CN112495444A - TiO22Preparation method and application of @ HKUST-1 composite photocatalyst - Google Patents
TiO22Preparation method and application of @ HKUST-1 composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000000243 solution Substances 0.000 claims abstract description 55
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 109
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 238000003911 water pollution Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- -1 and finally Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling 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
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/39—
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- B01J35/396—
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- 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
-
- 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
Abstract
The invention relates to a TiO compound2A preparation method and application of a @ HKUST-1 composite photocatalyst. The preparation method comprises the following steps: dissolving PVP in Cu (NO) sufficiently3)2Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion2Aqueous solution and N2H4·H2Observing the color of the O solution from green to yellow, stirring uniformly, centrifuging, washing with ethanol and deionized water for several times, and adding Cu2Synthesis of TiO by using O as sacrificial template2@Cu2O; using mixed solution of trimesic acid, benzyl alcohol and ethanol, and adding into the mixed solutionAdding TiO into2@Cu2O solution, washing the precipitate obtained after reaction and centrifugation with methanol, and synthesizing TiO by in-situ growth method2@Cu2O @ HKUST-1; adding TiO into the mixture2@Cu2Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging, repeatedly washing with methanol to obtain TiO dispersed in methanol2@ HKUST-1. The composite material is applied to selective adsorption and H separation2、N2、O2、CO2、CH4Gas, industrial three-waste treatment, dye degradation, organic pollutant-containing wastewater treatment and the like. The synthesis method has the characteristics of low cost, high yield, strong repeatability, stable product performance and the like.
Description
Technical Field
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 TiO2A 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 mineralizes or directly degrades organic pollutants into small molecules such as H by utilizing the interaction between light and a catalyst2O、CO2And a non-toxic inorganic acid, is an ideal method for degrading environmental pollutants, and has wide application prospect in solving the problem of environmental pollution. TiO in semiconductor photocatalyst2Most typically, it is very oxidizing and capable of degrading and mineralizing organic pollutants in water. However, single component TiO2The problems of low pollutant degrading 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 MOFs have good adsorbability due to the ultra-large specific surface area and high porosity, can better enrich pollutants in water, and have stable chemical properties (O.M. Yaghi, M.O' Keeffe, N.W.Ockwig, H.K.Chae, M.Eddaoudi, J.Kim, Nature 2003,423,705; P.Li, N.A.Vermeulen, C.D.Maliakas, D.A.G.mez Gualdr n, A.J.Howarth, B.L.Mehdi, A.Dohn)alkova, n.d. browning, m.o' Keeffe, o.k. farha, Science 2017,356,624; a. corma, h.garci, f.x.lalabres, i.xamena, chem.rev.2010,110, 4606). HKUST-1 is a typical MOFs with regular pore structure, if HKUST-1 and TiO are used2The nano reactor formed by compounding can well adsorb pollutant molecules in water, and HKUST-1 and TiO are simultaneously used2The composite structure can also effectively reduce the photoproduction electron-hole recombination rate (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 TiO2The 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 TiO2The 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 TiO2The preparation method of the @ HKUST-1 composite photocatalyst successfully prepares TiO by utilizing an in-situ growth technology and a hydrothermal method2The 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 TiO2The preparation method of the @ HKUST-1 composite photocatalyst comprises the following steps:
step 1: dissolving a certain amount of PVP in Cu (NO)3)2Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion2Aqueous solution and N2H4 .H2Observing the color of the O solution from green to yellow, stirring, centrifuging, washing with ethanol and deionized water for several times, and finally, TiO2@Cu2O 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 TiO2@Cu2Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO2@Cu2O@HKUST-1；
And step 3: adding a certain amount of TiO2@Cu2Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging at 5000rpm/5min, repeatedly washing with methanol to obtain TiO dispersed in methanol2@HKUST-1。
In the step 1, the method comprises the following steps of,
the PVP is 1-2g, Cu (NO)3)2The solution is 50-200mL and 0.01 mol/L.
The TiO is2The water solution is 50-100mL, N2H4 .H2The 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 ratio of 1: 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 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 is2@Cu2The O solution is 0.5-10 mL.
In step 3, the TiO2@Cu2The dosage of O @ HKUST-1 is 0.5-1g, the heating temperature is 80-100 ℃, and the heating time is 12-15 hours.
The TiO is obtained by the preparation method2@ HKUST-1 composite photocatalyst.
TiO22The @ 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 synthesizes Yolk-Shell configuration by using in-situ growth technology and hydrothermal methodNano reactor TiO2@ HKUST-1, for TiO2The 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 invention2The @ 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 spectrum is the Ti 2p3/2 spectrum of TiO2@ HKUST-1.
(c) The Cu 2p spectrum of TiO2@ HKUST-1.
