CN110614091A - Fusiform mesogenic TiO2Composite photocatalyst, preparation method and application thereof - Google Patents
Fusiform mesogenic TiO2Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- CN110614091A CN110614091A CN201910940269.0A CN201910940269A CN110614091A CN 110614091 A CN110614091 A CN 110614091A CN 201910940269 A CN201910940269 A CN 201910940269A CN 110614091 A CN110614091 A CN 110614091A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 33
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 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 10
- 238000001782 photodegradation Methods 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 13
- 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 10
- 239000000725 suspension Substances 0.000 claims description 10
- 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
- 238000004887 air purification Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 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
- 239000011651 chromium Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000007613 environmental 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
- 238000009472 formulation Methods 0.000 description 1
- -1 hydroxyl modified titanium dioxide Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 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
- 238000012029 structural testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- B01J35/39—
-
- 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
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a method for preparing a hydroxyl-rich TiO film2A composite photocatalyst formed by spindle mesomorphism 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 the solvothermal method is adopted to prepare TiO with rich hydroxyl on the surface2A spindle mesogen. The invention prepares TiO on the basis of not additionally adding any template and auxiliary agent2The fusiform mesocrystal is added with trace nitric acid, so that the hydroxyl content on the surface of the crystal is effectively improved, and the rate of photodegradation of formaldehyde is improved. The method is simple to operate, can be completed in one step, and is economic and environment-friendly; when the surface rich in hydroxyl is constructed, only a trace amount of nitric acid is added, so that the using amount is small, but the modification effect is obvious. The product prepared is in a moldThe formaldehyde is efficiently degraded under the condition of simulating sunlight, and the activity is high.
Description
Technical Field
The invention relates to a TiO with rich hydroxyl on the surface2A composite photocatalyst formed by spindle-shaped mesocrystals, a preparation method and application thereof. The composite photocatalyst can be used in the field of photocatalytic purification of pollutants in air and photodegradation of organic pollutants, in particular to formaldehyde in the environment.
Technical Field
By using TiO2The photocatalyst has the following advantages of degrading pollutants in the air: TiO 22Stable chemical property, low price and low toxicity; the reaction can be excited to occur only by illumination; the product is nontoxic H2O and CO2. But TiO 22There are two limitations: the forbidden band width is large (3.2ev), and only ultraviolet light in sunlight can be utilized; secondly, the recombination rate of the photo-generated electrons and holes is high, and thus the quantum yield is low.
TiO2Mesoscopic crystals (TiO for short)2Mesogen) is made of TiO2The super structure formed by directionally assembling the nano crystals has a plurality of unique properties, such as high crystallinity, porosity, single crystal-like property and the like. Thus, TiO is used2The appearance of the mesoscopic crystal is a feasible idea for improving the photocatalytic performance of the mesoscopic crystal. For example, the article Organic Small Molecule-Assisted Synthesis of High Active TiO, 2010 volume 12 and 2073 and 2078 pages 2078 of the CrystEngComm journal2In Rod-Like TiO 2-Lite Mesocrystals2Application of mesogen to AIn the degradation of the base orange, the prepared rod-shaped mesogen has higher catalytic performance than that of the commercial P25. Nanoscale journal 2011, paper Synthesis of regenerated Anatase TiO 1910. 19162TiO reported by Mesocrystals with Wulff Shape applied by ordered Attachment2The mesogen has higher crystallinity and specific surface area than P25, thereby having higher photodegradation effect on rhodamine B.
But TiO 22Mesoscopic crystals are often complex to prepare and require reliance on inorganic templates or organic auxiliaries. Chinese patent 201110128919.5 discloses a rod-like rutile type TiO2Preparation method of mesogen, and nano-rod-shaped rutile TiO2The mesocrystal is composed of 3-5nm superfine nanowires, the length of the mesocrystal is 200-300nm, and the diameter of the mesocrystal is 50-80 nm; the preparation method is to mix TiO2Mixing with potassium hydroxide solution, reacting at high temperature for 2-4 days, washing with dilute nitric acid, and stirring for 5-15 days. It is obvious from the above preparation method that a large amount of acidic and alkaline waste liquid is generated in the implementation process of the method, which is not environment-friendly and time-consuming and labor-consuming. Chinese patent 201410276619.5 discloses a method for preparing spherical titanium ore type TiO with controllable size by using n-butyl titanate as titanium source, acetic acid as solvent and benzoic acid as surfactant2Mesogen with an average particle size of 230-270 nm.
