CN112495444B - TiO2 2 Preparation method and application of @ HKUST-1 composite photocatalyst - Google Patents

TiO2 2 Preparation method and application of @ HKUST-1 composite photocatalyst Download PDF

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CN112495444B
CN112495444B CN202011503823.8A CN202011503823A CN112495444B CN 112495444 B CN112495444 B CN 112495444B CN 202011503823 A CN202011503823 A CN 202011503823A CN 112495444 B CN112495444 B CN 112495444B
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乔宇
杨帅
吕娜
徐娜
车广波
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Jilin Normal University
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Abstract

The invention relates to a method based on TiO 2 A preparation method and application of a @ HKUST-1 composite photocatalyst. The preparation method is to fully dissolve PVP in Cu (NO) 3 ) 2 Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion 2 Aqueous solution and N 2 H 4 . H 2 Observing the color of the O solution from green to yellow, stirring uniformly, centrifuging, washing with ethanol and deionized water for several times, and adding Cu 2 Synthesis of TiO by using O as sacrificial template 2 @Cu 2 O; using the mixed solution of trimesic acid, benzyl alcohol and ethanol, adding TiO 2 @Cu 2 O solution, washing the precipitate obtained after reaction and centrifugation with methanol, and synthesizing TiO by in-situ growth method 2 @Cu 2 O @ HKUST-1; adding TiO into the mixture 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging, washing with methanol repeatedly to obtain TiO product dispersed in methanol 2 @ HKUST-1. The method has the characteristics of low cost, high yield, strong repeatability, stable product performance and the like.

Description

TiO2 2 Preparation method and application of @ HKUST-1 composite photocatalyst
The invention belongs to the field of catalytic degradation of organic pollutants in water under visible light, and particularly relates to a catalyst based on TiO 2 A preparation method and application of a @ HKUST-1 composite photocatalyst.
Background
Environmental pollution is a major problem facing the human society at present, is directly related to ecological stability and human health, and is an environmental problem to be solved urgently at present. The semiconductor photocatalysis technology is a high-grade catalysis technology which is researched more at present, and mainly utilizes the interaction between light and a catalyst to mineralize or directly degrade organic pollutants into small molecules such as H 2 O、CO 2 And a non-toxic inorganic acid, is an ideal method for degrading environmental pollutants and has wide application range in solving the problem of environmental pollutionThe application prospect of (1). TiO in semiconductor photocatalyst 2 Most typically, it is very oxidizing and capable of degrading and mineralizing organic pollutants in water. However, single component TiO 2 The problems of low pollutant degradation speed, easy aggregation, difficult recycling and the like of the nano-catalyst generally exist. In recent years, the nano-reactor is widely applied to the fields of optics, drug delivery, biological materials and the like as a novel material.
In recent years, the nano-reactor MOFs, a porous material, has been studied and reported in a great deal in the field of photocatalytic degradation of pollutants in water. The ultra-large specific surface area and high porosity of MOFs provide good adsorption, better concentration of contaminants in water, and stable MOFs chemistry (o.m.yaghi, m.o 'Keeffe, n.w.ockwig, h.k.chae, m.eddaodi, j.kim, nature 2003,423,705 p. Li, n.a.vermeulen, c.d.mallakaas, d.a.g. mez Gualdr n, a.j.howarth, b.l. Mehdi, a.dohnakova, n.d.browning, m.o' Keeffe, o.k.farha, science 2017, 356,624 a.corma, h.garci, f.x.labbr, chem, rena.110, 2010, 4606). HKUST-1 is a typical MOFs with regular pore structure, if HKUST-1 and TiO are used 2 The nano reactor formed by compounding can well adsorb pollutant molecules in water, and HKUST-1 and TiO are simultaneously used 2 The composite structure of (1) can also effectively reduce the rate of photo-generated electron-hole recombination (Q.L.Zhu, Q.xu, chem.Soc.Rev.2014,43,5468, K.S.Lin, A.K.Adhikari, C.N.Ku, C.L.Chiang, H.Kuo, int.J.Hydrogen.Energ.2012, 37, 13865). Currently, HKUST-1 nanocrystals are utilized with TiO 2 The nano-reactor with the Yolk-Shell configuration assembled by the nano-catalyst has not been reported.
Disclosure of Invention
Aiming at the problem of the existing photocatalytic degradation material source, the invention aims to provide a material based on TiO 2 The preparation method and application of the @ HKUST-1 composite photocatalyst ensure that the composite photocatalyst has better catalytic property while maintaining the adsorption property of the composite photocatalyst. The preparation method of the composite photocatalyst is simple, the raw materials are low in price, and the synthesized photocatalyst has good visible light response capability.
