CN112958061B - Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof - Google Patents
Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof Download PDFInfo
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- CN112958061B CN112958061B CN202110154774.XA CN202110154774A CN112958061B CN 112958061 B CN112958061 B CN 112958061B CN 202110154774 A CN202110154774 A CN 202110154774A CN 112958061 B CN112958061 B CN 112958061B
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 230000007246 mechanism Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000011941 photocatalyst Substances 0.000 claims abstract description 68
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 67
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
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- 239000000243 solution Substances 0.000 claims description 31
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- 239000001257 hydrogen Substances 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 15
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- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
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- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 51
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000000864 Auger spectrum Methods 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
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- 230000032900 absorption of visible light Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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—
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- B01J35/615—
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- B01J35/647—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2The photocatalyst and the preparation method thereof are characterized in that the Z-shaped mesoporous Cu excited by the oxygen vacancy2O/TiO2The heterostructure composite photocatalyst is TiO with a mesoporous structure2Medium composite Cu2O to form a heterojunction structure composite photocatalyst; the preparation method uses TiCl4,(NH4)2SO4The method comprises the steps of using urea as a raw material, using ethylene glycol as a pore-forming agent, adopting a solvothermal method, and roasting to obtain TiO with a mesoporous structure2Then adding Cu2TiO loaded with O to mesoporous structure2To obtain Z-type mesoporous Cu with oxygen vacancy promotion2O/TiO2A heterostructure composite photocatalyst; the invention has the advantages that: the precursor is cheap inorganic titanium chloride, the preparation process is simple, and the cost is low; the method can prepare Z-type mesoporous Cu with promoted oxygen vacancy2O/TiO2The heterostructure composite photocatalyst has high photocatalytic efficiency, and has good photocatalytic activity for hydrogen production by water photolysis, hydrogen production by seawater photolysis and photocatalytic degradation of organic pollutants in water.
Description
Technical Field
The invention belongs to the field of new energy environment, relates to a photocatalyst used in the fields of hydrogen new energy and environment purification, and particularly relates to an oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2A photocatalyst and a preparation method thereof.
Background
With the rapid development of the world economy and human civilization, the problems of energy shortage and environmental deterioration become more serious. Without doubt, hydrogen is one of the most promising clean energy sources, and photocatalytic water splitting for hydrogen production is receiving wide attention. The seawater accounts for 96.5 percent of the total water storage of the earth, and has the advantages of wide distribution, inexhaustibility and inexhaustibility. Due to interference of complex ionic components and impurities in seawater, and severe photo-corrosion, the activity and stability of the photocatalyst are reduced. Therefore, the development of the efficient and stable seawater cracking hydrogen production photocatalyst becomes the key for the development and utilization of new hydrogen energy. In addition, the photocatalyst can generate free hydroxyl and active oxygen with strong oxidation capability on the surface under the irradiation of light, can also oxidize and decompose various organic compounds and partial inorganic substances, can destroy cell membranes of bacteria and proteins of viruses so as to kill the bacteria, decomposes organic pollutants into pollution-free water and carbon dioxide, oxidizes and decomposes harmful gases in the air, and is widely applied to the field of environmental purification.
TiO2Has a wide application prospect in the field of photocatalysis and is concerned with. However, tiO2The photocatalyst still has the problems of low visible light absorptivity and fast recombination of photo-generated electron-hole pairs. To solve these problems, tiO is added2The formation of heterojunctions coupled with narrow bandgap semiconductors has proven to be a promising strategy to achieve enhanced photocatalytic performance by providing visible light absorption. Of the widely studied narrow bandgap semiconductor materials, cu2O has a band gap of 2.2ev and is considered to be one of the most promising materials due to its abundant reserves, environmental compatibility and high visible light absorption. However, since Cu2O is easily corroded by light and the activity and stability are reduced. Therefore, cu with high activity, high stability and enhanced visible light response is constructed2O/TiO2A heterostructure photocatalyst is a technical problem in the field of development and utilization of new hydrogen energy and environmental purification.
