CN112958061A - 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
- Publication number
- CN112958061A CN112958061A CN202110154774.XA CN202110154774A CN112958061A CN 112958061 A CN112958061 A CN 112958061A CN 202110154774 A CN202110154774 A CN 202110154774A CN 112958061 A CN112958061 A CN 112958061A
- Authority
- CN
- China
- Prior art keywords
- tio
- mesoporous
- photocatalyst
- water
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000001301 oxygen Substances 0.000 title claims abstract description 27
- 230000007246 mechanism Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 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 84
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011941 photocatalyst Substances 0.000 claims abstract description 68
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 239000011148 porous material 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
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 239000010949 copper Substances 0.000 claims description 55
- 238000005406 washing Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 32
- 239000004005 microsphere Substances 0.000 claims description 27
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000013535 sea water Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000191940 Staphylococcus Species 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013169 thromboelastometry Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
-
- 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—
-
- B01J35/615—
-
- B01J35/647—
-
- 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
-
- 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)2SO4Urea as material and glycol as pore forming agent, and through solvothermal process and roasting to obtain mesoporous TiO structure2Then adding Cu2TiO loaded with O to mesoporous structure2To obtain Z-type mesoporous Cu with promoted oxygen vacancy2O/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 good photocatalytic activity for hydrogen production by photolysis of water, hydrogen production by photolysis of seawater 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 been demonstrated by providing visible light absorptionOne promising strategy to achieve enhanced photocatalytic performance. 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.
Existing 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/TiO2The heterojunction photocatalyst has the defects of low specific surface, few heterojunction active sites, low photoproduction electron/hole separation efficiency, low seawater hydrogen production efficiency and the like, and provides the 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 promoterDirect Z mechanism mesoporous Cu2O/TiO2The photocatalyst and the preparation method thereof are characterized in that the Cu is2O/TiO2The photocatalyst has a mesoporous structure, Cu2O-loaded 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, and TiO with a mesoporous structure is obtained by adopting a solvothermal method through 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 0.5-6 h;
(2) dropwise adding 1-30ml of ethylene glycol into the mixed solution obtained in the step (1) to enable the volume ratio of water to the ethylene glycol to be 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 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. The photocatalyst has good photocatalytic activity and stability for photocatalytic water splitting hydrogen production, photocatalytic seawater splitting hydrogen production in the field of novel hydrogen energy and photocatalytic water organic pollutant degradation in the field of environmental purification, bacteriostasis, air purification and the like.
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 diameter 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 the mesoporous Cu prepared in the first embodiment2O/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 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.
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 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 0.15g 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, 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 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 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)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 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)2Ultrasonically dispersing microspheres, washing with water, centrifuging, ultrasonically dispersing into a 5mM sodium hydroxide solution, 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 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)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 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, 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 0.1g 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)2Each diffraction peak pairThe corresponding indices of the crystal planes are 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 spectrum 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 favors the collection and transfer of the catalyst photo-generated charge. From the binding energy of Cu LMM auger spectrum 570.2eV in the graph c, it can be confirmed that Cu in the composite sample is Cu (I), indicating that 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. The isotherm type in graph a corresponds to the hysteresis loop of type H1 in a typical type IV isotherm, indicating that Cu is present2O/TiO2The microsphere has a cylindrical mesoporous structure with openings at two ends and uniform pipe diameter distribution, and the BET specific surface area is 125.92m 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 10 nm.
FIG. 5 shows the mesoporous Cu prepared in the first embodiment2O/TiO2TEM photographs of photocatalyst single microsphere with different multiples are taken from 3 TEMs with alternate light and shade and obvious contrastAs can be seen from the photographs, Cu2O/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 5-10 nm.
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 as isolated nanoparticles in the TiO2Surface, 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 simulated sunlight xenon lamp irradiation. 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 on photocatalytic water splitting for hydrogen production is the lowest. The '1 + 1' is much larger than 2, the photocatalytic performance is improved, and the Z mechanism mesoporous Cu promoted by oxygen vacancies is sourced2O/TiO2And the heterostructure retains holes and electrons with strong oxidation and reduction capabilities. The high photocatalytic activity has important 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 described in comparative example II2The hydrogen production quantity of the seawater subjected to photocatalytic decomposition by the O catalyst is plotted against time. As can be seen from the figure, mesoporous Cu2O/TiO2Photocatalytic decomposition of heterostructure composite photocatalystThe yield of the seawater hydrogen production is far higher than that of the 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 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 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 and 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 growth of the staphylococcus aureusZ-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/TiO2The photocatalyst and the preparation method thereof are characterized in that the Cu is2O/TiO2The photocatalyst has a mesoporous structure, Cu2O-loaded 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, and TiO with a mesoporous structure is obtained by adopting a solvothermal method through 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 0.5-6 h;
