CN107469817B - Silver nanorod-titanium dioxide composite material and preparation method and application thereof - Google Patents
Silver nanorod-titanium dioxide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN107469817B CN107469817B CN201710658532.8A CN201710658532A CN107469817B CN 107469817 B CN107469817 B CN 107469817B CN 201710658532 A CN201710658532 A CN 201710658532A CN 107469817 B CN107469817 B CN 107469817B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- silver
- composite material
- nanorod
- silver nanorod
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 147
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 100
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 99
- 239000004332 silver Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 85
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000002073 nanorod Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000001782 photodegradation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 15
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 41
- 239000011248 coating agent Substances 0.000 description 40
- 235000019441 ethanol Nutrition 0.000 description 23
- 238000001035 drying Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002042 Silver nanowire Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GMMZXKSNKIUKOW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(C)O Chemical compound [O-2].[O-2].[Ti+4].C(C)O GMMZXKSNKIUKOW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B01J35/39—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a silver nanorod-titanium dioxide composite material as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: the titanium dioxide particle is partially grown on the surfaces of the silver nanorods in situ, and the other part of the titanium dioxide particle is dispersed among gaps of the silver nanorods. The weight ratio of the silver nanorods to the titanium dioxide is (0.0025-1): 1, providing a silver nanorod-titanium dioxide composite material capable of effectively performing photocatalytic degradation on gas-phase pollutants, and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a silver nanorod-titanium dioxide composite material as well as a preparation method and application thereof.
Background
The titanium dioxide has the advantages of stable physical and chemical properties, chemical and photo corrosion resistance, no toxicity, low price and the like, so that the titanium dioxide is an ideal semiconductor material and is widely applied to the fields of solar cells, photocatalytic hydrogen production, photocatalytic degradation of organic and inorganic pollutants and the like. But TiO22The wide-band-gap semiconductor material has some obvious defects, and the forbidden band width of the wide-band-gap semiconductor material is too large, so that the wide-band-gap semiconductor material has a narrow photoresponse range to light and can only be excited by ultraviolet light; the ultraviolet light only accounts for 5% in the solar spectrum, so that the utilization of the solar energy is greatly reduced; in addition, TiO2The electron-hole pairs generated by excitation are easy to recombine, and the photocatalytic efficiency is also reduced, so that the method has a plurality of limitations in practical application. To solve this problem, researchers have reduced the recombination of photogenerated electron-hole pairs or optimized oxygen by doping or loading certain elements or compoundsThe light absorption performance of titanium-based photocatalytic material is improved by using the titanium-based photocatalytic material2The obtained heterostructure mainly comprises Sn/TiO2 and Cu/TiO2、CeO2/TiO2And graphene/TiO2These heterostructures are semiconductor/TiO2The energy band is bent or changed, so that the absorption edge is red-shifted to absorb more visible light, the utilization of a solar spectrum is increased, and the aim of increasing the photocatalytic efficiency is fulfilled. However, the photocatalytic performance of titanium dioxide is mainly influenced by the electron-hole recombination rate and the light absorption capacity, while the semiconductor/TiO2The method is optimized only for the factor that the light absorption capacity of titanium dioxide is weak, and the synergistic effect influence between the hole recombination rate and the light absorption capacity is ignored.
The patent discloses a silver/titanium dioxide composite heterostructure and a preparation method thereof (publication number CN103721708B), and discloses a silver/titanium dioxide composite heterostructure and a preparation method thereof. According to the invention, the bead chain titanium oxide structure is grown on the surface of the silver nanowire to form the composite material, so that the light absorption capacity of the material is optimized, the separation efficiency of photogenerated electrons and holes in the titanium oxide is improved, and the effect of the composite material in liquid phase photocatalysis is further improved. However, the method still has a plurality of problems in the degradation of gas-phase organic pollutants: firstly, under the traditional liquid phase photocatalysis condition, the concentration of pollutant molecules is higher, the pollutant molecules are contacted with the photocatalyst through random motion and degraded on the surface of the photocatalyst, but under the gas phase condition, the concentration of the pollutant is low, and the retention time is short, so that the photocatalytic material is required to have a larger contact area and can effectively adsorb the pollutant molecules; secondly, the silver nanowires have smooth surfaces and limited enhancement effect on light, and cannot fully utilize the plasma resonance effect on the surface of the noble metal.
According to the problems in the prior art, the invention provides a silver nanorod-titanium dioxide composite material capable of effectively performing photocatalytic degradation on gas-phase pollutants, and a preparation method and application thereof.
Disclosure of Invention
The invention provides the following technical scheme:
a silver nanorod-titanium dioxide composite, comprising: the titanium dioxide particle is partially grown on the surfaces of the silver nanorods in situ, and the other part of the titanium dioxide particle is dispersed among gaps of the silver nanorods.
Preferably, the weight ratio of the silver nanorods to the titanium dioxide is (0.0025-1): 1.
preferably, the length of the silver nanorod is 100-10000 nm; the particle diameter of the titanium dioxide is 5-100 nm.
Preferably, the weight ratio of the silver nanorods to the titanium dioxide is (0.0025-0.01): 1; the particle diameter of the titanium dioxide is 10-20 nm.
A preparation method of a silver nanorod-titanium dioxide composite material comprises the following steps:
s1: preparing a silver nanorod dispersion liquid: dispersing silver nanorods with the length of 100-10000 nm in a dispersing agent, and then performing ultrasonic dispersion to obtain a uniform and stable silver nanorod dispersion liquid;
s2: preparing a silver nanorod-titanium dioxide suspension: adding an organic titanium source into the silver nanorod dispersion liquid in S1, adding deionized water while stirring, and stirring for 20min to obtain a silver nanorod-titanium dioxide suspension;
s3: preparing the silver nanorod-titanium dioxide composite material: and (3) putting the silver nanorod-titanium dioxide suspension in the S3 into a reaction kettle, controlling the temperature to be 120-180 ℃, carrying out centrifugal washing after the reaction lasts for 4-16 hours, and finally carrying out vacuum drying to obtain the silver nanorod-titanium dioxide composite material.
Preferably, the silver nanorods in S1 are washed by isopropanol and ethanol in sequence and then are dispersed in the dispersant; wherein the number of washing times using the isopropyl alcohol and the ethanol is 3 times, respectively.
Preferably, the dispersant in S1 is an organic solvent, and the organic solvent is at least one of ethanol, methanol, isopropanol, ethylene glycol, toluene, and acetone.
Preferably, the mass ratio of the silver nanorods to the organic titanium source in S2 is (0.0025-1): 1.
preferably, the rotation speed of the centrifugal washing in the S3 is 1000-10000 rpm; the temperature and the time of the vacuum drying are respectively 50-80 ℃ and 2-12 h.
An application of a silver nanorod-titanium dioxide composite material in photodegradation of gas-phase pollutants: the silver nanorod-titanium dioxide composite material can be dispersed in an organic solvent, and is sequentially subjected to ball milling and coating to prepare a silver nanorod-titanium dioxide composite material coating, and then the silver nanorod-titanium dioxide composite material coating is placed in an environment with gas-phase pollutants.
Preferably, the coating is knife coating, spray coating or spin coating.
Preferably, the ball milling time is 1-48 h, and slurry with solid content of 1-10% is obtained after ball milling.
Preferably, the coating is to coat the slurry on a substrate, and the substrate is made of a metal, ceramic or glass substrate.
Preferably, the coating amount of the silver nanorod-titanium dioxide composite material on the substrate is 10-20 g/m2。
The invention has the beneficial effects that:
1. the silver nanorod and the titanium dioxide form a heterojunction structure, so that a photon-generated carrier is in a semiconductor/TiO2The interface is effectively separated, and the recombination rate of electron hole pairs is reduced; the ends and the surfaces of the silver nanorods have strong plasma resonance effect, and the plasma resonance effect is further enhanced due to the special appearance of the ends, so that the absorption of titanium oxide attached to the surfaces of the silver nanorods to solar spectrums is effectively increased; the specific principle is as follows: the one-dimensional structure of the silver nanorod has unique advantages in the aspect of electron transmission, and compared with nanoparticles, the silver nanorod can rapidly conduct electrons out and accelerate the separation of photo-generated electrons and holes, so that the recombination rate of photo-generated electron holes is effectively inhibited,the photoproduction electrons and the holes separated under the illumination condition can respectively generate chemical reaction with oxygen, water and the like adsorbed on the surface of the material to generate superoxide radical and hydroxyl radical, and more active radicals are generated, so that the photocatalytic activity of the composite material is greatly improved; in addition, the silver nanorods have strong surface plasma resonance effect, so that the silver nanorod/titanium dioxide composite material can absorb more visible light, thereby increasing the utilization of solar spectrum and finally achieving the purpose of improving the photocatalytic efficiency, so that the silver nanorod-titanium dioxide composite material provided by the invention has excellent photocatalytic performance;
2. the titanium dioxide nanoparticles filled in the gaps of the silver nanorods obviously increase the contact area between the silver nanorod-carbon dioxide composite material and a coating prepared from the silver nanorod-carbon dioxide composite material and air, and improve the adsorption capacity of the material on pollutant gas molecules, so that the silver nanorod-titanium dioxide composite material provided by the invention still has a good photodegradation effect even in the environment;
3. in the invention, the weight ratio of the silver nanorods to the titanium dioxide is strictly controlled to be (0.0025-1): 1, and more preferably (0.0025 to 0.01): 1; because of the catalytic performance of the composite material and the Ag nano rod and TiO2When the content of the Ag nano-rods is too much, namely the mass ratio is higher than 0.01, the photocatalytic performance of the composite material is greatly reduced because the content of the titanium dioxide playing the main photocatalytic role is too little; when the content of the Ag nano-rods is too low, namely the mass ratio is lower than 0.0025, the photocatalytic performance of the composite material is also greatly reduced due to the serious agglomeration phenomenon of titanium dioxide particles, so that the weight of the silver nano-rods and the weight of the titanium dioxide are controlled to be (0.0025-1): 1;
4. the preparation method is simple, the experimental raw materials are cheap and easy to obtain, the requirements on experimental equipment are low, the experimental conditions are easy to control and achieve, the reagents in the preparation process can be recycled, the resources are saved, and the large-scale production and application are facilitated.
Drawings
FIG. 1 is an SEM photograph of a silver nanorod/titanium dioxide composite material prepared in example 1;
FIG. 2 is an SEM photograph of the silver nanorod/titanium dioxide composite material prepared in example 2;
FIG. 3 is a scanned view of the distribution of Ag, Ti and O elements in the silver nanorod/titanium dioxide composite material prepared in example 3;
FIG. 4 is a graph showing different silver nanorods/TiO according to comparative examples 1-2 and examples 1-42Respectively carrying out degradation curves on acetaldehyde gas by the composite coating prepared from the photocatalytic material according to the weight ratio under visible light;
FIG. 5 shows different silver nanorods/TiO according to comparative examples 1-2 and examples 5-82Respectively carrying out degradation curves on acetaldehyde gas by the composite coating prepared from the photocatalytic material according to the weight ratio under visible light;
FIG. 6 is a reuse test result of the silver nanorod/titanium dioxide composite material prepared in example 2;
wherein: A0.25T is the sample from example 1; A0.5T is the sample from example 2; A0.75T is the sample from example 3; A1T is the sample prepared in example 4; A2T is the sample prepared in example 5; A3T is the sample prepared in example 6; A4T is the sample prepared in example 7; A5T is the sample prepared in example 8; A0T is the sample prepared in comparative example 1; AgT0 is the sample from comparative example 2.
Detailed Description
Example 1
Dispersing 0.875mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, transferring the mixture into a 50ml reaction kettle after full stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 0.25%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 2
Dispersing 1.75mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, fully stirring, transferring to a 50ml reaction kettle, drying at 160 ℃ for 10 hours in an oven, then performing centrifugal washing, and drying to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 0.5%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 3
Dispersing 2.625mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, transferring the mixture into a 50ml reaction kettle after full stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 0.75%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 4
Dispersing 3.5mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, transferring the mixture into a 50ml reaction kettle after fully stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 1%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 5
Dispersing 7mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20min, transferring the mixture into a 50ml reaction kettle after fully stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 2%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 6
Dispersing 10.5mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, transferring the mixture into a 50ml reaction kettle after full stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 3%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 7
Dispersing 14mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20min, transferring the mixture into a 50ml reaction kettle after fully stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 4%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Example 8
Dispersing 17.5mg of silver nanorods in 30ml of ethanol, performing ultrasonic dispersion for 30 minutes to obtain a silver nanorod dispersion liquid with good uniform stability and dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion liquid, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20 minutes, transferring the mixture into a 50ml reaction kettle after full stirring, performing centrifugal washing and drying in an oven at 160 ℃ for 10 hours to obtain silver nanorod-titanium dioxide composite material powder, wherein the weight ratio of the silver nanorods is 5%.
Taking 0.2g of silver nanorod-titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain a silver nanorod-titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate with the thickness of 5cm by 10cm, and naturally drying to obtain a silver nanorod-titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Comparative example 1
And (2) carrying out ultrasonic treatment on 30ml of ethanol for 30 minutes to obtain a solution with good uniform and stable dispersibility, adding 1.5ml of tetrabutyl titanate into the dispersion, continuously stirring, dropwise adding 1ml of deionized water, continuously stirring for 20min, fully stirring, transferring to a 50ml reaction kettle, carrying out centrifugal washing in an oven at 160 ℃ for 10 hours, and drying to obtain the titanium dioxide material powder.
Taking 0.2g of pure titanium dioxide powder, adding 2g of absolute ethyl alcohol, carrying out ball milling for 24h to obtain titanium dioxide ethanol dispersion, carrying out scratch coating on a glass plate of 5cm x 10cm, and naturally drying to obtain a titanium dioxide coating, wherein the quality of the coating is controlled to be 0.1 g.
Comparative example 2
And cleaning the silver nanorods with isopropanol for three times, then cleaning the silver nanorods with ethanol for three times, and finally ultrasonically dispersing 0.2g of the silver nanorods in ethanol to obtain uniform and stable ethanol dispersion liquid of the silver nanorods. The silver nano-rod coating is coated on a glass plate with the thickness of 5cm by 10cm by scraping, and the silver nano-rod coating is obtained by natural drying, and the quality of the coating is controlled to be 0.1 g.
As shown in FIGS. 4 to 5, the silver nanorod-titanium dioxide composite coatings prepared in comparative examples 1 to 2 and examples 1 to 4, in different weight ratios, were subjected to degradation rate tests, and their photo-degradation rates for gaseous pollutants were tested. The experimental conditions are as follows: under the condition of a fluorescent lamp with the visible light illumination condition of 4X 65W; introducing acetaldehyde gas with different concentrations, wherein the minimum concentration of the introduced acetaldehyde gas is 500 ppm: the statistics of the data of the degradation rate of the silver nanorod/titanium dioxide composite material with different specific gravity to the mobile phase acetaldehyde gas are shown in table 1:
TABLE 1
| Abbreviated code | The content of the silver nano-rod is wt% | Visible light degradation Rate (%) |
| A0.25T (example 1) | 0.0025 | 51±5 |
| A0.5T (example 2) | 0.005 | 72±5 |
| A0.75T (example 3) | 0.0075 | 63±5 |
| A1T (example 4) | 0.01 | 44±5 |
| A2T (example 5) | 0.02 | 30±5 |
| A3T (example 6) | 0.03 | 23±5 |
| A4T (example 7) | 0.04 | 14±5 |
| A5T (example 8) | 0.5 | 9±5 |
| A0T (comparative example 1) | 0 | 37±5 |
| AgT0 (comparative example 2) | 1.0 | 1±5 |
As can be seen from the data in the table, the samples prepared according to the method for preparing the silver nanorod-titanium dioxide composite material provided by the invention all have photodegradation, wherein the prepared silver nanorod-titanium dioxide composite material has higher photodegradation rate when the content of the silver nanorods reaches the preferred content provided by the invention.
As shown in fig. 6, a sample A0.5T is selected to perform a photocatalytic cycling stability test, and the specific experimental content is that, within a specific time, the same sample A0.5T is repeatedly placed in a fluorescent lamp with visible light illumination conditions of 4 × 65W and the initial concentration of acetaldehyde gas is 500ppm for 6 times, and the photodegradation rate of the sample A0.5T to acetaldehyde gas each time is measured, as can be seen from fig. 6, after the sample is repeatedly used for 6 times, the photodegradation rate of the sample A0.5T is still as high as 72% (± 5%), so that it can be proved that the silver nanorod-titanium dioxide composite material and the coating prepared by using the same have good photocatalytic cycling stability and can be repeatedly used for multiple times.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and substitutions can be made in the embodiments described in the foregoing embodiments, or some features of the embodiments may be replaced with other features. Any modification, substitution and improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (6)
1. A silver nanorod-titanium dioxide composite material is characterized by comprising:
the nano-silver rod comprises a silver nano-rod and titanium dioxide particles, wherein the length of the silver nano-rod is 100-10000 nm, the particle diameter of the titanium dioxide is 10-20 nm, and the weight ratio of the silver nano-rod to the titanium dioxide particles is (0.0025-0.01): 1;
and part of the titanium dioxide particles grow on the surfaces of the silver nanorods in situ, and the other part of the titanium dioxide particles is dispersed among gaps of the silver nanorods.