Conventional Cu2O/TiO2Hetero-structure of either Cu2O is easily corroded by light, the activity and the stability are obviously reduced, the specific surface is low, the number of heterojunction active sites is small, or an all-solid-state direct Z mechanism is difficult to construct, so that the photoproduction electron/hole separation efficiency is low.
Disclosure of Invention
The invention aims at the Cu prepared in the prior art2O/TiO2Heterojunction photocatalyst, low specific surface area, heterojunction active siteFew defects of low separation efficiency of photoproduction electrons/holes, low efficiency of preparing hydrogen by seawater and the like, provides a mesoporous TiO2Stabilized Cu2+An ion adsorption reduction strategy is adopted to construct all-solid-state direct Z-mechanism mesoporous Cu2O/TiO2A preparation method of a heterostructure photocatalyst. Firstly, preparing TiO with mesoporous structure by taking inorganic titanium source as raw material2Micro-spheres in the presence of Cu2+Ion adsorption reduction of Cu2Mesoporous TiO with O nano-species supported on high specific surface2The surface and the inside of the pore channel of the microsphere are simultaneously in Cu2O/TiO2Oxygen defects are introduced to the surface, and oxygen vacancy promotion full-solid direct Z mechanism mesoporous Cu is constructed2O/TiO2A photocatalyst. The method has simple process, and the photocatalytic activity of the photocatalyst is greatly improved. Therefore, the photocatalytic performance of the photocatalyst in seawater is improved, and an effective solution is provided for the design and preparation of efficient and stable seawater hydrogen production and environment purification photocatalysts. The invention is realized by adopting the following technical scheme:
oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2The photocatalyst and the preparation method thereof are characterized in that the Cu2O/TiO2The photocatalyst has a mesoporous structure, cu2O-loaded to mesoporous TiO2The surface and the inside of the pore canal, the mesoporous Cu2O/TiO2The photocatalyst has an oxygen vacancy promoted all-solid-state direct Z mechanism; the preparation of the photocatalyst is carried out by mesoporous TiO2Stabilized Cu2+The method is realized by adopting an ion adsorption reduction strategy, titanium tetrachloride, ammonium sulfate and urea are used as raw materials, ethylene glycol is used as a pore-forming agent, a solvothermal method is adopted, and TiO with a mesoporous structure is obtained by roasting2Then adding Cu2O-loaded mesoporous TiO2To obtain the direct Z mechanism mesoporous Cu promoted by oxygen vacancy2O/TiO2The heterostructure composite photocatalyst specifically comprises the following steps:
(1) Weighing 0.1-10g of titanium tetrachloride, 0.1-10g of ammonium sulfate and 0.1-10g of urea, dissolving in 1-40ml of deionized water cooled in an ice bath, and stirring for 0.5-6h;
(2) Dropwise adding 1-30ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:4-4:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 80-200 ℃ for 1-24h, taking out the high-pressure kettle, cooling to room temperature, performing centrifugal separation, washing with deionized water and ethanol for 3 times respectively, and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.01-1.0 g of copper acetate, dissolving in 15ml of water, and adding 0.1-1.0g of the mesoporous TiO obtained in the step (3)2Dispersing microspheres by ultrasonic for 1-20min, washing with water, centrifuging, dispersing into 1-10mM sodium hydroxide solution by ultrasonic, repeatedly soaking in copper acetate and sodium hydroxide solution for 2-3 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.1-3mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 40-200 ℃ for 1-24h, taking the autoclave out, cooling the autoclave to room temperature, performing centrifugal separation, washing the sample for 3 times by using deionized water and ethanol respectively, and performing vacuum drying to obtain the mesoporous Cu2O/TiO2A photocatalyst.
