CN111389421B - Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material - Google Patents
Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material Download PDFInfo
- Publication number
- CN111389421B CN111389421B CN202010285528.3A CN202010285528A CN111389421B CN 111389421 B CN111389421 B CN 111389421B CN 202010285528 A CN202010285528 A CN 202010285528A CN 111389421 B CN111389421 B CN 111389421B
- Authority
- CN
- China
- Prior art keywords
- nbo
- preparation
- hti
- htn
- solution
- 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
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 16
- 239000010936 titanium Substances 0.000 title claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- -1 hydrogen ions Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 56
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 7
- 230000004298 light response Effects 0.000 abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 3
- 239000012153 distilled water Substances 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—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
Abstract
The invention discloses a preparation method and application of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material. The preparation method firstly adopts a simple high-temperature solid phase method to prepare the layered CsTi 2 NbO 7 As a precursor, obtaining acidified HTi by proton exchange reaction with nitric acid 2 NbO 7 Then HTi is performed 2 NbO 7 Dispersing in distilled water, and stripping to obtain pillared HTi 2 NbO 7 Suspending liquid of nanosheet, precipitating with low-concentration acid, and centrifuging to obtain H with recombined hydrogen ions + Ti 2 NbO 7 ‑ And (4) nano-sheet sol. And carrying out hydrothermal treatment on the HTN nanosheets and the BiOCl nanosheets to obtain the BiOCl/HTN nanosheet composite heterojunction. The preparation method has the advantages of simple process and low cost, and the obtained composite material has a typical layer-layer structure, more surface active areas, visible light response and stable photocatalytic performance, so the preparation method has great potential application value in preparing novel photocatalysts.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a preparation method and application of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material.
Background
With the rapid development of the industry in China, the discharge amount of industrial wastewater is increased year by year, and the serious pollution to the environment is caused. At present, the traditional organic pollution wastewater treatment methods comprise a physical adsorption method, a chemical precipitation method, a biochemical method and the like, but all have the problems of certain secondary pollution, low treatment efficiency, high required cost and the like, and can not meet the sustainable development requirement, and the photocatalytic degradation technology applied to the field of environmental control has the advantages of high efficiency, greenness, economy, effective utilization of solar energy and the like.
At present, the photocatalytic material faces the problems of complex synthesis process, low utilization rate of visible light, low catalytic efficiency, high energy consumption and the like, so that the photocatalytic material is limited in industrial production and practical application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a two-dimensional layered bismuth oxychloride and titanium niobate compound photocatalytic material comprises the following steps:
and 6, washing and drying the obtained composite heterojunction of the two-dimensional BiOCl/HTN nanosheets to obtain the BiOCl/HTN nanosheet composite material (BHT).
As a modification, the raw material Cs used in step 1 2 CO 3 、Nb 2 O 5 、TiO 2 The temperature rise speed of the high-temperature calcination is kept between 5 and 10 ℃/min, and the temperature is respectively kept at 750 ℃,950 ℃ and 1050 ℃ for 12 hours in the calcination process.
As a modification, 5g of CsTi is added in step 2 2 NbO 7 Adding 500mL of HNO with the concentration of 1mol/L 3 In the solution, the solution is added with a solvent,stirring at 60 deg.C for 72 hr, and changing HNO every 24 hr 3 And (3) solution.
As a modification, the rate of centrifugation in step 3 was 3000r/min.
As an improvement, the HNO concentration in the step 4 is low 3 The solution was 0.1mol/L.
The improvement is that the upper layer stripping nanosheet sol is centrifuged in the step 3, and the centrifugation speed is 3000r/min.
As an improvement, the low concentration of HNO used in step 4 3 Solution sedimentation, HNO 3 The concentration was 0.1mol/L.
As a modification, the specific steps of washing and drying in the step 6 are as follows: and (3) washing the composite heterojunction of the two-dimensional BiOCl/HTN nanosheets for 5-10 times by using an absolute ethyl alcohol aqueous solution with the volume ratio of 1:1, then placing the heterojunction in a vacuum environment at 60 ℃ for drying, and washing to remove residual impurities on the surface of BHT.
The two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material prepared by the method is applied to degradation of RhB solution.