The technical scheme of the invention is as follows:
based on TiO 2 The preparation method of the @ HKUST-1 composite photocatalyst successfully prepares TiO by utilizing an in-situ growth technology and a hydrothermal method 2 The nano-particles are coated in a Shell layer formed by HKUST-1, and a nano-reactor with a Yolk-Shell configuration is synthesized.
Based on TiO 2 The preparation method of the @ HKUST-1 composite photocatalyst comprises the following steps:
step 1: dissolving a certain amount of PVP in Cu (NO) 3 ) 2 Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion 2 Aqueous solution and N 2 H 4 . H 2 Observing the color of the O solution from green to yellow, stirring, centrifuging, washing with ethanol and deionized water for several times, and finally, obtaining TiO 2 @Cu 2 O is dispersed in benzyl alcohol, and the obtained product is stored at low temperature;
step 2: adding trimesic acid into a mixed solution of benzyl alcohol and ethanol, performing ultrasonic dispersion to obtain a uniform solution, and taking a certain amount of TiO 2 @Cu 2 Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO 2 @Cu 2 O@HKUST-1；
And 3, step 3: adding a certain amount of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging at 5000rpm/5min, repeatedly washing with methanol to obtain TiO dispersed in methanol 2 @HKUST-1。
In the step 1, the method comprises the following steps of,
the PVP is 1-2g, cu (NO) 3 ) 2 The solution is 50-200mL and 0.01mol/L.
The TiO is 2 The aqueous solution is 50-100mL, N 2 H 4 . H 2 The O solution is 60-300 mu L.
The ultrasonic dispersion time is 30-90 minutes, and the stirring time is 2-20 minutes.
The ethanol and deionized water are washed for a plurality of times according to the proportion of 1-3, the amount of the ethanol and the deionized water dispersed in the benzyl alcohol is 2.5-10mL, and the low-temperature storage temperature is 0-4 ℃.
In the step (2), the first step is that,
0.01-0.21g of trimesic acid, 1.5-15mL of benzyl alcohol and 0.1-10mL of ethanol;
the ultrasonic dispersion time is 30-90 minutes, tiO 2 @Cu 2 The O solution is 0.5-10mL.
In step 3, the TiO 2 @Cu 2 The dosage of O @ HKUST-1 is 0.5-1g, the heating temperature is 80-100 deg.C, and the heating time is 12-15 hr.
The TiO prepared by the preparation method 2 A @ HKUST-1 composite photocatalyst.
TiO2 2 The @ HKUST-1 composite photocatalyst is applied to the fields of degradation of volatile organic compounds and water pollution control.
The invention has the beneficial effects that:
1. the invention utilizes an in-situ growth technology and a hydrothermal method to synthesize the TiO nanoreactor with a Yolk-Shell configuration 2 @ HKUST-1, for TiO 2 The photocatalyst is modified, so that an effective separation platform is provided for photoproduction electrons and holes, the recombination of electron holes is effectively inhibited, and the visible light catalytic performance of the semiconductor is further improved;
2. the material prepared by the invention is essentially different from the existing material, and the nano reactor prepared by the invention has the advantages of larger specific surface area, abundant and regular pore structure, high-dispersion active sites, rapid degradation of organic pollutants and the like;
3. TiO prepared by the invention 2 The @ HKUST-1 has good catalytic activity on pollutants, is convenient to separate from a solution, and has wide application prospect in the field of treating refractory organic matters in wastewater;
4. the method has the advantages of simple process, good repeatability and higher yield, and meets the requirement of green chemistry. The synthesis method has the advantages of good repeatability, high yield and stable product performance.
Drawings
FIG. 1 (a) is an XPS survey of TiO2@ HKUST-1.
(b) The profile is the Ti 2p3/2 of TiO2@ HKUST-1.
(c) Cu 2p spectra for TiO2@ HKUST-1.
(d) The O1s spectrum is TiO2@ HKUST-1.
(e) The spectrum is the C1s of TiO2@ HKUST-1.
FIG. 2 (a) is a scanning electron microscope photograph of HKUST-1 crystal.
(b, c) is TiO 2 Scanning electron microscopy images of @ HKUST-1.
(d) Is TiO 2 Transmission electron microscopy images of @ HKUST-1.
FIG. 3 is TiO 2 Fluorescence spectrum of @ HKUST-1.