(d) The spectrum is O1s of TiO2@ HKUST-1.
(e) The spectrum is C1s of TiO2@ HKUST-1.
FIG. 2(a) is a scanning electron microscope photograph of the HKUST-1 crystal.
(b, c) is TiO2Scanning electron microscopy images of @ HKUST-1.
(d) Is TiO2Transmission electron microscopy images of @ HKUST-1.
FIG. 3 is TiO2Fluorescence spectrum of @ HKUST-1.
FIG. 4 is a graph showing 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 TiO2And metalOrganic framework Materials (MOFs), in particular to TiO synthesized by in-situ growth technology and hydrothermal method2The @ HKUST-1 composite material is used for catalyzing and degrading organic pollutants in water under visible light. With PVP, Cu (NO)3)2And 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 configuration2@HKUST-1。
The invention provides visible light responding TiO2The preparation method of the @ HKUST-1 composite material comprises the following steps:
(1) dissolving a certain amount of PVP in 50-100-200 mL, 0.01mol/L, Cu (NO)3)2Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion2An aqueous solution and 60 to 100 to 300 mu LN2H4 .H2Observing the O solution, changing the color from green to yellow, stirring for 2-10-20 minutes, centrifuging the product at 8000rpm/10min, washing for a plurality of times by using ethanol and deionized water, and finally, TiO2@Cu2Dispersing O in 2.5-5-10 mL of benzyl alcohol, and storing at 0-4 ℃.
(2) Adding 0.05-0.5-1.0 mmol (0.01-0.1-0.21 g) of trimesic acid into a mixed solution of 1.5-10 mL of benzyl alcohol and 0.1-5-10 mL of ethanol, performing ultrasonic dispersion for 30-100 minutes to obtain a uniform solution, and taking 0.5-5-10 mL of TiO2@Cu2Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO2@Cu2O@HKUST-1。
(3) Adding a certain amount of TiO2@Cu2O @ HKUST-1 is dispersed in a methanol solution and heated at 80-100 ℃ for 12-15 hours, the product is centrifuged at 5000rpm/5min, and the methanol is repeatedly washed to obtain a product TiO dispersed in the methanol2@HKUST-1。
TiO in the invention2The 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 method2The @ 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 TiO2Nanoparticles are coated therein, HKUST-1 nanocrystals have uniform particle size, and TiO2Certain 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 configuration2The @ HKUST-1 nano-reactor was successfully synthesized.
Another object of the invention is: TiO composite material2@ 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 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:
TiO2@Cu2preparation of O: 1g of polyvinylpyrrolidone (PVP) was dissolved in 50mL of 0.01mol/L Cu (NO)3)2In the solution, magnetically stirring, ultrasonically dispersing for 30 minutes, and rapidly adding 50mL TiO2Aqueous solution and 60 μ L N2H4 .H2Observing the color of the O solution to change from green to yellow, stirring for 2 min, centrifuging the product at 8000rpm for 10min, washing with ethanol and deionized water (1:1) for several times, and finally TiO2@Cu2O was dispersed in 2.5mL of benzyl alcohol and stored at 4 ℃.
TiO2@Cu2Preparation 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 TiO2@Cu2Adding 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 product2@Cu2O@HKUST-1。
TiO2Manufacture of @ HKUST-1 nano reactorPreparing: 0.5g of TiO2@Cu2Dispersing 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 product2@ HKUST-1 was dispersed in methanol.
Example 2:
TiO2@Cu2preparation of O: 1g PVP was dissolved well in 90mL, 0.01mol/L, Cu (NO)3)2Magnetically stirring the solution, ultrasonically dispersing the solution for 40 minutes, and quickly adding 70mL of TiO2Aqueous solution and 90 μ L N2H4 .H2O solution, observing the color change from green to yellow, stirring for 8 min, centrifuging the product at 8000rpm for 10min, washing with ethanol and deionized water (1:1.5) for several times, and finally TiO2@Cu2O was dispersed in 5mL of benzyl alcohol and stored at 2 ℃.
TiO2@Cu2Preparation of O @ HKUST-1: adding trimesic acid (0.3mmol, 0.063g) into mixed solution of 7.5mL benzyl alcohol and 0.5mL ethanol, performing ultrasonic dispersion for 40 minutes to obtain uniform solution, and taking 4.5mL TiO2@Cu2Adding 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 product2@Cu2O@HKUST-1。
TiO2The preparation of a @ HKUST-1 nano reactor: 0.6g of TiO2@Cu2Dispersing 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 product2@ HKUST-1 was dispersed in methanol.
