CN110614091B - Spindle-shaped mesogenic TiO 2 Composite photocatalyst, preparation method and application thereof - Google Patents
Spindle-shaped mesogenic TiO 2 Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 title description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001782 photodegradation Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001112695 Clostridiales Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000006862 quantum yield reaction Methods 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention discloses a TiO with surface rich in hydroxyl 2 A composite photocatalyst formed by shuttle-shaped mesogen and a preparation method thereof. In a preferred embodiment, n-butyl titanate (TBOT) is used as a titanium source, acetic acid is used as a solvent, a trace amount of nitric acid is added into a reaction system, and then a solvothermal method is adopted to prepare the TiO with the surface rich in hydroxyl groups 2 And a shuttle mesogen. The invention prepares TiO on the basis of not adding any template and auxiliary agent 2 The shuttle mesogen, and through adding trace nitric acid, the hydroxyl content of the crystal surface is effectively improved, and the photodegradation rate of formaldehyde is improved. The invention has simple operation, one-step completion, economy and environmental protection; when the surface rich in hydroxyl groups is constructed, only a small amount of nitric acid is added, so that the use amount is small, but the modification effect is obvious. The prepared product can efficiently degrade formaldehyde under the condition of simulating sunlight, and has high activity.
Description
Technical Field
The invention relates to a TiO with surface rich in hydroxyl 2 A composite photocatalyst formed by shuttle mesogen, a preparation method and application thereof. The composite photocatalyst can be used for purifying pollutants in air by photocatalysis and degrading organic pollutants, in particular formaldehyde in the environment.
Technical Field
TiO is adopted 2 Degradation of contaminants in air as photocatalysts has the following advantages: tiO (titanium dioxide) 2 Stable chemical property, low price and low toxicity; only illumination is needed to excite the reaction; the product being non-toxic H 2 O and CO 2 . But TiO 2 There are two limitations: the forbidden bandwidth is larger (3.2 ev), and only ultraviolet light in sunlight can be utilized; second, the recombination rate of photogenerated electrons and holes is high, and thus the quantum yield is low.
TiO 2 Mesocrystals (TiO for short) 2 Mesogenic) means a material composed of TiO 2 The super structure formed by directional assembly of the nanocrystals has a plurality of unique properties, such as high crystallinity, porosity, monocrystal-like quality, and the like. Thus, tiO is used 2 The morphology of mesoscopic crystals is a viable idea to improve the photocatalytic performance. For example, the article Organic Small Molecule-Assisted Synthesis of High Active TiO by CrystEngComm journal 2010, 12, volumes 2073-2078 2 Rod-shaped TiO is used in Rod-Like Mesocrystals 2 The mesogen is applied to the degradation of methyl orange, and as a result, the prepared rod-shaped mesogen has higher catalytic performance than commercial P25. Nanoscale journal 2011Article Synthesis of Recrystallized Anatase TiO on pages 1910-1916 of the 3 rd volume 2 Mesocrystals with Wulff Shape Assisted by Oriented Attachment then reports TiO 2 Compared with P25, the mesogen has higher crystallinity and specific surface area, thereby having higher photodegradation effect on rhodamine B.
But TiO 2 The preparation process of mesoscopic crystals is often complex and depends on inorganic templates or organic auxiliaries. Chinese patent 201110128919.5 discloses a bar-shaped rutile TiO 2 Preparation method of mesogen, nano rod-like rutile TiO 2 The mesogen consists of 3-5nm superfine nano wires, the length of the mesogen is 200-300nm, and the diameter is 50-80nm; the preparation method comprises the steps of preparing TiO 2 Mixing with potassium hydroxide solution, reacting at high temperature for 2-4 days, washing with dilute nitric acid, and stirring for 5-15 days. From the preparation method, it is easy to see that a large amount of acidic and alkaline waste liquid is generated in the implementation process of the method, so that the method is not environment-friendly and is time-consuming and labor-consuming. Chinese patent 201410276619.5 uses n-butyl titanate as titanium source, acetic acid as solvent, and benzoic acid as surfactant to prepare spherical titanium ore TiO with controllable size 2 Mesogens with average particle size of 230-270nm.