FIG. 4 is a diagram of the effect of photocatalytic degradation of rhodamine B under visible light conditions.
FIG. 5 is a graph showing the effect of the present application on photocatalytic degradation of methylene blue under visible light conditions.
Detailed Description
The invention relates to a semiconductor material TiO 2 With Metal Organic Frameworks (MOFs), in particular to the synthesis of TiO by in-situ growth technology and hydrothermal method 2 The @ HKUST-1 composite material is used for catalyzing and degrading organic pollutants in water under visible light. With PVP, cu (NO) 3 ) 2 And trimesic acid is taken as a raw material, and the in-situ growth technology and the hydrothermal method are utilized to synthesize the composite photocatalyst TiO with the Yolk-Shell configuration 2 @HKUST-1。
The invention provides visible light responding TiO 2 The preparation method of the @ HKUST-1 composite material comprises the following steps:
(1) Dissolving PVP in 50-100-200mL, 0.01mol/L, cu (NO) 3 ) 2 Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion 2 Aqueous solution and 60 to 100 to 300 mu LN 2 H 4 . H 2 O solution, observing the color to change from green to yellow, stirring for 2-10-20 min, centrifuging the product at 8000rpm/10min, washing with ethanol and deionized water for several times, and finally TiO 2 @Cu 2 O is dispersed in 2.5-5-10 mL of benzyl alcohol and stored at 0-4 ℃.
(2) Mixing 0.05-0.5-1.0mmol (0.01-0.1-0.21 g) of trimesic acidAdding into mixed solution of 1.5-10-15 mL of benzyl alcohol and 0.1-5-10 mL of ethanol, performing ultrasonic dispersion for 30-100 minutes to obtain uniform solution, and taking 0.5-5-10 mL of TiO 2 @Cu 2 Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO 2 @Cu 2 O@HKUST-1。
(3) Adding a certain amount of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 80-100 deg.C for 12-15 hr, centrifuging at 5000rpm/5min, repeatedly washing with methanol to obtain TiO dispersed in methanol 2 @HKUST-1。
TiO in the invention 2 The composition of the @ HKUST-1 composite material is determined by X-ray photoelectron spectroscopy (XPS), and characteristic peaks of Ti, cu, O and C appear in the XPS spectrogram; the map shows that the TiO prepared by the synthesis method 2 The @ HKUST-1 composite contains all of the elements it has.
Through a Transmission Electron Microscope (TEM), we can clearly see that the shell layer formed by HKUST-1 has successfully formed TiO 2 Nanoparticles are coated therein, HKUST-1 nanocrystals have uniform particle size, and TiO 2 Certain gaps exist between the Shell structures formed by the nano particles and the HKUST-1 nano crystals, which proves that TiO with the Yolk-Shell configuration 2 The @ HKUST-1 nano-reactor was successfully synthesized.
Another object of the invention is: mixing the composite material TiO 2 @ HKUST-1 is used as a photocatalytic material for catalyzing and degrading organic pollutants in water under visible light.
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1:
TiO 2 @Cu 2 preparation of O: 1g of polyvinylpyrrolidone (PVP) was dissolved well in 50mL of a solution at 0.01mol/L of Cu (NO) 3 ) 2 In solution, magnetically stirringStirring, ultrasonically dispersing for 30 minutes, and rapidly adding 50mL of TiO 2 Aqueous solution and 60. Mu.L of N 2 H 4 . H 2 O solution, observed to change color from green to yellow, stirred for 2 minutes, product centrifuged at 8000rpm,10min, washed several times with ethanol, deionized water (1 2 @Cu 2 O was dispersed in 2.5mL of benzyl alcohol and stored at 4 ℃.
TiO 2 @Cu 2 Preparation of O @ HKUST-1: adding trimesic acid (0.05mmol, 0.01g) into mixed solution of 1.5mL of benzyl alcohol and 0.1mL of ethanol, performing ultrasonic dispersion for 30 minutes to obtain uniform solution, and collecting 0.5mL of TiO 2 @Cu 2 Adding O solution, shaking by hand to thoroughly mix, reacting for about 2 hr, reacting for about 1 hr at room temperature, centrifuging, washing precipitate with methanol for several times to obtain TiO product 2 @Cu 2 O@HKUST-1。
TiO 2 The preparation of a @ HKUST-1 nano reactor: 0.5g of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 80 deg.C for 12 hr, centrifuging at 5000rpm for 5min, repeatedly washing with methanol to obtain TiO product 2 @ HKUST-1 was dispersed in methanol.