The invention has the advantages that: the precursor is cheap inorganic titanium chloride, the preparation process is simple, and the cost is low; the all-solid-state direct Z mechanism photocatalyst is constructed through surface oxygen defects, and Cu is reserved2O/TiO2Holes and electrons with strong oxidation reduction capability in the heterojunction photocatalyst enable invalid carriers to be compounded, and Cu is restrained to a great extent2Photo-corrosion of O in water and seawater. Surface oxygen vacancies favor water molecules, hydroxyl groups and H+Adsorption of (C), cu2O/TiO2The porous structure of the photocatalyst is beneficial to multiple reflection and scattering of incident light in a channel, and light absorption is improved. The mesoporous structure has an enhanced capillary effect and promotes the permeation and diffusion of the solution in the nano-pores. At the same time, fine Cu2TiO with O nano particles tightly decorated in porous structure2The surface and the inside of the pore canal have stronger mass transfer capacity and more active centers, which are beneficial to H+And H2Rapid migration of the product. For the hydrogen production and photolysis by photolysis water in the field of novel hydrogen energyThe photocatalytic degradation of organic pollutants in water, bacteriostasis, air purification and the like in the fields of seawater hydrogen production and environmental purification have good photocatalytic activity and stability.
Drawings
FIG. 1 shows the mesoporous Cu prepared in the first embodiment2O/TiO2XRD spectrum of photocatalyst agent.
FIG. 2 shows the mesoporous Cu prepared in the first embodiment2O/TiO2XPS spectra (a), O1s spectra (b) and Cu LMM auger spectra (c) of the photocatalyst.
FIG. 3 shows the mesoporous Cu prepared in the first embodiment2O/TiO2Nitrogen adsorption and desorption isotherms and pore size distribution maps of the photocatalyst.
FIG. 4 shows the mesoporous Cu prepared in the first embodiment2O/TiO2SEM photographs of the photocatalyst at different magnifications.
FIG. 5 shows the mesoporous Cu prepared in the first embodiment2O/TiO2TEM photographs of photocatalyst single microspheres with different multiples.
FIG. 6 shows mesoporous Cu prepared in example one2O/TiO2HRTEM photograph of photocatalyst.
FIG. 7 shows mesoporous Cu prepared by the methods of the first, second and third embodiments2O/TiO2Photocatalyst, tiO prepared by the method of comparative example2Cu prepared by the method of comparative example II2The relationship graph of the hydrogen quantity and the time of the water produced by photocatalytic decomposition of the O catalyst.
FIG. 8 shows mesoporous Cu prepared by the methods of the first, second and third embodiments2O/TiO2Photocatalyst, tiO prepared by the method of comparative example2Cu prepared by the method described in comparative example II2The hydrogen production quantity of the seawater subjected to photocatalytic decomposition by the O catalyst is plotted against time.
Detailed Description
The invention is illustrated in more detail below by way of examples:
the first embodiment is as follows:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 20ml of deionized water cooled by an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.3g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 0.3g of mesoporous TiO obtained in the step (3)2Ultrasonically dispersing microspheres, washing with water, centrifuging, ultrasonically dispersing into 2mM sodium hydroxide solution, repeatedly soaking into copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 96 ℃ for 10 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Example two:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 20ml of deionized water cooled in an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.15g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 0.3g of mesoporous TiO obtained in the step (3)2Ultrasonically dispersing microspheres, washing with water, centrifuging, ultrasonically dispersing into 2mM sodium hydroxide solution, repeatedly soaking into copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 96 ℃ for 10 hours, and then using deionized waterWashing with water and ethanol for 3 times respectively, and vacuum drying to obtain mesoporous Cu2O/TiO2A photocatalyst.
Example three:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 20ml of deionized water cooled by an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.6g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 0.3g of the mesoporous TiO obtained in the step (3)2Carrying out ultrasonic dispersion on microspheres, washing with water, centrifuging, dispersing into a 2mM sodium hydroxide solution by ultrasonic dispersion again, repeatedly soaking into a copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 96 ℃ for 10 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Example four:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 10ml of deionized water cooled in an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 30ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:3;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.3g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 3g of the mesoporous TiO obtained in the step (3)2Dispersing microspheres by ultrasonic, washing with water, centrifuging, and dispersing to 5mM sodium hydroxide by ultrasonicRepeatedly soaking in copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 60 ℃ for 10 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Example five:
(1) Weighing 6.84g of titanium tetrachloride, 3.16g of ammonium sulfate and 2.4g of urea, dissolving in 20ml of deionized water cooled by an ice bath, and uniformly stirring;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.6g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 0.3g of mesoporous TiO obtained in the step (3)2Carrying out ultrasonic dispersion on microspheres, washing with water, centrifuging, dispersing into a 2mM sodium hydroxide solution by ultrasonic dispersion again, repeatedly soaking into a copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 2mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 96 ℃ for 10 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Example six:
(1) 1.71g of titanium tetrachloride, 0.79g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 30ml of deionized water cooled in an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 10ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 3:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 96 ℃ for 12 hours, taking out the high-pressure reaction kettle, and coolingCentrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.15g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 0.1g of mesoporous TiO obtained in the step (3)2Ultrasonically dispersing microspheres, washing with water, centrifuging, ultrasonically dispersing into 1mM sodium hydroxide solution, repeatedly soaking into copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.2mM glucose solution, transferring the sample into an autoclave, heating the sample at a constant temperature of 150 ℃ for 2h, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Example seven:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 20ml of deionized water cooled by an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.3g of copper acetate, dissolving the copper acetate in 15ml of water, and adding 3.0g of the mesoporous TiO obtained in the step (3)2Ultrasonically dispersing microspheres, washing with water, centrifuging, ultrasonically dispersing into 2mM sodium hydroxide solution, repeatedly soaking into copper acetate and sodium hydroxide solution for 2 times, washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 80 ℃ for 6 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the washed sample in vacuum to obtain the mesoporous Cu2O/TiO2A photocatalyst. The first comparative example is as follows:
(1) 3.42g of titanium tetrachloride, 1.58g of ammonium sulfate and 1.2g of urea are weighed and dissolved in 20ml of deionized water cooled by an ice bath, and the mixture is stirred uniformly;
(2) Dropwise adding 20ml of ethylene glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the ethylene glycol is 1:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 95 ℃ for 12 hours, taking out the high-pressure reaction kettle, cooling, centrifuging, washing and drying to obtain mesoporous TiO2Microspheres;
comparative example two:
(1) Weighing 0.3g of copper acetate, dissolving in 15ml of water, adding into 2mM sodium hydroxide solution, stirring uniformly, washing with water, and centrifuging; (5) Ultrasonically dispersing the sample obtained in the step (1) into a 0.5mM glucose solution, transferring the sample into an autoclave, heating the sample at a constant temperature of 96 ℃ for 10 hours, washing the sample with deionized water and ethanol for 3 times respectively, and drying the sample in vacuum to obtain Cu2And (3) O photocatalyst.
FIG. 1 shows the mesoporous Cu prepared in the first embodiment2O/TiO2XRD spectrum of photocatalyst agent. As can be seen from the figure, the main diffraction peaks can be identified as TiO with anatase structure according to the standard card (JCPDS No. 21-1271)2The index of the crystal plane corresponding to each diffraction peak is indicated in the figure. But no significant Cu was observed2Diffraction peaks of O, probably due to Cu in the product2Low O content, high dispersity or low crystallinity.
FIG. 2 shows the mesoporous Cu prepared in the first embodiment2O/TiO2XPS spectra (a), O1s spectra (b) and Cu LMM Auger spectra (c) of the photocatalyst. As can be seen from the graph a, the sample contains three elements of Ti, O and Cu, and the peak area of Cu is very small, which indicates that the content of Cu is very low. From the O1s spectra in fig. b it can be seen that there are two states of O in the sample, the characteristic peak appearing at 529.9eV corresponds to the lattice oxygen of the Ti-O and Cu-O species, the fitted weak peak at 531.1eV matches well with the oxygen vacancies, indicating the presence of oxygen vacancies at the sample surface, which facilitates the aggregation and transfer of the catalyst photo-generated charge. The combination energy of the Cu LMM auger spectrum 570.2eV in the graph c can confirm that Cu in the composite sample is Cu (I), which indicates TiO2Cu is loaded on the microsphere2O。
FIG. 3 shows the mesoporous Cu prepared in the first embodiment2O/TiO2Nitrogen adsorption and desorption isotherms and pore diameter distribution maps of the photocatalyst. In figure aThe isotherm type fits the H1 hysteresis loop in a typical type IV isotherm, indicating that Cu2O/TiO2The microsphere has a cylindrical mesoporous structure with openings at two ends and uniform pipe diameter distribution, and the BET specific surface area is 125.92 m calculated by an adsorption-desorption isotherm2The results in g show that the samples obtained have a very high specific surface area. The BJH pore size distribution plot in panel b shows that the sample has pore sizes centered at 3-10nm, further illustrating Cu2O/TiO2The photocatalyst has a mesoporous structure.