The working principle is as follows: on one hand, the BiOCl nanosheet has a special energy band structure and certain visible light response capability; on the other hand, the layer-layer heterojunction structure formed after the materials are compounded can be beneficial to the rapid separation of photo-generated electron-hole pairs, so that the quantum yield is improved, and the photocatalytic degradation performance is also improved within the visible light response range.
Has the advantages that:
compared with the prior art, the preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material has the advantages that: firstly, preparing the layered CsTi by adopting a high-temperature solid-phase method 2 NbO 7 As a precursor, a pillared exfoliation reaction was performed by proton exchange of tetrabutylammonium hydroxide (TBAOH) solution with nitric acid to obtain HTi 2 NbO 7 And (3) precipitating the nanosheet suspension by using dilute nitric acid to obtain hydrogen ion recombined nanosheet sol HTN. With KCl and Bi (NO) 3 ) 3 ·5H 2 O is taken as a reaction precursor of the BiOCl nano-sheet, and certain amounts of KCl and Bi (NO) are added 3 ) 3 ·5H 2 Adding HTN into O, uniformly stirring, and carrying out hydrothermal treatment, thereby successfully synthesizing the novel 2D/2D BiOCl/HTN nanosheet (BHT) composite material. The preparation method has the advantages of simple process, low equipment requirement and low cost, and the prepared layered composite material has high photocatalytic efficiency and excellent degradation effect on RhB.
Drawings
FIG. 1 is an XRD pattern of samples CsTi2NbO7, HTi2NbO7, HTN, BHT prepared in each step in example 1 of the present invention, wherein BiOCl is a sample prepared in comparative example 1;
FIG. 2 is an electron micrograph of the sample produced in inventive example 1, and of BiOCl produced in comparative example 1: (a) a FEEM image of HTN nanosheets, (b) a FESEM image of BiOCl, (c) a FESEM image of BHT, (d), (e) and (f) HRTEM images of BHT;
FIG. 3 is a graph of the visible photocatalytic RhB solution degradation of HTN and BHT samples of example 1 of the present invention, wherein BiOCl is a sample prepared according to comparative example 1;
fig. 4 is a graph of uv-vis spectra corresponding to different times when the BHT composite material in example 1 of the present invention catalyzes the degradation of RhB solution by visible light;
FIG. 5 is a graph showing the effect of visible light on the catalytic degradation of RhB solution after 5 cycles of the layered BHT composite material in example 1 of the present invention;
FIG. 6 is a schematic view of the condensing apparatus of the present invention.
Detailed description of the preferred embodiment
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) The CsTi2NbO7 is synthesized by a high-temperature solid phase method, namely analytically pure Cs2CO3, nb2O5 and TiO2 are adopted as raw materials, mixed according to a molar ratio of 1.112 hours, the heating rate is 10 ℃/min, and a precursor CsTi is synthesized 2 NbO 7 。
(2) Preparation of HTi by ion exchange 2 NbO 7 : 5.0g of CsTi 2 NbO 7 Adding 500mL of HNO 3 (1 mol/L) solution, treating for 72 hours at 60 ℃ under continuous stirring, and changing HNO with the same volume concentration every 24 hours 3 The sample was washed to neutral drying treatment.
(3) 3.0g of layered HTi 2 NbO 7 Dispersed in 300mL of deionized water, and a certain amount of tetrabutylammonium hydroxide solution (TBAOH) is added into the suspension drop by drop until the pH value reaches 9.5-10.0, and the mixture is stirred for 7 days at room temperature. Centrifuging the obtained solution in a high-speed centrifuge, and collecting supernatant to obtain HTi 2 NbO 7 Nano-sheet sol, weighing the dried mass of the residual powder, and determining HTi 2 NbO 7 Concentration of nanosheet sol, HTi determined by volume concentration 2 NbO 7 Stirring the nano-sheet sol continuously and uniformly, and dropwise adding a certain amount of 0.1mol/L HNO 3 The solution is settled to obtain H + Recombinant HTN.
(4) 60mL of HTN is magnetically stirred for 0.5 hour to ensure that the HTN nanosheets are uniformly re-dispersed; then 0.4mmol of KCl and 0.4mmol of Bi (NO) 3 ) 3 ·5H 2 Dropwise adding O into the solution, magnetically stirring for 1 hour, transferring the obtained solution into a hydrothermal reaction kettle, and reacting for 24 hours at 160 ℃; finally, the obtained sample is washed for a plurality of times by using a mixed solution of deionized water and absolute ethyl alcohol, and is dried at 60 ℃ to obtain the layered BiOCl/HTN composite material (abbreviated as BHT).
