CN114849733A - Application of nanotube array in preparation of photocatalytic material - Google Patents
Application of nanotube array in preparation of photocatalytic material Download PDFInfo
- Publication number
- CN114849733A CN114849733A CN202111624876.XA CN202111624876A CN114849733A CN 114849733 A CN114849733 A CN 114849733A CN 202111624876 A CN202111624876 A CN 202111624876A CN 114849733 A CN114849733 A CN 114849733A
- Authority
- CN
- China
- Prior art keywords
- nanotube
- photocatalytic material
- preparation
- tio
- nanotube array
- 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.)
- Pending
Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000010936 titanium Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 239000002105 nanoparticle Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000003911 water pollution 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an application of a nanotube array in preparing a photocatalytic material, which comprises titanium sheet pretreatment; calcining the titanium dioxide nanotube; respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution; wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to an application of a nanotube array in preparation of a photocatalytic material.
Background
TiO 2 The photocatalytic performance of the material is discovered only in 1972, and the research focus is mainly on how to utilize the material to create more materials and values for people. Because the environment situation of the 21 st century is severe, the fog in the air frequently occurs, the water pollution frequently becomes urgent, and the like, the photocatalytic degradation is regarded as TiO 2 The most potential uses of the material. TiO 2 2 The material can degrade most organic pollutants in gas and liquid, and is particularly applied to substances which are difficult to degrade in common materials, such as degradation of dyes commonly used in textile dyeing and finishing, degradation of toxic substances such as nitric oxide in air and the like, degradation of toxic organic matters in water, and degradation final products are harmless salts such as carbon dioxide, water and the like, so that the material has great prospect in the aspect of product cleaning. With the development of scientific technology, the degradation time can be shortened greatly.
When light irradiates the surface of a semiconductor, only light quanta with relatively strong energy can play a role, because only the wavelength of the light is short enough to prevent conduction band electrons and valence band holes from being recombined, and the light can not be released in the form of heat energy or other forms. The semiconductor anatase type has a forbidden band width of 3.2eV, that is, only light with a wavelength less than 387.5nm irradiates the TiO 2 The surface of the semiconductor material can make the electrons on the surface of the semiconductor material transit. It has been attempted to coat a large number of materials, such as semiconductors with narrower gap bands, on TiO 2 The nanotube surface is used for further improving the performance and increasing the photoelectrochemical activity of a visible light region.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
As one aspect of the invention, the invention provides an application of a nanotube array in preparing a photocatalytic material.
In order to solve the technical problems, the invention provides the following technical scheme: an application of a nanotube array in preparing a photocatalytic material comprises,
pretreating a titanium sheet;
calcining the titanium dioxide nanotube;
respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution;
wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the titanium sheet is pretreated by ultrasonically cleaning the titanium sheet with acetone and ultrasonically cleaning the titanium sheet with isopropanol for 1-5 min; ultrasonically cleaning the substrate for 1-5 min by using methanol; and then chemically polishing the titanium sheet by using the volume ratio of HF, nitric acid and water of 1 to (3-4) to (3-5), and cleaning with deionized water.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: and calcining the titanium dioxide nanotube, namely, anodizing the pretreated titanium sheet by using 0.5-1% of ammonium fluoride as electrolyte, and then calcining the anodized titanium sheet.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: calcining the titanium dioxide nanotube, wherein the calcining is carried out at 400-500 ℃ for 2-5 h to prepare TiO 2 A nanotube.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the pretreated titanium sheet is subjected to anodic oxidation, and the electrolytic voltage is 60V.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the calcination is to prepare TiO for 2.5h at 450 DEG C 2 And (4) nano.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the photocatalytic material is catalytically degraded under visible light.
As a preferred scheme of the application of the nanotube array in the preparation of the photocatalytic material, the method comprises the following steps: the AgNO 3 The concentration of the solution was 0.1 mol/L.