Example 3:
TiO2@Cu2preparation of O: 1.5g PVP was dissolved well in 120mL, 0.01mol/L, Cu (NO)3)2In the solution, magnetically stirring, ultrasonically dispersing for 50 minutes, and rapidly adding 80mL of TiO2Aqueous solution and 120. mu. L N2H4 .H2O solution, observing the color change from green to yellow, stirring for 10min, centrifuging the product at 8000rpm for 10min, and removing with ethanolWashing several times with ionized water (1:2), and finally TiO2@Cu2O was dispersed in 7.5mL of benzyl alcohol and stored at 1 ℃.
TiO2@Cu2Preparation 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 TiO2@Cu2Adding 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 product2@Cu2O@HKUST-1。
TiO2The preparation of a @ HKUST-1 nano reactor: 0.8g of TiO2@Cu2Dispersing 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 product2@ HKUST-1 was dispersed in methanol.
Example 4:
TiO2@Cu2preparation of O: 2g PVP was dissolved well in 150mL, 0.01mol/L, Cu (NO)3)2In the solution, magnetically stirring, ultrasonically dispersing for 60 minutes, and rapidly adding 80mL of TiO2Aqueous solution and 200. mu. L N2H4 .H2Observing the color of the O solution to change from green to yellow, stirring for 15 minutes, centrifuging the product at 8000rpm for 10min, washing with ethanol and deionized water (1:2) for several times, and finally TiO2@Cu2O was dispersed in 10mL of benzyl alcohol and stored at 1 ℃.
TiO2@Cu2Preparation of O @ HKUST-1: adding trimesic acid (0.6mmol, 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 taking 8mL of TiO2@Cu2Adding 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 product2@Cu2O@HKUST-1。
TiO2The preparation of a @ HKUST-1 nano reactor: 0.8g of TiO2@Cu2Dispersing 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 product2@ HKUST-1 was dispersed in methanol.
Example 5:
TiO2@Cu2preparation of O: 2g PVP was dissolved well in 200mL, 0.01mol/L, Cu (NO)3)2Magnetically stirring the solution, ultrasonically dispersing for 90 min, and rapidly adding 100ml of TiO2Aqueous solution and 300. mu. L N2H4 .H2Observing the color of the O solution to change from green to yellow, stirring for 20 minutes, centrifuging the product at 8000rpm for 10min, washing with ethanol and deionized water (1:2) for several times, and finally TiO2@Cu2O was dispersed in 10mL of benzyl alcohol and stored at 2 ℃.
TiO2@Cu2Preparation of O @ HKUST-1: adding trimesic acid (1.0mmol, 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 TiO2@Cu2Adding 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 product2@Cu2O@HKUST-1。
TiO2The preparation of a @ HKUST-1 nano reactor: 1g of TiO2@Cu2Dispersing 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 product2@ HKUST-1 was dispersed in methanol.
Claims (7)
1. TiO22The 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 TiO2The nano-particles are coated in a Shell layer formed by HKUST-1, and a nano-reactor with a Yolk-Shell configuration is synthesized.
2. A TiO according to claim 12A preparation method of a @ HKUST-1 composite photocatalyst, which is characterized in that: the method comprises the following steps:
step 1: dissolving a certain amount of PVP in Cu (NO)3)2Adding a certain amount of TiO into the solution quickly after ultrasonic dispersion2Aqueous solution and N2H4 .H2Observing the color of the O solution from green to yellow, stirring, centrifuging, washing with ethanol and deionized water for several times, and finally, TiO2@Cu2O 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 TiO2@Cu2Adding O solution, washing the precipitate obtained after reaction and centrifugation for several times with methanol to obtain product TiO2@Cu2O@HKUST-1；
And step 3: adding a certain amount of TiO2@Cu2Dispersing O @ HKUST-1 in methanol solution, heating, centrifuging at 5000rpm/5min, repeatedly washing with methanol to obtain TiO dispersed in methanol2@HKUST-1。
3. A TiO according to claim 22The 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)2The solution is 50-200mL and 0.01 mol/L.
The TiO is2The water solution is 50-100mL, N2H4 .H2The 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 ratio of 1: 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 ℃.
4. A TiO according to claim 22The preparation method of the @ HKUST-1 composite photocatalyst is characterized by comprising the following steps of: 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 is2@Cu2The O solution is 0.5-10 mL.
5. A TiO according to claim 22The preparation method of the @ HKUST-1 composite photocatalyst is characterized by comprising the following steps of: in step 3, the TiO2@Cu2The dosage of O @ HKUST-1 is 0.5-1g, the heating temperature is 80-100 ℃, and the heating time is 12-15 hours.
6. A TiO compound obtained by the production method according to any one of claims 1 to 52@ HKUST-1 composite photocatalyst.
7. A TiO compound according to claim 62The @ HKUST-1 composite photocatalyst is applied to the fields of degradation of volatile organic compounds and water pollution control.
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