Example 2
(1) Synthesis of CsTi by high temperature solid phase method 2 NbO 7 Namely, the raw material is analytically pure Cs 2 CO 3 、Nb 2 O 5 、TiO 2 Mixing the components according to a molar ratio of 1.1CsTi 2 NbO 7 。
(2) Preparation of HTi by ion exchange 2 NbO 7 : 5.0g of CsTi 2 NbO 7 Adding 500mL of HNO 3 (1 mol/L) solution, treating for 72 hours at 60 ℃ under continuous stirring, and changing HNO with the same volume concentration every 24 hours 3 The sample was washed to neutral drying treatment.
(3) 3.0g of layered HTi 2 NbO 7 Dispersing in 300mL of deionized water, adding a certain amount of tetrabutylammonium hydroxide solution (TBAOH) into the suspension dropwise until the pH value reaches 9.5-10.0, and stirring at room temperature for 7 days. Centrifuging the obtained solution in a high-speed centrifuge, and collecting supernatant to obtain HTi 2 NbO 7 Nano-sheet sol, weighing the dried mass of the residual powder, and determining HTi 2 NbO 7 Concentration of nanosheet sol, HTi determined by volume concentration 2 NbO 7 Stirring the nano-sheet sol continuously and uniformly, and dropwise adding a certain amount of 0.1mol/L HNO 3 The solution is settled to obtain H + Recombinant HTN.
(4) 60mL of HTN is magnetically stirred for 0.5 hour to ensure that the HTN nanosheets are uniformly re-dispersed; then 0.2mmol of KCl and 0.4mmol of KCl are added into the solution drop by drop and are stirred by magnetic force for 1 hour, the obtained solution is transferred to a hydrothermal reaction kettle and reacts for 24 hours at 160 ℃; finally, the obtained sample is washed for a plurality of times by using a mixed solution of deionized water and absolute ethyl alcohol, and is dried at 60 ℃ to obtain the layered BiOCl/HTN composite material (abbreviated as BHT).
Example 3
(1) Synthesis of CsTi by high temperature solid phase method 2 NbO 7 Namely, the raw material is analytically pure Cs 2 CO 3 、Nb 2 O 5 、TiO 2 Mixing the components according to a molar ratio of 1.1 2 NbO 7 。
(2) By ion exchangePreparation of HTi 2 NbO 7 : 5.0g of CsTi 2 NbO 7 Added to 500mL of HNO 3 (1 mol/L) solution, treating for 72 hours at 60 ℃ under continuous stirring, and changing HNO with the same volume concentration every 24 hours 3 The sample was washed to neutral drying treatment.
(3) 3.0g of layered HTi 2 NbO 7 Dispersing in 300mL of deionized water, adding a certain amount of tetrabutylammonium hydroxide solution (TBAOH) into the suspension dropwise until the pH value reaches 9.5-10.0, and stirring at room temperature for 7 days. Centrifuging the obtained solution in a high-speed centrifuge, and collecting supernatant to obtain HTi 2 NbO 7 Nano-sheet sol, weighing the dried mass of the residual powder, and determining HTi 2 NbO 7 Concentration of nanosheet sol, HTi determined by volume concentration 2 NbO 7 Stirring the nano-sheet sol continuously and uniformly, and dropwise adding a certain amount of 0.1mol/L HNO 3 The solution is settled to obtain H + Recombinant HTN.
(4) 60mL of HTN is magnetically stirred for 0.5 hour to ensure that the HTN nanosheets are uniformly re-dispersed; then, 0.6mmol of KCl and 0.4mmol of KCl are added into the solution drop by drop, magnetic stirring is carried out for 1 hour, the obtained solution is transferred to a hydrothermal reaction kettle, and the reaction is carried out for 24 hours at 160 ℃; finally, the obtained sample is washed for a plurality of times by using a mixed solution of deionized water and absolute ethyl alcohol, and is dried at 60 ℃ to obtain the layered BiOCl/HTN composite material (abbreviated as BHT).