The invention has the beneficial effects that: the invention is toCdS and Ag nano-particles with diameter of 20nm are coated on TiO 2 The walls of the nanotubes. TiO 2 2 The nano tube array is sensitized by Ag and CdS nano particles, so that the reaction and the photocurrent of visible light are obviously enhanced, and the photoelectrochemical performance is higher. This study also showed that the TiO coating was applied through two or more semiconductors 2 Nanotube surface, enhanced TiO 2 Nanotube photoelectrochemical properties, which ensures more efficient use of a wider range of visible radiation. Meanwhile, the changes of the morphology, the crystal form and the photocatalytic performance of the Ag-doped nanotube are contrastively analyzed, and the method specifically comprises the following steps: (1) TiO prepared by anodic oxidation 2 The nano tubes are uniformly distributed on the surface of the titanium sheet, have high catalytic efficiency, and can improve the degradation rate of methyl orange from 10% to about 74% after 4 hours. (2) Preparation of TiO 2 The optimal conditions for the nanotubes are: the electrolysis voltage is 60V, the electrolysis time is 3 hours, and the exercise temperature and the exercise time are respectively 450 ℃ and 2.5 hours.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an SEM image of a nanotube array prepared according to the present invention.
FIG. 2 is TiO 2 Nanotubes (a), CdS-doped TiO 2 The ultraviolet-visible spectrum of the nanotube (b) and the nanotube array (c) of the present invention.
FIG. 3 shows (a) TiO 2 Nanotube, CdS-doped TiO 2 The instant current reaction of the nanotube and the nanotube array of the present invention. (b) TiO doped with CdS and Ag 2 Nanotube surface charge distribution schematic.
FIG. 4 shows TiO irradiation under visible light 2 Nanotube, CdS-doped TiO 2 PC and PEC plots of RHBs for nanotubes, nanotube arrays of the invention.
FIG. 5 is a graph of degradation rates at 30min, 60min, 90min and 120 min.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
firstly, ultrasonically cleaning a titanium sheet by using acetone; ultrasonically cleaning the isopropanol for 5 min; ultrasonically cleaning with methanol for 5 min; then 11.6g of HF, 56.4g of nitric acid and 50g of water are weighed according to the volume ratio of 1: 4: 5 to the HF, the nitric acid and the water respectively for chemical polishing and deionized water cleaning. 0.5% ammonium fluoride was used as the electrolyte.
Titanium sheets are subjected to anodic oxidation according to a conventional method and calcined at 450 ℃ for 2.5h to prepare TiO 2 A nanotube.
50ml of AgNO with the concentration of 0.02mol/L are prepared respectively 3 Solution and 0.1mol/L of Na 2 S and Cdcl 2 And (3) solution.
Subjecting the TiO to a reaction 2 The nano tube is firstly subjected to AgNO of 0.02mol/L 3 Soaking in the solution for 30min, and then soaking at 0.1mol/LNa 2 S and Cdcl 2 And soaking in the solution for 30min to obtain the co-doped nanotube array.
Immersing in methyl orange solution (solution concentration of 0.01g/L) for half an hour, and irradiating under 200W ultraviolet lamp with height controlled at 40 cm.
Calculating the degradation rate: obtaining TiO by the photocatalytic degradation rate of methyl orange 2 The higher the degradation rate of the nanotube is, the better the photocatalytic effect of the sample is, and the degradation rate is related to the measured absorbance value.
FIG. 1 is an SEM image of a nanotube array prepared according to the present invention. FIG. 2 shows TiO 2 Nanotubes (a), CdS-doped TiO 2 Nanotubes (b), the ultraviolet-visible spectrum of the nanotube array (c) of the present invention. FIG. 2 shows TiO 2 Nanotube sample, TiO with CdS nanoparticles 2 Nanotube sample, TiO with CdS and Ag nanoparticles 2 Ultraviolet absorption spectrum of nanotube sample. Curve a in FIG. 3 shows TiO 2 Nanotubes absorb most of the ultraviolet light with wavelengths shorter than 400 nm. After the CdS nanoparticles are deposited, the absorption edge is largely shifted to the visible region as shown by the absorption spectrum. After further sensitization of Ag nanoparticles, TiO 2 Nanotubes absorb all visible light throughout the solar spectrum, making them promising photosensitive materials for solar applications. Testing of TiO by intermittent visible radiation 2 Transient photocurrent response of the nanotubes. During the cyclic switching, the circuit photocurrent density is instantaneous and reproducible. FIG. 3(a) TiO 2 Nanotube, CdS-doped TiO 2 Nanotubes, the instant current response of the nanotube arrays of the present invention. (b) TiO doped with CdS and Ag 2 Nanotube surface charge distribution schematic.
As shown in a of FIG. 3, TiO due to its poor optical absorption property 2 The nanotube electrode did not show any significant enhancement in photocurrent density, only 0mA/cm 2 。TiO 2 The photocurrent density of the saturated nanotube was 15.2mA/cm 2 Higher photocurrent density means more photoinduced electrons from the TiO 2 The nanotubes are transferred to an external circuit counter electrode. This result indicates higher TiO content 2 The nanotube photocurrent is due to visible light absorption by the Ag nanoparticles and efficient transfer of electrons. FIG. 3 (b) shows TiO 2 Microscopic view of charge carrying transfer of nanotube electrodesThe method is described. The narrower band Ag will be readily activated by low energy visible light and attracted by electron-hole pairs. Most of Ag conducts more efficiently than CdS, and Ag is transferred to CdS and TiO 2 Will be suppressed. The quantum effect of Ag nanoparticles can change the conduction band position. The nanometer size of Ag nanoparticles can cause separation of conduction bands, the position of the conduction band is more negative than that of CdS, and electrons are injected from the light-excited Ag to the CdS conduction band. Photoelectrons are collected from Ag, transferred to CdS nanoparticles through interfaces of heterostructures and then transferred to TiO 2 The nanotube surface. Electrons from TiO by an external electrostatic field 2 Nanotube surface, through TiO 2 Interface with Ti into the external loop. And transferring the light generation hole of the valence band of the CdS nano-particles to the Ag nano-particles, and then obtaining a counter electrode. In this way, photo-induced electron-hole pairs are efficiently separated.
FIG. 4 shows TiO irradiation under visible light 2 Nanotube, CdS-doped TiO 2 PC and PEC plots of RHBs for nanotubes, nanotube arrays of the invention. TiO coated with CdS and Ag nanoparticles under visible light irradiation for 5 hours 2 70.6% of RHB were available for nanotube transfer, and TiO coated with CdS nanoparticles for the same exposure time 2 Nanotube transferred RHB and TiO 2 Only 44.2% and 11.8% were available in the RHB for nanotube transfer. TiO with CdS and Ag nanoparticles 2 The nanotubes have higher visible light photocatalytic activity due to their more efficient acquisition of photo-charges and reduced probability of electron pair coalescence.
To study the catalytic time with TiO 2 The relation of the nanotube photocatalysis performance is that firstly, the nanotube is dipped in AgNO of 0.02mol/L 3 Reducing different illumination reduction time in the solution, wherein the selected time is respectively 30min, 60min, 90min and 120min, the degradation rate is as shown in figure 5, and the nanotube catalytic effect curves under different illumination reduction time have common characteristics according to figure 5: with the increase of the illumination time, the degradation rate of the methyl orange is gradually increased, the degradation speed of the methyl orange is fast in 0 to 3 hours, and the degradation rate of the methyl orange is obviously reduced and is smooth in 3 to 4 hours. It can also be seen from the figure thatThe degradation rate of the methyl orange of the nanotube after reduction for 90min is the fastest, and the degradation rate of the solution after 4 hours is about 90 percent at the highest. The photocatalytic efficiency of the nanotube with the reduction time of 120min, 60min, 30min and 15min is slightly worse than that of the nanotube, namely, the photocatalytic efficiency of the nanotube is respectively 87.5%, 84.8%, 79.2% and 77.5%, so that the nanotube array with the reduction time of 90min has the best catalytic effect.