In addition, TiO is added2The content of surface hydroxyl groups can also increase its photocatalytic activity. For example, the Journal of Catalysis 2018, volume 367, 126 and 138, the Acetic Acid Functionalized TiO2In the/Kaolinite Composite photocatalyst with Enhanced Photocatalytic performanceme Regulating Interfacial Charge Transfer, the TiO is impregnated with acetic acid2-Kaolin composite catalyst for preparing hydroxyl-rich TiO2A surface. Research results show that surface hydroxyl can be used as Lewis acid sites, which is beneficial to prolonging the service life of photon-generated carriers, thereby improving the photocatalytic activity. Applied Catalysis B, Environmental journal 2017 volume 206, 293 page 299, Photocatalytic reduction behavor of univalent chromium on hydroxyl modified titanium dioxide, mesoporous TiO 22The NaOH solution impregnation method is adopted to prepare a structure with a surface rich in hydroxyl, so that the reduction rate of Cr (VI) is improved. However, these methods are all based on TiO2The hydroxyl content of the surface of the raw material is improved by adopting an immersion method.
Therefore, it is necessary to provide a method for preparing TiO2The one-step solvothermal method of mesomorphism does not need to add any auxiliary agent or template, and is simple to operate, economic and environment-friendly.
Disclosure of Invention
The invention aims to provide a TiO with rich hydroxyl on the surface2A composite photocatalyst formed by spindle mesomorphism and a preparation method thereof. The method is to prepare TiO2The one-step solvothermal method of mesomorphism does not need to add any auxiliary agent or template, and the prepared product has the function of degrading formaldehyde in the air under the irradiation of simulated sunlight 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 rich in hydroxyl group on the surface2The composite photocatalyst formed by the spindle mesogen is prepared by the method comprising 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 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 carrying out alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) and (4) 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 the original reaction system is adopted, and compared with the method adopted in the prior art, two steps are combined into one step substantially, so that the time and the raw material cost are greatly saved, and the generation amount of waste liquid is reduced.
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 present invention, glacial acetic acid plays multiple 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 to 20: 100. here, the volume 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 performed by, for example, dropwise addition.
In step (2) of the present invention, a trace amount of concentrated nitric acid (e.g., 65 to 68 wt% concentrated nitric acid) is added for the purpose of increasing TiO2The content of surface hydroxyl groups. The addition amount of the concentrated nitric acid is determined according to the amount of TBOT, Ti and NO3The molar ratio of (A) to (B) can be controlled in a range of 1: 0.001-1: 1. The content of the concentrated nitric acid is not suitable to be too large, and the appearance of the fusiform mesomorphic crystal can be damaged to a certain extent due to the addition of the concentrated nitric acid. Preferably, Ti: NO3In a molar ratio of 1: 0.01-1: 0.2; more preferably, Ti: NO3In a molar ratio of 1: 0.01-1:0.1.
In the step (3) of the present invention, the reaction temperature may be 100-. The reaction time can be 6-72 hours, preferably 18-24 hours; the cooling method is preferably natural cooling. The reaction kettle can be a reactor such as an autoclave.
In the step (4) of the present invention, the alcohol washing and the water washing are preferably carried out three or more times, and the drying temperature is preferably 70 to 120 ℃. The alcohol used in the alcohol washing is preferably ethanol.
In the step (5) of the present invention, the temperature of the calcination may be 300-. The calcination time may be 3 to 9 hours, preferably 3 to 6 hours. Calcination may be carried out in a muffle furnace under air conditions and the rate of temperature rise may be 2 ℃/min.
In the composite photocatalyst prepared by the invention, the prepared TiO2The appearance is fusiform mesomorphism.
The composite photocatalyst can be used for photocatalytic air purification to eliminate formaldehyde in the air by photodegradation.
On the other hand, in order to achieve the object of the invention, the inventionAlso provides a method for preparing the TiO rich in hydroxyl on the surface2A method of forming a composite photocatalyst from a mesogen in the form of a fusiform form crystal, the method 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 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 carrying out alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) and (4) calcining the composite material prepared in the step (4) at a high temperature.
In the step (1) of the above method, the solvent used is preferably glacial acetic acid, and the titanium source used is preferably n-butyl titanate; the volume ratio of n-butyl titanate to glacial acetic acid is preferably 0.1: 100-20:100.
In the step (3) of the method, the reaction temperature may be controlled to be 220 ℃ C. and the temperature for the high-temperature calcination in the step (5) may be controlled to be 600 ℃ C. and 300 ℃ C.
The invention adopts a nitric acid-assisted one-step solvothermal method to prepare TiO with rich hydroxyl on the surface2The final product of the spindle mesomorphic crystal is used for photocatalytic air purification to eliminate formaldehyde in the air through photodegradation. Advantages of the present invention include, but are not limited to:
A. the operation is simple, the operation is completed in one step, and the method is economic and environment-friendly;
B. in the preparation of TiO2No auxiliary agent or template is added in the mesomorphic process, only a trace amount of nitric acid is added into the original reaction system on the surface rich in hydroxyl, the raw materials are simple and easy to obtain, the using amount 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 will be further described with reference to the following detailed description and the accompanying drawings; it is to be understood that these specific embodiments are merely illustrative of the invention and are not to be construed as limiting the invention. The technical solutions of the present invention can be modified or substituted for those of ordinary skill in the art without departing from the scope of the present invention.
Drawings
Figure 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);
figure 3 is an FTIR spectrum of a TBHN catalyst;
figure 4 shows the photocatalytic performance of TBHN catalyst: (a) the photodegradation formaldehyde curve of the TBHN catalyst; (b) TBHN In (C)0The curve is plotted against t/C).
In the above drawings, TBHN represents TiO prepared by the invention and rich in hydroxyl on the surface2The number after the composite photocatalyst formed by the fusiform mesogen represents the percentage content of nitrate radical and titanium atoms. The specific formulation of each catalyst can be obtained from the examples.
Detailed Description
The invention is further illustrated below with reference to preparation examples and test examples, which are conventional process steps unless otherwise specified. The starting materials are all commercially available from the open.
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 small amount of concentrated nitric acid (65-68 wt%) was added to the system and stirring was continued for a certain period of time to form a clear suspension. And 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 in a muffle furnace under the air condition at high temperature. The catalyst prepared was designated TBHN, after which the numbers indicate the percentage of nitrate and titanium atoms. The following table lists the specific raw material compositions and reaction conditions for examples 1-4.
Structural testing
Figure 1 is an XRD spectrum of a TBHN photocatalyst; as can be seen, the prepared TBHN catalyst is in anatase type, 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, TiO2Exists in spindle-shaped mesomorphism with the length of about 60 +/-10 nm and the width of about 40 +/-10 nm; while the graph can be seen from d-f, after adding HNO3Later, the size and aspect ratio of the mesogen decreases, being about 40 + -10 nm long and 30 + -10 nm wide. This represents HNO3The method has certain destructive effect on the growth of mesomorphism;
FIG. 3 is an FTIR spectrum of TBHN-0 and TBHN-8; as can be seen from the figure, the hydroxyl peak of TBHN-8 is obviously stronger than that of TBHN-0, which indicates that HNO is added into the hydrothermal reaction system3Can be effectively on TiO2The surface increases the content of hydroxyl groups.
Formaldehyde degradation test
From fig. 4a, the TBHN catalyst has a strong degradation effect on formaldehyde under simulated natural light conditions. Within 35min, 80% of formaldehyde can be degraded. This is because TiO2The fusiform mesomorphic crystal has a high proportion of a high-activity crystal face (001); and has rich pore channel structure. Adding HNO in hydrothermal reaction3After 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 (10)
1. TiO with rich hydroxyl on surface2The composite photocatalyst formed by the spindle mesogen is prepared by the method comprising 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 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 carrying out alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) and (4) calcining the composite material prepared in the step (4) at a high temperature.
2. The composite photocatalyst of claim 1, wherein the solvent used in step (1) is glacial acetic acid, and the titanium source used is n-butyl titanate; wherein the volume ratio of the n-butyl titanate to the glacial acetic acid is 0.1: 100-20:100.
3. The composite photocatalyst of claim 1, wherein the amount of concentrated nitric acid added in step (2) is based on the amount of the titanium source, such that Ti to NO3In a molar ratio of 1: 0.001-1: 1.
4. the composite photocatalyst as claimed in claim 1, wherein the reaction temperature in step (3) is controlled to be 100-.
5. The composite photocatalyst as claimed in claim 1, wherein the temperature of the high-temperature calcination in the step (5) is controlled to be 300-600 ℃, preferably 400-500 ℃.
6. The composite photocatalyst of claim 1, wherein the TiO produced is2The appearance is fusiform mesomorphism.
7. The composite photocatalyst of claim 1, wherein the composite photocatalyst is used for photocatalytic air purification to eliminate formaldehyde in air by photodegradation.
8. Preparation of hydroxyl-rich TiO2A method of forming a composite photocatalyst from a mesogen in the form of a fusiform form crystal, the method 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 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 carrying out alcohol washing and water washing on the product obtained in the step (3), and then drying;
(5) and (4) calcining the composite material prepared in the step (4) at a high temperature.
9. The method according to claim 8, wherein the solvent used in step (1) is glacial acetic acid, and the titanium source used is n-butyl titanate; the volume ratio of the n-butyl titanate to the glacial acetic acid is 0.1: 100-20:100.
10. The method as claimed in claim 8, wherein the reaction temperature in step (3) is controlled to be 220 ℃ and the temperature for the high-temperature calcination in step (5) is controlled to be 600 ℃ and 300 ℃.
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Citations (8)
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