Example 4
(1) Synthesis of CsTi by high temperature solid phase method 2 NbO 7 Namely, the raw material is analytically pure Cs 2 CO 3 、Nb 2 O 5 、TiO 2 Mixing the components according to a molar ratio of 1.1 2 NbO 7 。
(2) Preparation of HTi by ion exchange 2 NbO 7 : 5.0g of CsTi 2 NbO 7 Added to 500mL of HNO 3 (1 mol/L) solution, treating for 72 hours at 60 ℃ under continuous stirring, and changing HNO with the same volume concentration every 24 hours 3 The sample was washed to neutral drying treatment.
(3) 3.0g of layered HTi 2 NbO 7 Dispersed in 300mL of deionized water, and a certain amount of tetrabutylammonium hydroxide solution (TBAOH) is added into the suspension drop by drop until the pH value reaches 9.5-10.0, and the mixture is stirred for 7 days at room temperature. Centrifuging the obtained solution in a high-speed centrifuge, and collecting supernatant to obtain HTi 2 NbO 7 Nano-sheet sol, weighing the dried mass of the residual powder, and determining HTi 2 NbO 7 Concentration of nanosheet sol, HTi determined by volume concentration 2 NbO 7 Stirring the nano-sheet sol continuously and uniformly, and dropwise adding a certain amount of 0.1mol/L HNO 3 The solution is settled to obtain H + Recombinant HTN.
(4) 60mL of HTN is magnetically stirred for 0.5 hour to ensure that the HTN nanosheets are uniformly re-dispersed; then 0.8mmol of KCl and 0.4mmol of KCl are added into the solution drop by drop and are stirred magnetically for 1 hour, the obtained solution is transferred to a hydrothermal reaction kettle and reacts for 24 hours at 160 ℃; finally, the obtained sample is washed by a mixed solution of deionized water and absolute ethyl alcohol for a plurality of times and dried at 60 ℃ to obtain the layered BiOCl/HTN composite material (abbreviated as BHT).
Preparation of comparative example BiOCl alone
Slowly dropwise adding 8mL of isopropyl titanate into 60mL of distilled water, magnetically stirring for 1 hour, uniformly stirring, transferring the obtained solution into a hydrothermal reaction kettle, and reacting for 24 hours at 160 ℃; and finally, washing the obtained sample for a plurality of times by using a mixed solution of deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the single BiOCl.
Performance testing
In order to verify and analyze the self-quality and catalytic performance of the two-dimensional layered composite photocatalyst obtained in the embodiment of the present invention, the experimental example performs experiments on the BiOCl/HTN composite photocatalysts obtained in embodiments 1 to 4 and a single BiOCl, and the test analysis results show better performance, specifically, embodiment 1 is taken as an experimental example to explain:
first, the test example identified the samples to be tested, and respectively identified CsTi 2 NbO 7 The results of X-ray powder diffraction analysis tests of HTN and layered composite BiOCl/HTN nanosheets (BHT) are shown in FIG. 1, and CsTi is compared according to the index 2 NbO 7 The XRD pattern of the sample was consistent with that of a standard card (PDF: 73-0680). CsTi thus prepared 2 NbO 7 I.e. features that appear as a layer-rod structure. While the acidified stripping strut H + Recombined HTN, with original layer rod-like CsTi 2 NbO 7 Compared with the prior art, all characteristic peaks disappear, only the characteristic diffraction peak of the main crystal plane (020) deflects to a small angle, which indicates that the crystallinity is reduced, the original layered structure disappears, and the stacking of the stripped nanosheets causes the (020) image to deflect to a small angle. For comparison, biOCl alone was also successfully prepared, with XRD results consistent with standard card (PDF: 82-0485). BHT has similar XRD diffraction peaks as BiOCl, with several major (001), (002) and (101) strong characteristic diffraction peaks at 2 θ =10 °,24 ° and 26 ° indicating the formation of BiOCl in the layered composite, but some of the HTN's layered characteristic diffraction peaks, such as (020) this layered structure diffraction peak, were found to disappear, and it is likely that upon analysis the layered composite formed during hydrothermal processing, and the strong diffraction peaks of BiOCl covered the HTN's characteristic diffraction peaks. In combination with the above, the BiOCl nano-sheets are generated and uniformly distributed on the HTN nano-sheets to form a surface-to-surface contact two-dimensional layered heterojunction structure.
