrying out solvothermal reaction at 160-180 ℃, naturally cooling after the reaction is finished, centrifuging, washing, and drying to obtain bismuth-doped halloysite;
and 2, ultrasonically dispersing bismuth-doped halloysite in water, adding cadmium acetate dihydrate and zinc acetate dihydrate, ultrasonically stirring, adding thioacetamide, ultrasonically stirring for reaction, centrifuging, washing and drying to obtain the zinc-cadmium-sulfur-bismuth-doped halloysite composite photocatalyst, wherein the molar ratio of the cadmium acetate dihydrate, the zinc acetate dihydrate and the thioacetamide is 1:4:5, and the ratio of the bismuth-doped halloysite to the thioacetamide is 100mg:1 mmol.
2. The method according to claim 1, wherein in step 1, the molar ratio of bismuth nitrate pentahydrate to halloysite is 1: 5.
3. the method according to claim 1, wherein in step 1, the halloysite is ultrasonically dispersed in a saturated aluminum trichloride solution and then stirred until the mixture is uniformly mixed.
4. The process according to claim 1, wherein in the step 1, the stirring and mixing time is 0.5 hours or more, and the solvothermal reaction time is 24 hours or more.
5. The method according to claim 1, wherein in step 1, the centrifugation rate is 9000r/min, and the drying temperature is 60-80 ℃.
6. The preparation method according to claim 1, wherein in the step 2, the ultrasonic stirring reaction time is more than 2h, the centrifugal rate is 9000r/min, and the drying temperature is 60-80 ℃.
7. The zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The application of the zinc-cadmium-sulfur-bismuth doped halloysite composite photocatalyst in photocatalytic degradation of organic dyes according to claim 7.
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