In conclusion, CdS and Ag nano-particles with the diameter of 20nm are coated on TiO 2 The walls of the nanotubes. TiO 2 2 The nano tube array is sensitized by Ag and CdS nano particles, so that the reaction and the photocurrent of visible light are obviously enhanced, and the photoelectrochemical performance is higher. This study also showed that two or more semiconductors were coated on TiO 2 Nanotube surface, enhanced TiO 2 Nanotube photoelectrochemical properties, which ensures more efficient use of a wider range of visible radiation. Meanwhile, the changes of the morphology, the crystal form and the photocatalytic performance of the Ag-doped nanotube are contrastively analyzed, and the method specifically comprises the following steps: (1) TiO prepared by anodic oxidation 2 The nano tubes are uniformly distributed on the surface of the titanium sheet, have high catalytic efficiency, and can improve the degradation rate of methyl orange from 10% to about 74% after 4 hours. (2) Preparation of TiO 2 The optimal conditions for the nanotubes are: the electrolytic voltage is 60V, the electrolytic time is 3 hours, and the exercise temperature and the exercise time are respectively 450 ℃ and 2.5 hours
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. An application of a nanotube array in preparing a photocatalytic material is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
pretreating a titanium sheet;
calcining the titanium dioxide nanotube;
respectively soaking the titanium dioxide nanotubes in AgNO 3 Solution, Na 2 S and Cdcl 2 Obtaining a photocatalytic material in the solution;
wherein, the AgNO 3 The concentration of the solution is 0.02-0.2 mol/L; the Na is 2 The concentration of S is 0.1-0.2 mol/L, and the Cdcl 2 The concentration of the solution is 0.1-0.2 mol/L.
2. Use of the nanotube array of claim 1 for the preparation of a photocatalytic material, characterized in that: the titanium sheet is pretreated by ultrasonically cleaning the titanium sheet with acetone and ultrasonically cleaning the titanium sheet with isopropanol for 1-5 min; ultrasonically cleaning the substrate for 1-5 min by using methanol; and then chemically polishing the titanium sheet by using the volume ratio of HF, nitric acid and water of 1 to (3-4) to (3-5), and cleaning with deionized water.
3. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: and calcining the titanium dioxide nanotube, namely, anodizing the pretreated titanium sheet by using 0.5-1% of ammonium fluoride as electrolyte, and then calcining the anodized titanium sheet.
4. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: calcining the titanium dioxide nanotube, wherein the calcining is carried out at 400-500 ℃ for 2-5 h to prepare TiO 2 A nanotube.
5. Use of the nanotube array of claim 3 for the preparation of a photocatalytic material, characterized in that: the pretreated titanium sheet is subjected to anodic oxidation, and the electrolytic voltage is 60V.
6. Use of the nanotube array of claim 4 for the preparation of a photocatalytic material, wherein: the calcination is to prepare TiO for 2.5h at 450 DEG C 2 And (4) nano.
7. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: the photocatalytic material is catalytically degraded under visible light.
8. Use of the nanotube array of claim 1 or 2 for the preparation of a photocatalytic material, characterized in that: the AgNO 3 The concentration of the solution was 0.1 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111624876.XA CN114849733A (en) | 2021-12-28 | 2021-12-28 | Application of nanotube array in preparation of photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111624876.XA CN114849733A (en) | 2021-12-28 | 2021-12-28 | Application of nanotube array in preparation of photocatalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114849733A true CN114849733A (en) | 2022-08-05 |
Family
ID=82627219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111624876.XA Pending CN114849733A (en) | 2021-12-28 | 2021-12-28 | Application of nanotube array in preparation of photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114849733A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104249993A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for producing hydrogen and oxygen through solar photocatalysis of water based on metal oxide photocatalyst |
| CN105363477A (en) * | 2015-10-23 | 2016-03-02 | 南昌航空大学 | Method for preparing silver/cadmium sulfide/titanium dioxide composite photocatalytic material |