To further prove the above-mentioned partial speculation on substance identification and further analyze and study the microscopic morphological characteristics of HTN, biOCl and BHT photocatalytic materials, the experimental examples performed scanning electron microscopy, transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) on them, and the results are shown in fig. 2. As can be seen with reference to fig. 2 (a), the HTN approximates a single-layer thin-film layer-by-layer packing, and it can be considered that the precursor titanonibate has been successfully exfoliated into nanosheets. As shown in FIG. 2 (b), the single BiOCl nanosheets are in the shape of small round flakes, are uniform in size, are tightly stacked, have uneven material surfaces, and may be formed by irregularly stacking the nanosheets. Further observing the morphology of the compound BHT, as shown in FIG. 2 (c), the structures of the layered nanosheets and the pure round flaky BiOCl nanosheets with regular original HTN shapes disappear, the compound presents a flaky structure with uniform size and irregular arrangement, and more holes are formed on the surface; to further verify the successful preparation of the layered composite, fig. 2 (e) visually shows that the successful recombination of two sets of nanosheet structures forms a heterojunction structure characterized by the lattice parameter of fig. 2 (d), and the interplanar spacing d =0.282nm, i.e., the BiOCl nanosheet exposed crystal plane (004), and the lattice parameter d =0.182nm of fig. 2 (f), i.e., the HTN (002) exposed crystal plane. The presence of both sets of components in the complex was confirmed, as well as the successful synthesis of the complex.
Further, in order to verify the degradation capability of the BHT visible light catalyst, the experiment also performs a comprehensive visible light photocatalytic degradation RhB experiment on the sample prepared in example 1, a 300W xenon lamp is used as a simulation light source, a filter is arranged in front of the xenon lamp to filter out ultraviolet light with the wavelength shorter than 420nm and retain the visible light spectrum, a RhB solution with the concentration of 10mg/L is used to simulate a sewage water body containing organic pollutants, the degradation effects of the prepared HTN, biOCl and BHT are mainly compared, the addition content of the photocatalyst is 100mg, a dark adsorption reaction is performed before illumination to achieve the effect that the catalyst is fully contacted with target molecules and is in an adsorption saturation state, after illumination begins, the photocatalytic reaction is performed in a commercially available double-layer beaker serving as a condensing device (as shown in fig. 6) to remove the influence of thermal effect on the catalytic performance in the illumination process, a group of samples is taken at an interval of 15min, and the concentration change of the target solution RhB solution is tested through liquid ultraviolet to characterize the photocatalytic performance of the catalyst. It can be seen from fig. 3 that the catalytic effect of the complex is significantly better than that of the single component. The ultraviolet-visible light spectroscopy is adopted to test the concentration change of the RhB solution in a timing and quantitative manner, and fig. 4 shows that the RhB solution is catalytically degraded by the composite BHT under visible light, and the concentration of the RhB solution is gradually reduced along with the increase of the photocatalytic time.
Further, in order to investigate the stability of the BHT sample prepared in example 1, in this test example, the photocatalyst was collected by recycling, a circulation device consisting of a sand core funnel, an external vacuum pump, and an aqueous filter membrane having a pore size of 0.45 μm was used, the solution after each circulation reaction was placed in the sand core funnel, the vacuum pump was turned on, the reaction solution was removed by suction filtration, the solid catalyst was collected at the filter membrane and subjected to the next set of circulation, thereby obtaining degradation RhB under visible light irradiation, and the photodegradation stability result of BHT was investigated. As shown in fig. 5, it can be clearly seen that after 3 times of repeated experiments, the photocatalyst is not significantly deactivated, and the inevitable catalyst loss during the collection process and the reduction degree of the catalytic performance are not changed, which indicates that the prepared layered BHT composite photocatalytic material shows excellent stability and RhB removal activity.