Example 2:
TiO 2 @Cu 2 preparation of O: 1g PVP was dissolved well in 90mL,0.01mol/L, cu (NO) 3 ) 2 Magnetically stirring the solution, ultrasonically dispersing the solution for 40 minutes, and quickly adding 70mL of TiO 2 Aqueous solution and 90. Mu.L of N 2 H 4 . H 2 O solution, observed to change color from green to yellow, stirred for 8 minutes, the product centrifuged at 8000rpm,10min, washed several times with ethanol, deionized water (1.5), and finally TiO 2 @Cu 2 O was dispersed in 5mL of benzyl alcohol and stored at 2 ℃.
TiO 2 @Cu 2 Preparation of O @ HKUST-1: adding trimesic acid (0.3mmol, 0.063g) into mixed solution of 7.5mL of benzyl alcohol and 0.5mL of ethanol, performing ultrasonic dispersion for 40 minutes to obtain uniform solution, and taking 4.5mL of TiO 2 @Cu 2 Adding O solution, shaking by hand to mix thoroughly, reacting for about 2 hoursContinuously reacting for about 1 hour at room temperature, centrifuging, washing precipitate with methanol for several times to obtain product TiO 2 @Cu 2 O@HKUST-1。
TiO 2 The preparation of a @ HKUST-1 nano reactor: 0.6g of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 80 deg.C for 12 hr, centrifuging at 5000rpm for 5min, repeatedly washing with methanol to obtain TiO product 2 @ HKUST-1 was dispersed in methanol.
Example 3:
TiO 2 @Cu 2 preparation of O: 1.5g PVP was dissolved well in 120mL,0.01mol/L, cu (NO) 3 ) 2 In the solution, the mixture is stirred by magnetic force, dispersed by ultrasonic for 50 minutes and added with 80mL TiO rapidly 2 Aqueous solution and 120. Mu.L of N 2 H 4 . H 2 O solution, observed to change color from green to yellow, stirred for 10min, the product centrifuged at 8000rpm,10min, washed several times with ethanol, deionized water (1 2 @Cu 2 O was dispersed in 7.5mL of benzyl alcohol and stored at 1 ℃.
TiO 2 @Cu 2 Preparation of O @ HKUST-1: adding trimesic acid (0.5mmol, 0.105g) into a mixed solution of 9mL of benzyl alcohol and 4.5mL of ethanol, performing ultrasonic dispersion for 60 minutes to obtain a uniform solution, and taking 7mL of TiO 2 @Cu 2 Adding the O solution into the mixture, shaking by hand to mix thoroughly, reacting for about 2 hours, continuing to react for about 1 hour at room temperature, centrifuging, washing the precipitate with methanol for several times to obtain the product TiO 2 @Cu 2 O@HKUST-1。
TiO 2 The preparation of a @ HKUST-1 nano reactor: 0.8g of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 85 deg.C for 13 hr, centrifuging at 5000rpm for 5min, repeatedly washing with methanol to obtain TiO product 2 @ HKUST-1 was dispersed in methanol.
Example 4:
TiO 2 @Cu 2 preparation of O: 2g of PVP was dissolved thoroughly in 150mL,0.01mol/L, cu (NO) 3 ) 2 Magnetically stirring in solution, ultrasonic dispersing for 60 min80mL TiO was added quickly 2 Aqueous solution and 200. Mu.L of N 2 H 4 . H 2 O solution, observed to change color from green to yellow, stirred for 15 minutes, the product centrifuged at 8000rpm,10min, washed several times with ethanol, deionized water (1 2 @Cu 2 O was dispersed in 10mL of benzyl alcohol and stored at 1 ℃.
TiO 2 @Cu 2 Preparation of O @ HKUST-1: adding trimesic acid (0.6 mmol, 0.126g) into mixed solution of 12mL of benzyl alcohol and 7.5mL of ethanol, performing ultrasonic dispersion for 80 minutes to obtain uniform solution, and collecting 8mL of TiO 2 @Cu 2 Adding O solution, shaking by hand to thoroughly mix, reacting for about 2 hr, reacting for about 1 hr at room temperature, centrifuging, washing precipitate with methanol for several times to obtain TiO product 2 @Cu 2 O@HKUST-1。
TiO 2 The preparation of a @ HKUST-1 nano reactor: 0.8g of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 90 deg.C for 14 hr, centrifuging at 5000rpm for 5min, repeatedly washing with methanol to obtain TiO product 2 @ HKUST-1 was dispersed in methanol.