In addition, tiO is increased 2 The content of surface hydroxyl groups can also improve the photocatalytic activity thereof. For example, paper Acetic Acid Functionalized TiO on pages 126-138 of the volume 367 of journal Journal of Catalysis, 2018 2 in/Kaolinite Composite Photocatalysts with Enhanced Photocatalytic Performance through Regulating Interfacial Charge Transfer, tiO is impregnated with acetic acid 2 Composite catalyst of kaolin to prepare TiO rich in hydroxyl 2 A surface. Research results show that the surface hydroxyl can be used as Lewis acid sites, which is favorable for prolonging the service life of a photo-generated carrier, thereby improving the photo-catalytic activity. Applied Catalysis B paper Photocatalytic reduction behavior of hexavalent chromium onhydroxyl modified titanium dioxide, pages 293-299 of Environmetal journal 2017, is applied to mesoporous TiO 2 The structure with rich hydroxyl on the surface is prepared by adopting the method of dipping in NaOH solution, thereby improving the reduction rate of Cr (VI). However, these methods are all based on TiO 2 The hydroxyl content of the surface of the raw material is improved by adopting an impregnation method.
Therefore, it is necessary to provide a method for preparing TiO 2 The one-step solvothermal method of mesogen does not need any auxiliary agent or template, and is simple to operate, economical and environment-friendly.
Disclosure of Invention
The invention aims to provide TiO with surface rich in hydroxyl groups 2 A composite photocatalyst formed by shuttle-shaped mesogen and a preparation method thereof. The method is to prepare TiO 2 The mesogenic one-step solvothermal method does not need to add any auxiliary agent or template, and the prepared product has the effect of degrading formaldehyde in the air by simulating solar irradiation and has good photodegradation effect on organic pollutants.
In order to achieve the above object of the present invention, the present invention provides a TiO having a surface rich in hydroxyl groups 2 A composite photocatalyst formed of a shuttle-like mesogen, the composite photocatalyst being prepared by a process comprising the steps of:
(1) Slowly adding a titanium source into the solvent under the action of strong stirring, and continuously stirring;
(2) Adding a trace amount of concentrated nitric acid into the system obtained in the step (1), and continuously stirring to form a transparent suspension;
(3) Transferring the suspension obtained in the step (2) into a reaction kettle, heating for reaction, and then cooling to room temperature;
(4) Respectively performing alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) And (3) calcining the composite material prepared in the step (4) at a high temperature.
In the invention, in order to construct the surface rich in hydroxyl, a method of adding trace nitric acid into an original reaction system is adopted, and compared with the method adopted in the prior art, the method essentially combines two steps into one step, thereby greatly saving time and raw material cost and reducing the production amount of waste liquid.
In step (1) of the present invention, the titanium source used is preferably n-butyl titanate (TBOT), and the solvent is preferably glacial acetic acid. In the invention, glacial acetic acid plays a plurality of roles: reacting with TBOT; inducing oriented crystallization; porogens, and the like. The volume ratio of TBOT to glacial acetic acid may be 0.1: 100-10:100. Preferably 0.1:100-20:100. here, the volumetric ratio of TBOT to glacial acetic acid can be used to control the size of the final product: the smaller the ratio, the larger the final mesogenic size. The slow addition may be dropwise addition or the like.
In step (2) of the present invention, a trace amount of concentrated nitric acid (e.g., 65 to 68wt% of concentrated nitric acid) is added to increase TiO 2 Content of surface hydroxyl groups. The adding amount of the concentrated nitric acid is according to the amount of TBOT, ti: NO 3 The molar ratio of (2) can be controlled at 1:0.001-1: 1. The content of the concentrated nitric acid is not excessively large, because the addition of the concentrated nitric acid damages the morphology of the shuttle mesogen to a certain extent. Preferably, ti-NO 3 The molar ratio of (2) is 1:0.01-1:0.2; more preferably, ti-NO 3 The molar ratio of (2) is 1:0.01-1:0.1.
In step (3) of the present invention, the reaction temperature may be 100 to 220℃and preferably 150 to 200 ℃. The reaction time may be from 6 to 72 hours, preferably from 18 to 24 hours; the cooling mode is preferably natural cooling. The reaction vessel may be a reactor such as an autoclave.
In the step (4) of the invention, the alcohol washing and the water washing are preferably performed for more than three times, and the drying temperature is preferably 70-120 ℃. The alcohol used in the alcohol washing is preferably ethanol.
In step (5) of the present invention, the calcination temperature may be 300 to 600 ℃, preferably 400 to 500 ℃. The calcination time may be 3 to 9 hours, preferably 3 to 6 hours. Calcination may be performed in a muffle furnace under air conditions, and the temperature rise rate may be 2 ℃/min.