2. The preparation method of the silver nanorod-titanium dioxide composite material is characterized by comprising the following steps:
s1: preparing a silver nanorod dispersion liquid: dispersing silver nanorods with the length of 100-10000 nm in a dispersing agent, and then performing ultrasonic dispersion to obtain a uniform and stable silver nanorod dispersion liquid;
s2: preparing a silver nanorod-titanium dioxide suspension: and (2) adding an organic titanium source into the silver nanorod dispersion liquid in the S1, wherein the mass ratio of the silver nanorods to the organic titanium source is (0.0025-1): 1, adding deionized water while stirring, and stirring for 20min to obtain a silver nanorod-titanium dioxide suspension;
s3: preparing the silver nanorod-titanium dioxide composite material: and (3) putting the silver nanorod-titanium dioxide suspension in the S2 into a reaction kettle, controlling the temperature to be 120-180 ℃, carrying out centrifugal washing after the reaction lasts for 4-16 hours, and finally carrying out vacuum drying to obtain the silver nanorod-titanium dioxide composite material.
3. The method for preparing the silver nanorod-titanium dioxide composite material of claim 2, wherein the silver nanorods in S1 are washed with isopropanol and ethanol in sequence and then re-dispersed in the dispersant; wherein the number of washing times using the isopropyl alcohol and the ethanol is 3 times, respectively.
4. The method of claim 2, wherein the dispersant in S1 is an organic solvent, and the organic solvent is at least one of ethanol, methanol, isopropanol, ethylene glycol, toluene and acetone.
5. The method for preparing the silver nanorod-titanium dioxide composite material according to claim 2, wherein the rotation speed of centrifugal washing in S3 is 1000-10000 rpm; the temperature and the time of the vacuum drying are respectively 50-80 ℃ and 2-12 h.
6. Use of the silver nanorod-titanium dioxide composite material of claim 1 in photodegradation of gas phase contaminants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710658532.8A CN107469817B (en) | 2017-08-04 | 2017-08-04 | Silver nanorod-titanium dioxide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710658532.8A CN107469817B (en) | 2017-08-04 | 2017-08-04 | Silver nanorod-titanium dioxide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107469817A CN107469817A (en) | 2017-12-15 |
| CN107469817B true CN107469817B (en) | 2020-05-22 |
Family
ID=60596912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710658532.8A Active CN107469817B (en) | 2017-08-04 | 2017-08-04 | Silver nanorod-titanium dioxide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107469817B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022146158A1 (en) * | 2020-12-28 | 2022-07-07 | Акционерное Общество "Наука И Инновации" | Method for producing a hybrid piezomaterial |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110909A (en) * | 2018-08-31 | 2019-01-01 | 江苏新亿源环保科技有限公司 | A kind of preparation method of Ag doping modification biological filtrate |
| CN113600184A (en) * | 2021-08-19 | 2021-11-05 | 曹洋 | Synthesis method and application of titanium dioxide coated metal nano material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103366961A (en) * | 2013-06-18 | 2013-10-23 | 奇瑞汽车股份有限公司 | Doped titanium dioxide and preparation method thereof as well as dye-sensitized solar cell |
| CN103721708A (en) * | 2014-01-08 | 2014-04-16 | 济南大学 | Silver/titanium dioxide composite heterostructure and preparation method thereof |
| CN104923216A (en) * | 2015-06-25 | 2015-09-23 | 青岛科技大学 | Precious metal loaded TiO2 nanorod photocatalyst preparation method |
| CN106696380A (en) * | 2016-12-12 | 2017-05-24 | 江阴通利光电科技有限公司 | Formaldehyde photodegradation film |
| CN106944042A (en) * | 2017-02-22 | 2017-07-14 | 浙江大学 | A kind of core shell structure Ag/TiO2/ ZnO nano-wire and preparation method thereof |
-
2017
- 2017-08-04 CN CN201710658532.8A patent/CN107469817B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103366961A (en) * | 2013-06-18 | 2013-10-23 | 奇瑞汽车股份有限公司 | Doped titanium dioxide and preparation method thereof as well as dye-sensitized solar cell |