Example 5:
TiO 2 @Cu 2 preparation of O: 2g PVP was dissolved well in 200mL,0.01mol/L, cu (NO) 3 ) 2 Magnetically stirring the solution, ultrasonically dispersing the solution for 90 minutes, and quickly adding 100ml of TiO 2 Aqueous solution and 300. Mu.L of N 2 H 4 . H 2 O solution, observed to change color from green to yellow, stirred for 20 min, product centrifuged at 8000rpm,10min, washed several times with ethanol, deionized water (1 2 @Cu 2 O was dispersed in 10mL of benzyl alcohol and stored at 2 ℃.
TiO 2 @Cu 2 Preparation of O @ HKUST-1: adding trimesic acid (1.0 mmol, 0.210g) into mixed solution of 15mL of benzyl alcohol and 10mL of ethanol, performing ultrasonic dispersion for 100 minutes to obtain uniform solution, and taking 10mL of TiO 2 @Cu 2 Adding O solution, shaking by hand to mix thoroughly, reacting for about 2 hr, and continuing to react at room temperatureAfter 1 hour, centrifugally separating, washing the precipitate for several times by using methanol to obtain a product TiO 2 @Cu 2 O@HKUST-1。
TiO 2 Preparation of a @ HKUST-1 nano reactor: 1g of TiO 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating at 100 deg.C for 15 hr, centrifuging at 5000rpm for 5min, repeatedly washing with methanol to obtain TiO product 2 @ HKUST-1 was dispersed in methanol.

Claims (5)

1. Based on TiO 2 The preparation method of the @ HKUST-1 composite photocatalyst is characterized by comprising the following steps of: successfully uses an in-situ growth technology and a hydrothermal method to prepare TiO 2 The nano-particles are coated in a Shell layer formed by HKUST-1 to synthesize a nano-reactor with a Yolk-Shell configuration;
the method comprises the following steps:
step 1: dissolving a certain amount of PVP in Cu (NO) 3 ) 2 Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion 2 Aqueous solution and N 2 H 4 . H 2 Observing the color of the O solution from green to yellow, stirring, centrifuging, washing with ethanol and deionized water for several times, and finally, obtaining TiO 2 @Cu 2 O is dispersed in benzyl alcohol, and the obtained product is stored at low temperature;
and 2, step: adding trimesic acid into a mixed solution of benzyl alcohol and ethanol, performing ultrasonic dispersion to obtain a uniform solution, and taking a certain amount of TiO 2 @Cu 2 Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO 2 @Cu 2 O@HKUST-1；
And step 3: a certain amount of TiO is added 2 @Cu 2 Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging at 5000rpm/5min, repeatedly washing with methanol to obtain TiO dispersed in methanol 2 @HKUST-1；
In step 3, the TiO is 2 @Cu 2 The dosage of O @ HKUST-1 is 0.5-1g, the heating temperature is 80-100 ℃, and the heating time is 12-15 hours.
2. A TiO-based composition according to claim 1 2 The preparation method of the @ HKUST-1 composite photocatalyst is characterized by comprising the following steps of: in the step 1, the method comprises the following steps of,
the PVP is 1-2g, cu (NO) 3 ) 2 The solution is 50-200mL and 0.01mol/L;
the TiO is 2 The aqueous solution is 50-100mL, N 2 H 4 . H 2 The O solution is 60-300 mu L;
the ultrasonic dispersion time is 30-90 minutes, and the stirring time is 2-20 minutes;
the ethanol and deionized water are washed for a plurality of times according to the proportion of 1-3, the amount of the ethanol and the deionized water dispersed in the benzyl alcohol is 2.5-10mL, and the low-temperature storage temperature is 0-4 ℃.
3. A TiO-based composition according to claim 1 2 The preparation method of the @ HKUST-1 composite photocatalyst is characterized by comprising the following steps: in the step 2, the step of the method is carried out,
0.01-0.21g of trimesic acid, 1.5-15mL of benzyl alcohol and 0.1-10mL of ethanol;
the ultrasonic dispersion time is 30-90 minutes, and TiO is 2 @Cu 2 The O solution is 0.5-10mL.
4. A TiO obtained by the production method according to any one of claims 1 to 3 2 @ HKUST-1 composite photocatalyst.
5. A TiO compound according to claim 4 2 The @ HKUST-1 composite photocatalyst is applied to the fields of degradation of volatile organic compounds and water pollution control.
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