In summary, in the preparation method of the two-dimensional layered bismuth oxychloride and titanonibate composite photocatalytic material of the embodiment of the invention, the layered CsTi2NbO7 is prepared as a precursor by a high-temperature solid-phase method, and H is stripped by acidification and support + And recombining to obtain HTN nanosheet suspension, and carrying out composite hydrothermal reaction on the HTN nanosheet suspension and BiOCl to successfully synthesize a novel layered-layered BiOCl/HTN nanosheet (BHT) composite heterojunction. The composite material prepared by the preparation method has strong visible light response, high photocatalytic efficiency and good degradation effect on RhB. Therefore, the layered composite photocatalyst and the preparation method provided by the embodiment of the invention can be widely applied to the field of photocatalytic degradation of organic sewage.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Claims (7)
1. A preparation method of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material is characterized by comprising the following steps:
step 1, weighing raw material Cs according to a molar ratio of 1.1 2 CO 3 、Nb 2 O 5 、TiO 2 Mixing and placing inFully grinding in a mortar, placing the ground powder in a muffle furnace, calcining at the high temperature of 750-1050 ℃ to synthesize a precursor CsTi 2 NbO 7 ；
Step 2, adding a precursor CsTi 2 NbO 7 With 1 to 2mol/L HNO 3 The solution is reacted, and the obtained sample is washed and dried to obtain HTi 2 NbO 7 ；
Step 3, adding HTi 2 NbO 7 Dispersing in deionized water to obtain suspension, adding tetrabutylammonium hydroxide solution into the suspension for stripping until the pH value reaches 9.5-10.0, stirring at room temperature for 7 days, centrifuging, and collecting supernatant to obtain HTi 2 NbO 7 Nano-sheet sol;
step 4, forming HTi 2 NbO 7 Adding 0.1 mM-0.5 mM of low-concentration HNO into the nano-sheet sol 3 The solution is settled to obtain H + Reconstituted HTi 2 NbO 7 Nano-sheet sol;
step 5, taking 60-80mL of H + Recombinant HTi 2 NbO 7 Magnetically stirring the nano-sheet sol for 0.5 hour to ensure uniform dispersion of HTN, and adding 0.4mmol of KCl and 0.4mmol of Bi (NO) 3 ) 3 ·5H 2 O, 0.2mmol of KCl and 0.4mmol of Bi (NO) 3 ) 3 ·5H 2 O, 0.6mmol of KCl and 0.4mmol of Bi (NO) 3 ) 3 ·5H 2 O, 0.8mmol of KCl and 0.4mmol of Bi (NO) 3 ) 3 ·5H 2 Dropwise adding O into the solution, magnetically stirring for 1 hour, transferring the uniform suspension into a high-pressure hydrothermal reaction kettle with a stainless steel outer sleeve and a polytetrafluoroethylene inner container, reacting for 24 hours at 160 ℃, and obtaining a precipitation product, namely a composite heterojunction of two-dimensional BiOCl/HTN nano sheets, through high-speed centrifugation;
and 6, washing and drying the obtained two-dimensional BiOCl/HTN nanosheet composite heterojunction to obtain the BiOCl/HTN nanosheet composite material.
2. The preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate compound photocatalytic material as claimed in claim 1, wherein the preparation method is characterized in thatRaw Material Cs used in step 1 2 CO 3 、Nb 2 O 5 、TiO 2 The temperature rise speed of the high-temperature calcination is kept between 5 and 10 ℃/min, and the temperature is respectively kept at 750 ℃,950 ℃ and 1050 ℃ for 12 hours in the calcination process.
3. The method for preparing the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material as claimed in claim 1, wherein in step 2, 5g of CsTi is added 2 NbO 7 Adding 500mL of HNO with the concentration of 1mol/L 3 Stirring at 60 deg.C for 72 hr, and changing HNO every 24 hr 3 And (3) solution.
4. The preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material as claimed in claim 1, wherein the centrifugation speed in step 3 is 3000r/min.
5. The preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material according to claim 1, wherein the HNO with low concentration in the step 4 is prepared from 3 The solution was 0.1mol/L.
6. The preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material as claimed in claim 1, wherein the specific steps of washing and drying in step 6 are as follows: and (3) washing the composite heterojunction of the two-dimensional BiOCl/HTN nanosheets for 5-10 times by using an absolute ethyl alcohol aqueous solution with the volume ratio of 1:1, and then drying in a vacuum environment at 60 ℃.