FIG. 4 shows the mesoporous Cu prepared in the first embodiment2O/TiO2SEM pictures of the photocatalyst in different times, wherein the low-power picture in the figure a shows that the sample is mainly microspheres with the particle size of about 2 microns, and the high-power picture in the figure b shows that Cu is contained2O/TiO2The microspheres have rough surfaces and are assembled by nano particles of about 10nm.
FIG. 5 shows mesoporous Cu prepared in example one2O/TiO2TEM photographs of photocatalyst single microsphere with different multiples show that Cu is visible from 3 TEM photographs with alternate light and shade and obvious contrast2O/TiO2The photocatalyst has a porous structure, and the circles in the high-power TEM photograph of FIG. c identify the porous structure in the sample, with the size of the voids being about 5-10nm.
FIG. 6 shows the mesoporous Cu prepared in the first embodiment2O/TiO2HRTEM photograph of the photocatalyst, from which Cu was seen2O is not present as a continuous coating, but rather as isolated nanoparticles in the TiO form2Surface, lattice spacing of 0.21nm in the figure corresponds to Cu2The (200) plane of O, the 0.35nm lattice fringe corresponding to TiO2The (101) crystal plane of (a). The existence of the two lattices in interaction, which indicates the formation of a close contact interface between the two semiconductors,
FIG. 7 shows mesoporous Cu prepared by the methods of the first, second and third embodiments2O/TiO2Photocatalyst, tiO prepared by the method of comparative example2Cu prepared by the method described in comparative example II2The relationship graph of the hydrogen quantity and the time of the water produced by photocatalytic decomposition of the O catalyst. The water photolysis experiment is carried out under the irradiation of a simulated sunlight xenon lampAnd (4) row by row. As can be seen from FIG. 7, mesoporous Cu2O/TiO2The yield of hydrogen production by photocatalytic decomposition of water by the heterostructure composite photocatalyst is far higher than that of mesoporous TiO2And Cu2The hydrogen production effect of the O sample reaches 66.6mmol/g after 6h, and the Cu yield reaches2The activity of O in producing hydrogen by photocatalytic water splitting is the lowest. The '1+1' is far more than 2, is used for improving the photocatalytic performance and is derived from Z mechanism mesoporous Cu promoted by oxygen vacancies2O/TiO2And the heterostructure retains holes and electrons with strong oxidation and reduction capabilities. The high photocatalytic activity has great significance for the development of hydrogen energy.
FIG. 8 shows mesoporous Cu prepared by the methods of the first, second and third embodiments2O/TiO2Photocatalyst, tiO prepared by the method of comparative example2Cu prepared by the method of comparative example II2The relation graph of the hydrogen production of the seawater decomposed by the photocatalysis of the O catalyst and the time. As can be seen from the figure, mesoporous Cu2O/TiO2The yield of hydrogen production by photocatalytic decomposition of seawater by the heterostructure composite photocatalyst is far higher than that of mesoporous TiO2And Cu2The hydrogen production effect of the O sample reaches 30.6mmol/g after 6h, and the photocatalytic hydrogen production efficiency is higher than that of seawater photocatalytic hydrogen production reported in most documents. The high photocatalytic activity has important significance for the practical development and utilization of seawater.