| CN109174123A (en) * | 2018-07-27 | 2019-01-11 | 广东工业大学 | A kind of Z-type CdS-Ag-TiO2Composite photocatalyst material and its preparation method and application |
| CN111675289A (en) * | 2020-06-28 | 2020-09-18 | 盐城工学院 | Preparation method of porous titanium-based lead dioxide electrode |
-
2021
- 2021-12-28 CN CN202111624876.XA patent/CN114849733A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104249993A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for producing hydrogen and oxygen through solar photocatalysis of water based on metal oxide photocatalyst |
| CN105363477A (en) * | 2015-10-23 | 2016-03-02 | 南昌航空大学 | Method for preparing silver/cadmium sulfide/titanium dioxide composite photocatalytic material |
| CN109174123A (en) * | 2018-07-27 | 2019-01-11 | 广东工业大学 | A kind of Z-type CdS-Ag-TiO2Composite photocatalyst material and its preparation method and application |
| CN111675289A (en) * | 2020-06-28 | 2020-09-18 | 盐城工学院 | Preparation method of porous titanium-based lead dioxide electrode |
Non-Patent Citations (2)
| Title |
|---|
| HAKAN KIZILTAŞ ET AL.: ""Increasing of Photocatalytic Performance of TiO2 Nanotubes by Doping AgS and CdS"" * |
| 高大伟等: ""二氧化钛纳米管的制备及其光催化性能"" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Recent advances in the TiO2/CdS nanocomposite used for photocatalytic hydrogen production and quantum-dot-sensitized solar cells | |
| Liu et al. | Highly stable CdS-modified short TiO2 nanotube array electrode for efficient visible-light hydrogen generation | |
| Yang et al. | Preparation of CdS/TiO2 nanotube arrays and the enhanced photocatalytic property | |
| Zhu et al. | CdS and PbS nanoparticles co-sensitized TiO2 nanotube arrays and their enhanced photoelectrochemical property | |
| CN102658130B (en) | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof | |
| Mahadik et al. | Highly efficient and stable 3D Ni (OH) 2/CdS/ZnIn2S4/TiO2 heterojunction under solar light: effect of an improved TiO2/FTO interface and cocatalyst | |
| CN102002746B (en) | Method for preparing iron oxide nano granule modified titanium dioxide nano tube array | |
| Zhang et al. | Enhanced charge collection and photocatalysis performance of CdS and PbS nanoclusters co-sensitized TiO2 porous film | |
| CN109647377B (en) | Electrochemical self-doping type WO3Particle-supported TiO2Nanotube and preparation method and application thereof | |
| CN104383950B (en) | A kind of Bi2o3-BiOI hetero-junctions visible-light-responsive photocatalyst and preparation method thereof | |
| Li et al. | Constructing stable NiO/N-doped TiO 2 nanotubes photocatalyst with enhanced visible-light photocatalytic activity | |
| Zhang et al. | Capability of coupled CdSe/TiO 2 heterogeneous structure for photocatalytic degradation and photoconductivity | |
| Wang et al. | CdS and SnS2 nanoparticles co-sensitized TiO2 nanotube arrays and the enhanced photocatalytic property | |
| Guo et al. | Effective photocathodic protection for 304 stainless steel by PbS quantum dots modified TiO2 nanotubes | |
| Hao et al. | Solar-responsive photocatalytic activity of amorphous TiO2 nanotube-array films | |
| Zhou et al. | Photoelectrochemical Performance of Quantum dot-Sensitized TiO 2 Nanotube Arrays: a Study of Surface Modification by Atomic Layer Deposition Coating | |
| CN114411168B (en) | Cobalt-lanthanum co-doped visible light response BiVO 4 Photoelectrode and method for producing the same | |
| Yang et al. | Double-shelled ZnO/TiO 2/CdS nanorod arrays for enhanced photoelectrocatalytic performance | |
| Guo et al. | Synthesis of ZnO/Cu 2 S core/shell nanorods and their enhanced photoelectric performance | |
| Kilic et al. | Carbon nanofiber based CuO nanorod counter electrode for enhanced solar cell performance and adsorptive photocatalytic activity | |
| CN108273486B (en) | Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof | |
| González et al. | Synthesis of ruthenium-doped TiO2 nanotube arrays for the photocatalytic degradation of terasil blue dye | |
| Kong et al. | The co-modification of MoS 2 and CdS on TiO 2 nanotube array for improved photoelectrochemical properties | |
| Wen et al. | Enhanced photocatalytic degradation of methyl orange by CdS quantum dots sensitized platelike WO3 photoelectrodes | |
| CN112811523A (en) | Preparation method and application of nanocomposite oxygen-doped molybdenum disulfide/titanium dioxide nanotube array |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220805 |