7. The application of the two-dimensional layered bismuth oxychloride and titanium niobate compound photocatalytic material prepared by the method of claim 1 in degradation of RhB solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010285528.3A CN111389421B (en) | 2020-04-13 | 2020-04-13 | Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010285528.3A CN111389421B (en) | 2020-04-13 | 2020-04-13 | Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111389421A CN111389421A (en) | 2020-07-10 |
| CN111389421B true CN111389421B (en) | 2022-11-25 |
Family
ID=71417492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010285528.3A Active CN111389421B (en) | 2020-04-13 | 2020-04-13 | Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111389421B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717958B (en) * | 2021-01-22 | 2022-06-21 | 江苏大学 | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst |
| CN115920930B (en) * | 2022-07-26 | 2023-11-10 | 江苏大学 | Bismuth oxychloride/molybdenum disulfide composite photocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881079A (en) * | 2017-02-09 | 2017-06-23 | 江苏大学 | A kind of preparation method of two dimensional oxidation tungsten/niobic acid tin nanometer sheet piece composite |
| CN107262085A (en) * | 2017-07-21 | 2017-10-20 | 江苏大学 | A kind of preparation method of bismuth/calcium niobate potassium plasma nano composite |
| CN109622007A (en) * | 2018-12-04 | 2019-04-16 | 盐城工学院 | A kind of N doping composite photo-catalyst and preparation method thereof |
-
2020
- 2020-04-13 CN CN202010285528.3A patent/CN111389421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881079A (en) * | 2017-02-09 | 2017-06-23 | 江苏大学 | A kind of preparation method of two dimensional oxidation tungsten/niobic acid tin nanometer sheet piece composite |
| CN107262085A (en) * | 2017-07-21 | 2017-10-20 | 江苏大学 | A kind of preparation method of bismuth/calcium niobate potassium plasma nano composite |
| CN109622007A (en) * | 2018-12-04 | 2019-04-16 | 盐城工学院 | A kind of N doping composite photo-catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111389421A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Bandgap engineering and enhanced interface coupling of graphene–BiFeO 3 nanocomposites as efficient photocatalysts under visible light | |
| CN111389421B (en) | Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material | |
| WO2016026339A1 (en) | Synthesis method for tio2 nanocrystal | |
| Yang et al. | Construction of a rod-like Bi 2 O 4 modified porous gC 3 N 4 nanosheets heterojunction photocatalyst for the degradation of tetracycline | |
| CN103864139A (en) | Preparation method of three-dimensional layered multilevel flower-shaped stannic oxide microsphere | |
| CN100509146C (en) | Method for preparing porous barium titanate photocatalyst | |
| Yu et al. | BiOBr hybrids for organic pollutant removal by the combined treatments of adsorption and photocatalysis | |
| Sun et al. | Crystallinity and photocatalytic properties of BiVO4/halloysite nanotubes hybrid catalysts for sunlight-driven decomposition of dyes from aqueous solution | |
| Zhang et al. | A novel study on preparation of H 2 TiO 3–lithium adsorbent with titanyl sulfate as titanium source by inorganic precipitation–peptization method | |
| Sui et al. | Sol–gel synthesis of linear Sn-doped TiO 2 nanostructures | |
| CN106517130B (en) | A method of di iron micro-nano powder material is prepared with rich phosphorus biomass | |
| WO2016026340A1 (en) | Tio2 nanocrystal and synthesis method therefor | |
| Wang et al. | Lignin-assisted solid-phase synthesis of nano-CuO for a photocatalyst with excellent catalytic activity and high performance supercapacitor electrodes | |
| CN109745992B (en) | Single-phase ferroelectric nano material with high photocatalytic activity and preparation method thereof | |
| Hui et al. | Ferroelectric-assisted charge carrier separation over Bi 2 MoO 6 nanosheets for photocatalytic dye degradation | |
| Yang et al. | Enhanced piezoelectric catalytic properties of NaNbO3 powder by defects engineering | |
| Pei et al. | Vanadium doping of strontium germanate and their visible photocatalytic properties | |
| CN108579773A (en) | A kind of perovskite-based composite nano materials and preparation method and purposes | |
| CN116651489A (en) | Magnetic modified three-dimensional flower-shaped N-Bi 2 O 2 CO 3 / g-C 3 N 4 Preparation method and application of photocatalytic material | |
| CN115970684A (en) | Ti 3 C 2 /TiO 2 Online heterojunction and preparation method and application thereof | |
| CN110563036A (en) | bismuth oxide nano material rich in oxygen vacancy and preparation method thereof | |
| CN110683518A (en) | Process for producing metal oxide | |
| CN108993572A (en) | A kind of preparation method of Fe2O3 doping tungstic acid-nitridation carbon compound film | |
| CN114505068A (en) | Piezoelectric catalyst and preparation method and application thereof | |
| CN113797919A (en) | High-exposure {001} crystal face bismuth niobate titanate nanosheet piezoelectric catalyst 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 |