In the composite photocatalyst prepared by the invention, the prepared TiO 2 The morphology is a shuttle mesogen.
The composite photocatalyst can be used for purifying air by photocatalysis, so as to remove formaldehyde in the air by photodegradation.
In another aspect, in order to achieve the object of the present invention, the present invention also provides a method for preparing a TiO having hydroxyl groups enriched from the surface 2 Method for forming composite photocatalyst by shuttle-shaped mesogen, and method for preparing composite photocatalyst by using methodThe method comprises the following steps:
(1) Slowly adding a titanium source into the solvent under the action of strong stirring, and continuously stirring;
(2) Adding a trace amount of concentrated nitric acid into the system obtained in the step (1), and continuously stirring to form a transparent suspension;
(3) Transferring the suspension obtained in the step (2) into a reaction kettle, heating for reaction, and then cooling to room temperature;
(4) Respectively performing alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) And (3) calcining the composite material prepared in the step (4) at a high temperature.
In the step (1) of the method, the solvent is preferably glacial acetic acid, and the titanium source is preferably n-butyl titanate; the volume ratio of the n-butyl titanate to the glacial acetic acid is preferably 0.1:100-20:100.
In the step (3) of the method, the reaction temperature can be controlled to be 100-220 ℃, and the temperature of high-temperature calcination in the step (5) can be controlled to be 300-600 ℃.
The invention adopts a nitric acid-assisted one-step solvothermal method to prepare the TiO with the surface rich in hydroxyl 2 The shuttle-shaped mesogenic final product is used for purifying air by photocatalysis so as to photodegradation and eliminate formaldehyde in the air. Advantages of the present invention include, but are not limited to:
A. the operation is simple, the completion is completed in one step, and the method is economical and environment-friendly;
B. in the preparation of TiO 2 No auxiliary agent or template is added in the mesogenic process, and only a trace amount of nitric acid is added in the original reaction system on the surface rich in hydroxyl groups, so that the raw materials are simple and easy to obtain, the dosage is small, and the modification effect is obvious;
C. the prepared product can efficiently degrade formaldehyde under the condition of simulating sunlight, and has high activity.
The invention is further described below in conjunction with the detailed description and the accompanying drawings; it is to be understood that these specific embodiments are merely illustrative of the invention and are not limiting thereof. Those skilled in the art can fully modify the specific embodiments of the present invention or make equivalent substitutions for certain technical features in the light of the present invention, but these modified or substituted technical solutions still fall within the protection scope of the present invention.
Drawings
FIG. 1 is an XRD spectrum of a TBHN catalyst;
FIG. 2 is a FESEM image of TBHN-0 (a, b, c) and TBHN-8 (d, e, f);
FIG. 3 is a FTIR spectrum of a TBHN catalyst;
fig. 4 is TBHN catalyst photocatalytic performance: (a) photodegradation formaldehyde curve of TBHN catalyst; (b) TBHN In (C) 0 Curves are plotted for/C) against t.
In the above figures, TBHN represents TiO prepared by the present invention and having hydroxyl groups on the surface 2 The numbers below represent the percentages of nitrate and titanium atoms of the composite photocatalyst formed by the shuttle mesogen. The specific formulation of each catalyst can be derived from the examples.
Detailed Description
The present invention is further illustrated below with reference to preparation examples and test examples, using conventional method steps unless otherwise specified. The starting materials are all commercially available from public sources.
Preparation examples 1 to 4
Taking a certain amount of glacial acetic acid, dropwise adding n-butyl titanate (TBOT) under the action of strong stirring, and continuously stirring for a certain time. A trace amount of concentrated nitric acid (65-68 wt%) was added to the system and stirring continued for a period of time to form a clear suspension. Transferring the obtained suspension into an autoclave, heating to a certain temperature, reacting for a certain time, and naturally cooling to room temperature. Washing with ethanol and water for several times, and oven drying. The prepared composite material is calcined at high temperature under the air condition in a muffle furnace. The catalyst prepared was designated as TBHN, and the figures hereafter represent the percentages of nitrate and titanium atoms. The following table sets forth the specific raw material compositions and reaction conditions for examples 1-4.