| CN103721708A (en) * | 2014-01-08 | 2014-04-16 | 济南大学 | Silver/titanium dioxide composite heterostructure and preparation method thereof |
| CN104923216A (en) * | 2015-06-25 | 2015-09-23 | 青岛科技大学 | Precious metal loaded TiO2 nanorod photocatalyst preparation method |
| CN106696380A (en) * | 2016-12-12 | 2017-05-24 | 江阴通利光电科技有限公司 | Formaldehyde photodegradation film |
| CN106944042A (en) * | 2017-02-22 | 2017-07-14 | 浙江大学 | A kind of core shell structure Ag/TiO2/ ZnO nano-wire and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "氧化硅改性的纳米Ag-TiO2复合体的制备及其光催化性能";范旭欣;《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》;20121015(第10（2012）期);B020-724 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022146158A1 (en) * | 2020-12-28 | 2022-07-07 | Акционерное Общество "Наука И Инновации" | Method for producing a hybrid piezomaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107469817A (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Maimaitizi et al. | In situ synthesis of Pt and N co-doped hollow hierarchical BiOCl microsphere as an efficient photocatalyst for organic pollutant degradation and photocatalytic CO2 reduction | |
| CN109078630B (en) | Composite photocatalyst and preparation method and application thereof | |
| WO2021120359A1 (en) | Wo3/tio2 nanotube having monoatomic noble metal anchored defects, and preparation and use thereof | |
| Fu et al. | Radiation synthesis of CdS/reduced graphene oxide nanocomposites for visible-light-driven photocatalytic degradation of organic contaminant | |
| CN107469817B (en) | Silver nanorod-titanium dioxide composite material and preparation method and application thereof | |
| Zhao et al. | Efficient visible light photocatalytic activity of p–n junction CuO/TiO 2 loaded on natural zeolite | |
| Liu et al. | Visible light-responsive carbon-decorated p-type semiconductor CaFe2O4 nanorod photocatalyst for efficient remediation of organic pollutants | |
| CN109331860B (en) | Low-platinum alloy composite nano photocatalyst for air purification and preparation method and application thereof | |
| Xu et al. | Fabrication of Bi2WO6 quantum dots/ultrathin nanosheets 0D/2D homojunctions with enhanced photocatalytic activity under visible light irradiation | |
| CN108654607B (en) | Preparation method of silver nanoparticle/carbon/titanium dioxide nano composite with core-shell structure | |
| Feng et al. | Two-step construction of WO3@ TiO2/CS-biochar S-scheme heterojunction and its synergic adsorption/photocatalytic removal performance for organic dye and antibiotic | |
| Gao et al. | Synthesis of “walnut‐like” BiOCl/Br solid solution photocatalyst by electrostatic self‐assembly method | |
| CN109876829B (en) | Pd/CdS/TOC photocatalyst and preparation method and application thereof | |
| CN112973744B (en) | Photoelectric catalyst and preparation method thereof | |
| US11896960B1 (en) | High-efficiency visible-light catalytic material and preparation method and application thereof | |
| Balta et al. | Facile synthesis of flake‒like Bi2WO6/carbon fiber heterojunction catalysts with enhanced photoactivity under visible light illumination | |
| CN109939697B (en) | Pd/CdS/TOC photocatalyst and preparation method and application thereof | |
| CN111229217A (en) | Preparation method of composite p-n type heterojunction photocatalyst and VOCs photocatalytic degradation method | |
| CN107497427A (en) | A kind of silver/graphite alkene/zinc oxide composite preparation method of degradable formaldehyde | |
| CN108940348B (en) | Silver chromate/sulfur-doped nitrogen carbon Z-type photocatalyst and preparation method thereof | |
| CN106732612A (en) | A kind of corronil nano wire/composite titania material and its preparation method and application | |
| Sun et al. | Adsorption coupling photocatalytic removal of gaseous n-hexane by phosphorus-doped g-C3N4/TiO2/Zn (OAc) 2-ACF composites | |
| CN114392770B (en) | Preparation method of cellulose-based photocatalytic material with weak photocatalytic performance | |
| CN110479386B (en) | High-dispersion composite photocatalyst and preparation method thereof | |
| CN110975906B (en) | Silver vanadate/silver carbonate p-n heterojunction composite photocatalyst and preparation method 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 |