Oxygen vacancy promoted direct Z mechanism mesoporous Cu prepared by the method2O/TiO2Photocatalyst having absorption of visible light relative to mesoporous TiO2Obviously enhanced, and the photocurrent density is also obviously enhanced. The all-solid-state direct Z mechanism photocatalyst is constructed through surface oxygen defects, and Cu is reserved2O/TiO2Holes and electrons with strong oxidation reduction capability in the heterojunction photocatalyst enable invalid carriers to be compounded, and Cu is restrained to a great extent2Photo-corrosion of O in water and seawater. Surface oxygen vacancies favor water molecules, hydroxyl groups and H+Adsorption of (C), cu2O/TiO2The porous structure of the photocatalyst is beneficial to multiple reflection and scattering of incident light in a channel, and light absorption is improved. The mesoporous structure hasThe enhanced capillary effect promotes the osmotic diffusion of the solution in the nano-pores. At the same time, fine Cu2TiO with O nano particles tightly decorated in porous structure2The surface and the inside of the pore canal have stronger mass transfer capacity and more active centers, which are beneficial to H+And H2The product is fast transferred, so the photocatalytic activity and catalytic stability are obviously improved. In addition, the oxygen vacancy prepared by the invention is promoted to be directly Z mechanism mesoporous Cu2O/TiO2The photocatalyst is applied to photocatalytic degradation of various organic dyes in aqueous solution, and absorption spectrum experiment results show that the maximum absorption peak of the organic dyes is rapidly reduced and disappears under the irradiation of a simulated sunlight xenon lamp, which shows that the photocatalyst also has good photocatalytic performance for photocatalytic degradation of the organic dyes in wastewater, and can be used for treatment of organic wastewater. Has good inhibition effect on the growth of escherichia coli and staphylococcus, has good photocatalytic removal efficiency on hydrogen sulfide gas, ammonia gas and formaldehyde gas in the air, and shows that the oxygen vacancy prepared by the method promotes the direct Z mechanism mesoporous Cu2O/TiO2The photocatalyst can be used in the fields of sterilization, bacteriostasis, air purification and other environmental purification.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, substitutions, simplifications, etc. without departing from the principle and process of the present invention are all equivalent substitutions and shall be included in the protection scope of the present invention.
Claims (1)
1. Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2A photocatalyst, characterized in that said Cu2O/TiO2The photocatalyst has a mesoporous structure, cu2O-loaded to mesoporous TiO2The surface and the inside of the pore canal, the mesoporous Cu2O/TiO2The photocatalyst has an oxygen vacancy promoted all-solid-state direct Z mechanism; the preparation of the photocatalyst is carried out by mesoporous TiO2Stabilized Cu2+The ion adsorption reduction is realized by taking ethylene glycol as a pore-forming agent to obtain oxygen vacancy-promoted aluminaZ-connected mechanism mesoporous Cu2O/TiO2The heterostructure composite photocatalyst specifically comprises the following steps:
(1) Weighing 0.1-10g of titanium tetrachloride, 0.1-10g of ammonium sulfate and 0.1-10g of urea, dissolving in 1-40mL of deionized water cooled in an ice bath, and stirring for 0.5-6h;
(2) Dropwise adding 1-30mL of glycol into the mixed solution obtained in the step (1) to ensure that the volume ratio of water to the glycol is 1:4-4:1;
(3) Transferring the mixed solution obtained in the step (2) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at the constant temperature of 80-200 ℃ for 1-24h, taking out the high-pressure reaction kettle, cooling to room temperature, performing centrifugal separation, washing with deionized water and ethanol for 3 times respectively, and drying to obtain mesoporous TiO2Microspheres;
(4) Weighing 0.01-1.0 g of copper acetate, dissolving in 15mL of water, and adding 0.1-1.0g of the mesoporous TiO obtained in the step (3)2Ultrasonically dispersing microspheres for 1-20min, then washing with water, centrifuging, ultrasonically dispersing into 1-10mM sodium hydroxide solution, repeatedly soaking into copper acetate and sodium hydroxide solution for 2-3 times, then washing with water, and centrifuging;
(5) Ultrasonically dispersing the sample obtained in the step (4) into a 0.1-3mM glucose solution, transferring the sample into an autoclave, heating the sample at the constant temperature of 40-200 ℃ for 1-24h, taking the autoclave out, cooling the autoclave to room temperature, performing centrifugal separation, washing the autoclave for 3 times respectively by using deionized water and ethanol, and performing vacuum drying to obtain the oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2A photocatalyst.
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