Structure testing
FIG. 1 is an XRD spectrum of TBHN photocatalyst; from the above, it can be seen that the prepared TBHN catalyst is in anatase form, and the TBHN catalyst has the characteristic of oriented growth towards the (001) crystal face direction;
FIG. 2 is a FESEM spectrum of a TBHN catalyst; as can be seen from FIGS. a-c, in TBHN-0, tiO 2 Is present as a clostridial mesogen of about 60.+ -.10 nm in length and about 40.+ -.10 nm in width; as can be seen from d-f, the HNO is added 3 Thereafter, both the size and aspect ratio of the mesogens were reduced to about 40.+ -.10 nm long by 30.+ -.10 nm wide. This means HNO 3 Has certain destructive effect on the growth of mesogen;
FIG. 3 is a FTIR spectrum of TBHN-0 and TBHN-8; as can be seen from the figure, the hydroxyl peak of TBHN-8 is obviously higher than that of TBHN-0, which indicates that HNO is added into the hydrothermal reaction system 3 Can be effectively used in TiO 2 The surface increases the hydroxyl content.
Formaldehyde degradation test
As can be seen from fig. 4a, the TBHN catalyst has a strong degradation effect on formaldehyde under the simulated natural light condition. Within 35min, 80% of formaldehyde can be degraded. This is because of TiO 2 The shuttle mesogen has a high proportion of high-activity crystal face (001) face; and has rich pore canal structure. HNO addition in hydrothermal reaction 3 After that, the activity of the catalyst is further improved. The formaldehyde degradation rate constant of TBHN-8 is 2.2 times that of TBHN-0.
Claims (9)
1. TiO (titanium dioxide) with surface rich in hydroxyl groups 2 A composite photocatalyst formed of a shuttle-like mesogen, the composite photocatalyst being prepared by a process comprising the steps of:
(1) Slowly adding titanium source n-butyl titanate into glacial acetic acid solvent under the action of strong stirring, and continuously stirring;
(2) Adding a trace amount of concentrated nitric acid into the system obtained in the step (1), and continuously stirring to form a transparent suspension; wherein the amount of the concentrated nitric acid is based on the amount of the titanium source, so that Ti: NO 3 The molar ratio of (2) is 1: between 0.001 and 1:1;
(3) Transferring the suspension obtained in the step (2) into a reaction kettle, heating to react at 100-220 ℃, and cooling to room temperature;
(4) Respectively performing alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) And (3) calcining the composite material prepared in the step (4) at a high temperature, wherein the temperature of the high-temperature calcination is controlled to be 300-600 ℃.
2. The composite photocatalyst of claim 1, wherein the volume ratio of n-butyl titanate to glacial acetic acid is 0.1:100-20:100.
3. The composite photocatalyst of claim 1, wherein Ti: NO 3 The molar ratio of (2) is 1:0.01 to 1: between 0.2.
4. The composite photocatalyst according to claim 1, wherein the reaction temperature in step (3) is controlled to 150-200 ℃.
5. The composite photocatalyst of claim 1, wherein the temperature of the high-temperature calcination in step (5) is controlled to be 400-500 ℃.
6. The use of a composite photocatalyst according to any one of claims 1 to 5 for photocatalytic purification of air, wherein the photocatalytic purification of air refers to photodegradation to eliminate formaldehyde from air.
7. Preparation of TiO with surface rich in hydroxyl 2 A method of forming a composite photocatalyst of a shuttle mesogen comprising the steps of:
(1) Slowly adding titanium source n-butyl titanate into glacial acetic acid solvent under the action of strong stirring, and continuously stirring;
(2) Adding a trace amount of concentrated nitric acid into the system obtained in the step (1), and continuously stirring to form a transparent suspension; wherein, the amount of the added concentrated nitric acid should beIn terms of the amount of titanium source, such that Ti: NO 3 The molar ratio of (2) is 1: between 0.001 and 1:1;
(3) Transferring the suspension obtained in the step (2) into a reaction kettle, heating to react at 100-220 ℃, and cooling to room temperature;
(4) Respectively performing alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) And (3) calcining the composite material prepared in the step (4) at a high temperature, wherein the temperature of the high-temperature calcination is controlled to be 300-600 ℃.
8. The method of claim 7, wherein the volume ratio of n-butyl titanate to glacial acetic acid in step (1) is 0.1:100-20:100.
9. The method of claim 7, wherein the reaction temperature in the step (3) is controlled to be 150-200 ℃, and the high-temperature calcination temperature in the step (5) is controlled to be 400-500 ℃.
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