(2) dropwise adding 1-30ml of ethylene glycol into the mixed solution obtained in the step (1) to enable the volume ratio of water to the ethylene glycol to be 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) 0.01-1.0 g of copper acetate is weighed and dissolved in15ml of water, 0.1 to 1.0g of the mesoporous TiO obtained in the step (3) is added2Ultrasonically 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 sample for 3 times by using deionized water and ethanol respectively, and performing vacuum drying to obtain the mesoporous Cu2O/TiO2A photocatalyst.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110154774.XA CN112958061B (en) | 2021-02-04 | 2021-02-04 | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof |
ZA2021/10717A ZA202110717B (en) | 2021-02-04 | 2021-12-21 | Oxygen vacancy stimulated direct z-scheme mesoporous cu2o/tio2 photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110154774.XA CN112958061B (en) | 2021-02-04 | 2021-02-04 | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112958061A true CN112958061A (en) | 2021-06-15 |
CN112958061B CN112958061B (en) | 2022-11-01 |
Family
ID=76275471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110154774.XA Active CN112958061B (en) | 2021-02-04 | 2021-02-04 | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN112958061B (en) |
ZA (1) | ZA202110717B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114272938A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Load type Ni-Mn/TiO for autothermal reforming of acetic acid to produce hydrogen2Catalyst and process for preparing same |
CN114984965A (en) * | 2022-05-30 | 2022-09-02 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
CN115282995A (en) * | 2022-07-04 | 2022-11-04 | 华南理工大学 | CuO (copper oxide) x /TiO 2 @ C-N photocatalyst and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786083A (en) * | 2012-06-08 | 2012-11-21 | 合肥工业大学 | Preparation method of titanium dioxide nano hollow ball |
CN107081166A (en) * | 2017-06-12 | 2017-08-22 | 青岛科技大学 | A kind of g C3N4/TiO2Multilevel hierarchy and preparation method thereof |
US20170274364A1 (en) * | 2014-08-29 | 2017-09-28 | Sabic Global Technologies B.V. | Photocatalytic hydrogen production from water over catalysts having p-n junctions and plasmonic materials |
-
2021
- 2021-02-04 CN CN202110154774.XA patent/CN112958061B/en active Active
- 2021-12-21 ZA ZA2021/10717A patent/ZA202110717B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786083A (en) * | 2012-06-08 | 2012-11-21 | 合肥工业大学 | Preparation method of titanium dioxide nano hollow ball |
US20170274364A1 (en) * | 2014-08-29 | 2017-09-28 | Sabic Global Technologies B.V. | Photocatalytic hydrogen production from water over catalysts having p-n junctions and plasmonic materials |
CN107081166A (en) * | 2017-06-12 | 2017-08-22 | 青岛科技大学 | A kind of g C3N4/TiO2Multilevel hierarchy and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
YING LU ET AL: "Cu2O nanocrystals/TiO2 microspheres film on a rotating disk containing long-afterglow phosphor for enhanced round-the-clock photocatalysis", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114272938A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Load type Ni-Mn/TiO for autothermal reforming of acetic acid to produce hydrogen2Catalyst and process for preparing same |
CN114984965A (en) * | 2022-05-30 | 2022-09-02 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
CN114984965B (en) * | 2022-05-30 | 2023-07-21 | 吉林大学 | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof |
CN115282995A (en) * | 2022-07-04 | 2022-11-04 | 华南理工大学 | CuO (copper oxide) x /TiO 2 @ C-N photocatalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN112958061B (en) | 2022-11-01 |
ZA202110717B (en) | 2022-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sun et al. | N self-doped ZnO derived from microwave hydrothermal synthesized zeolitic imidazolate framework-8 toward enhanced photocatalytic degradation of methylene blue | |
CN112958061B (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
CN100411730C (en) | Zeolite based nano-titanium dioxide double function material and its prepn. method | |
Liu et al. | Integration of nanosized ZIF-8 particles onto mesoporous TiO 2 nanobeads for enhanced photocatalytic activity | |
CN112892611B (en) | Fish scale tubular carbon nitride and preparation method and application thereof | |
CN107243340B (en) | Preparation method of cerium dioxide nanorod doped titanium dioxide nanoparticle photocatalyst | |
CN113289647B (en) | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application | |
Zhong et al. | Liquid phase deposition of flower-like TiO2 microspheres decorated by ZIF-8 nanoparticles with enhanced photocatalytic activity | |
Hou et al. | Preparation of Cu 2 O@ TiOF 2/TiO 2 and its photocatalytic degradation of tetracycline hydrochloride wastewater | |
Zhong et al. | Preparation of a novel composite photocatalyst BiOBr/ZIF-67 for enhanced visible-light photocatalytic degradation of RhB | |
CN107983353B (en) | TiO 22-Fe2O3Preparation method and application of composite powder | |
CN112774718A (en) | Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof | |
Chen et al. | ZnO@ ZIF-8 core–shell heterostructures with improved photocatalytic activity | |
CN102698727A (en) | Method for preparing supported TiO2 photocatalyst with high thermal stability | |
CN108927201B (en) | AgBr/g-C3N4Preparation method and application of composite powder | |
CN112973744B (en) | Photoelectric catalyst and preparation method thereof | |
CN113856702A (en) | Cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst and preparation method and application thereof | |
CN109046341B (en) | Preparation method of visible light response silver silicate/attapulgite composite catalyst | |
CN116212966B (en) | Indirect Z-type multicomponent bismuth-based MOF heterojunction and preparation method and application thereof | |
CN109078644B (en) | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof | |
CN115025783B (en) | Synthetic method and application of multi-niobium oxygen cluster/ZIF-67 derivative composite material | |
CN114192179A (en) | Preparation method, product and application of nitrogen-defect carbon nitride composite silver phosphate photocatalyst | |
CN110624532B (en) | TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof | |
CN114452969A (en) | Double-promoter supported photocatalyst and preparation method and application thereof | |
CN109701518B (en) | Composite photocatalyst, preparation method thereof and application of composite photocatalyst in degradation of organic dye |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20230627 Address after: No. 703, No. 28, Lane 819, Baizhang East Road, Dongliu Street, Yinzhou District, Ningbo City, Zhejiang Province, 315042 Patentee after: Zhang Jun Address before: 266000 Songling Road, Laoshan District, Qingdao, Shandong Province, No. 99 Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |