CN112573567A - Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface - Google Patents
Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface Download PDFInfo
- Publication number
- CN112573567A CN112573567A CN202011468135.2A CN202011468135A CN112573567A CN 112573567 A CN112573567 A CN 112573567A CN 202011468135 A CN202011468135 A CN 202011468135A CN 112573567 A CN112573567 A CN 112573567A
- Authority
- CN
- China
- Prior art keywords
- acid
- titanium oxide
- crystal
- polyhedral
- index
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 76
- 238000005530 etching Methods 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- -1 light emission Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a titanium oxide polyhedral nano/micron photocatalyst exposing high-index {114} surfaces. The preparation method mainly comprises the synthesis of the titanium oxide polyhedral mother crystal and the etching of the titanium oxide polyhedral mother crystal, and finally prepares the regular polyhedral TiO exposed with the high index {114} surface2. The invention combines two strategies of top-down and bottom-up and is used for regulating and controlling the appearance of the titanium oxide. Based on the twoThe favorable direction of the thermodynamics in the strategy controls the crystal growth, and anatase titanium oxide crystals with exposed {114} surfaces are obtained, and the obtained crystals are uniform in appearance. The exposure ratio of the 114 surface is adjustable, and the 114 surface shows excellent photocatalytic performance and photoelectrochemical performance due to the unique surface structure.
Description
Technical Field
The invention relates to preparation of an anatase titanium oxide catalyst, in particular to a preparation method of a titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surfaces.
Background
Among inorganic materials, anatase titanium oxide is an important semiconductor material, TiO2Due to their chemical and biological inertness, cost-effectiveness and strong oxidizing power of photogenerated cavities, they are of great interest for a wide range of applications in catalysis, photovoltaic cells, self-cleaning devices, sensors, lithium ion battery materials, light emission, water splitting, coatings, etc. How to further improve the performance and utilization efficiency of the titanium dioxide material is a key problem in the field. The activity of the catalyst can be realized by adjusting the size, the morphology, the crystal face proportion and exposing a new crystal face, namely by controlling the atomic arrangement structure of the surface (see the literature: Angew. chem.2011,123, 2181-2185; adv. Funct. Mater.2011,21, 3554-
Basic research on single crystal model catalysts indicates that the high index surface has a structure containing high density of step atoms, kink atoms and surface dangling bonds, and thus has better performance than the low index surface (see the literature: Nature, 1975,258, 580-583). Therefore, the preparation of nanocrystals that mainly expose high index faces is an important approach to the preparation of highly active and stable nanocatalysts. Subject groups such as the university of eastern China used hydrothermal synthesis of TiO with predominantly exposed {105} high energy surface2Octahedra (see literature: Angew. chem.2010, 123, 3848-3852). However, nanocrystals with exposed high index faces tend to be difficult to prepare because the high index faces tend to have high surface energies, resulting in crystal growthWith a fast growth rate and tends to disappear.
The growth of the high-index facets is closely related to the conditions under which they are prepared, and since the preparation of the high-index facets is thermodynamically unfavorable, the synthesis of the high-index facets is generally harsh and difficult to scale up. So far, many studies on the regulation and control of crystal faces and applications of titanium oxide have been reported at home and abroad, for example, truncated octahedron exposing {001} crystal face, octahedron mainly exposing {101} crystal face, cube mainly exposing {100} face, and titanium oxide polyhedrons such as nanorods mainly exposing {010} face are reported in turn.
The most common strategy for preparing the crystal with the exposed high-index surface is to selectively adsorb on the crystal surface by using a capping agent to change the surface energy of a crystal face, so as to realize the modulation of the growth rate of the crystal, thereby obtaining the crystal with the exposed high-index surface, however, at present, most of capping ions which are mature and used as the capping agent to regulate and control the high-energy surface are F-And the regulated crystal faces are all {001} crystal faces. And some ligand ions are difficult to completely remove, and interfere with the crystal face activity of the ligand ions.
The modulation of crystal growth kinetics is realized through the control of growth conditions, and selective high-energy surfaces can also be realized, however, the growth process of the crystal is sensitive to the conditions, and the change of any crystal growth condition can cause the change of the product appearance, which leads to the synthesis in a laboratory to be difficult to enlarge the production.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing an anatase titanium oxide polyhedral nano/micro photocatalyst exposing a high index face.
The technical scheme of the invention is as follows: the preparation method of the anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index surface comprises the following steps:
(1) synthesis of titanium oxide polyhedral mother crystal: dissolving titanium salt and acid in distilled water according to the molar ratio of the titanium salt to the acid of 0.02-400, treating the solution in an ultrasonic instrument for 10-20 min, transferring the solution into a reactor, reacting at 50-500 ℃ for 2-48 h, cooling to room temperature, pouring out supernatant, washing with absolute ethyl alcohol for 3-5 times, drying in an oven for 8-24 h to obtain solid, namely titanium oxide polyhedral particles exposing {101} and {001} crystal faces, and calcining the dried sample at 300-1200 ℃ for 1-48 h to obtain titanium oxide polyhedral mother crystals;
(2) etching the titanium oxide polyhedral mother crystal: and (2) placing the titanium oxide polyhedral mother crystal obtained in the step (1) in acid with the pH value of 1-7, carrying out ultrasonic treatment for 10-20 min, transferring the solution into a reactor, etching for 1-60 h at 10-250 ℃, cooling to room temperature, washing for 3-5 times with absolute ethyl alcohol, centrifugally collecting solids, and then drying in an oven for 8-24 h to obtain solids, namely the anatase titanium oxide polyhedral nano/micro photocatalyst with exposed high-index {114} surfaces (crystal faces of {101} and {001} still exist in the obtained catalyst, but the high-index {114} surfaces are newly exposed crystal faces and can reach a higher proportion).
Further, in the step (1), the titanium source is one of titanium chloride, titanyl sulfate, tetrabutyl titanate or titanium fluoride, and the titanium salt has the characteristics of easy acquisition and reasonable cost.
Further, in the step (1), the acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, oxalic acid, citric acid, ascorbic acid or oleic acid, and the acid is easy to obtain and has the characteristics of reasonable cost.
Further, in the step (2), the acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, oxalic acid, citric acid, ascorbic acid or oleic acid, and the acid is easy to obtain and has the characteristics of reasonable cost.
Further, in the step (1) and the step (2), the drying temperature is 60-80 ℃.
The anatase titanium oxide polyhedral nano/micro photocatalyst with exposed high-index surfaces, which is obtained by the preparation method, has excellent photodegradability and electrochemical properties.
According to the invention, specific acid is used as a chemical etching agent to etch titanium oxide crystals with different morphologies synthesized in the early stage, and the morphology of the titanium oxide crystals is modified for the second time, so that {114} planes are introduced into the nanoparticles. Due to the different etching time, the obtained nano-particle morphology is also different. The {114} plane is a particular high index crystal plane of titanium oxide crystals. So far, no reports are found. On one hand, since the newly exposed {114} face has a small surface atom density, it has a larger photocurrent intensity; in another aspect. The crystal face special structure can be used as a model catalyst, and provides beneficial guidance for the development of a titanium oxide-based high-efficiency catalyst.
The invention has the beneficial effects that:
the invention combines two strategies of top-down and bottom-up and is used for regulating and controlling the appearance of the titanium oxide. The crystal growth is controlled based on the favorable direction of the thermodynamics in the two strategies, the anatase titanium oxide crystal with the exposed {114} surface is obtained, and the obtained crystal is uniform in appearance.
(2) The titanium oxide polyhedron obtained by the invention mainly comprises crystal faces with indexes of {101}, {001} and {114} series, and the proportion of the crystal faces is adjustable, so that a good model catalyst is provided for researching surface heterojunction.
(3) The preparation method is simple.
(4) The {114} plane has the smallest concentration of titanium atoms compared to all reported exposed crystal planes of titanium oxide crystals, resulting in excellent photodegradability and electrochemical performance thereof.
Drawings
Fig. 1((a) - (d)) are scanned images of nanoparticles corresponding to examples 1,2,3,4, respectively, and polyhedrons mainly exposing {101} and {001} are gradually changed into polyhedrons mainly exposing {114} planes by etching.
FIG. 2 shows a polyhedron having different proportions of crystal planes in example 5 and a polyhedron having exposed different crystal planes of 2 to 3 μm in size in example 6, wherein (a) corresponds to example 5 and (b) corresponds to example 6.
FIG. 3 is a graph showing photodegradation characteristics of the titanium oxide crystals of examples 1 and 3.
FIG. 4 is an It curve corresponding to the titanium oxide crystal in examples 1 and 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1: synthesis of a titanium oxide polyhedron, 0.15g of titanyl sulfate and 0.6ml of HF (40 wt%) are dissolved in 120ml of distilled water, the solution is transferred to a reactor after being treated in an ultrasonic instrument for 20min, the solution is cooled to room temperature after being reacted at 160 ℃ for 8h, the supernatant is poured out, the solution is washed 3 times with absolute ethyl alcohol and then dried in an oven at 80 ℃ for 24h, and a solid sample is obtained after collection. As shown in FIG. 1(a), the synthesized crystal is a polyhedral particle of titanium oxide in which {101} and {001} crystal planes are exposed. And calcining the dried sample in air for 4 hours at 800 ℃ to obtain the titanium oxide polyhedral mother crystal with the size of about 2-3 microns.
Example 2: etching {114} face on the titanium oxide polyhedron mother crystal: 20ml of 3mol/L HCl are used as etching solution which is then transferred into a polytetrafluoroethylene liner, 0.1g of TiO2Immersing in etching solution, treating the solution by ultrasonic and stirring, and sealing the polytetrafluoroethylene-lined container by using a stainless steel autoclave. The hydrothermal etching treatment was carried out at 170 ℃ for 6 h. After the autoclave was cooled, the reaction solution was taken out of the reactor and washed with ethanol or deionized water. The samples were centrifuged in a centrifuge tube and then dried in air at 80 ℃ for 12 h.
Example 3: similar to the process of the embodiment 2, but in the etching, the etching time is controlled, and the proportion of the {114} surface is regulated. The etching time is 12h, twenty percent of the obtained crystal surface is {114} plane, as shown in figure 1 (c);
example 4: continuing for an extended period of time to 18h, a polyhedron with more than forty percent exposed {114} faces can be obtained, as shown in FIG. 1(d), when the crystal consists of {114}, {101} and {001} faces;
example 5: otherwise, the procedure was as in example 1 except that: when anatase titanium dioxide crystals are prepared, the dosage of titanyl sulfate is 0.4g, the dosage of hydrofluoric acid is 0.5ml, other conditions are unchanged, and the proportion of exposed crystal faces of the obtained polyhedron is different (figure 2 (a));
example 6: otherwise, the procedure was as in example 1 except that: when anatase titanium oxide crystals are prepared, the using amount of titanyl sulfate is 0.2g, the using amount of hydrofluoric acid is 0.2ml, the reaction time is shortened to 2h, other conditions are unchanged, the exposed crystal faces of the obtained crystals are different, and the proportion of the exposed crystal faces is also different (fig. 2 (b));
example 7: otherwise, the procedure was as in example 1 except that: when preparing anatase titanium oxide crystals, replacing titanium salt with titanium fluoride, changing the using amount to 0.12g, and keeping other conditions unchanged, wherein the obtained crystals are polyhedrons exposing crystal faces of {001} and {101} and having the size of about 2-3 μm;
example 8: otherwise, the procedure was as in example 1 except that: when preparing anatase titanium oxide crystals, replacing titanium salt with titanium sulfate, changing the using amount to 0.25g, and keeping other conditions unchanged, wherein the obtained crystals are polyhedrons exposing crystal faces of {001} and {101} and having the size of about 2-3 μm;
example 9: otherwise, the procedure was as in example 1 except that: when preparing anatase titanium oxide crystals, replacing a titanium source with tetrabutyl titanate, changing the using amount of tetrabutyl titanate into 5ml, adding 6ml of H2O2 (30%), and adding the using amount of HF into 0.8ml to obtain polyhedrons with crystal faces of {001} and {101} exposed and the size of about 100-200 nm;
example 10: otherwise, the procedure was as in example 2, except that: the polyhedron in the embodiment 5 is used as a precursor for etching, and polyhedrons with the size of about 2-3 microns and exposed {114} surfaces in different proportions can be obtained by controlling the etching time;
example 11: otherwise, the procedure was as in example 2, except that: the polyhedron in the embodiment 6 is used as a precursor for etching, and polyhedrons with the size of about 2-3 microns and exposed {114} surfaces in different proportions can be obtained by controlling the etching time;
example 12: otherwise, the procedure was as in example 2, except that: using sulfuric acid to replace hydrochloric acid, wherein the concentration of the sulfuric acid is 1.5mol/L, the etching temperature is 170 ℃, the etching rate is one time of that of the hydrochloric acid, and etching is carried out for 6 hours to obtain particles with the same etching degree as that of the particles in the graph 1 c;
example 13: otherwise, the procedure was as in example 2, except that: replacing hydrochloric acid with nitric acid, wherein the concentration of nitric acid is 3mol/L, the etching temperature is 170 ℃, the etching rate is slower than that of hydrochloric acid, and the particles with the same etching degree as that of the particles in the graph 1c are obtained after 24 hours of etching;
example 14: otherwise, the procedure was as in example 2, except that: replacing hydrochloric acid with oxalic acid, wherein the concentration of the oxalic acid is 3mol/L, the etching temperature is 170 ℃, the etching rate is slower than that of the hydrochloric acid, and the particles with the same etching degree as that of the particles in the graph 1c are obtained after 24 hours of etching;
example 15: and (3) testing the photodegradability of the titanium oxide polyhedron: the titanium oxide polyhedron product obtained in the embodiment is used as a catalyst, 100ml of 5mg/L rhodamine b solution and 10mg of the catalyst are respectively added into a 250ml photodegradation quartz glass vessel, the height of the quartz glass vessel is consistent with that of a light source every time, circulating water is opened, and constant temperature treatment of experiments is carried out. And opening the stirrer, and stirring for 30min under a dark condition until the degradation liquid and the catalyst reach adsorption equilibrium. After the reaction reached the adsorption equilibrium, the xenon lamp was turned on and the degradation solution was irradiated, 4ml of the degradation solution was taken out at intervals and centrifuged immediately, and then the supernatant was analyzed using a Hitachi U-3010 uv-vis spectrometer. The test results show that the degraded plastic of the sample of the final example 3 with etched {114} crystal face is TiO of the example 124.02 times of the mother crystal.
Example 16: and (3) testing the photodegradability of the titanium oxide polyhedron: taking the polyhedral titanium oxide product obtained in the example as a catalyst, putting 5mg of the catalyst and 0.5mg of carbon black into a solution of ethylene glycol and N, N-dimethylformamide with the molar ratio of 3:1, performing ultrasonic treatment for 60min, and uniformly coating the solution on a conductive surface of FTO conductive glass. It was used as a working electrode in an electrochemical workstation for It testing. The test results show that the photocurrent intensity of the sample etched with {114} crystal plane in the final example 3 is the same as that of TiO crystal in example 123.98 times of the mother crystal.
Claims (5)
1. The preparation method of the anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index surface is characterized by comprising the following steps:
(1) synthesis of titanium oxide polyhedral mother crystal: dissolving a titanium salt and an acid in distilled water according to the molar ratio of titanium to acid radical ions of 0.02-400, treating in an ultrasonic instrument for 10-20 min, transferring the solution into a reactor, reacting at 50-500 ℃ for 2-48 h, cooling to room temperature, pouring out supernatant, washing with absolute ethyl alcohol for 3-5 times, drying in an oven for 8-24 h to obtain solid, namely titanium oxide polyhedral particles exposing {101} and {001} crystal faces, and calcining the dried sample at 300-1200 ℃ for 1-48 h to obtain a titanium oxide polyhedral mother crystal;
(2) etching the titanium oxide polyhedral mother crystal: and (2) placing the titanium oxide polyhedral mother crystal obtained in the step (1) in acid with the pH value of 1-7, carrying out ultrasonic treatment for 10-20 min, transferring the solution into a reactor, etching for 1-60 h at 10-250 ℃, cooling to room temperature, washing for 3-5 times by using absolute ethyl alcohol, centrifugally collecting solids, and drying in an oven for 8-24 h to obtain the solids, namely the anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surfaces.
2. The method of claim 1 wherein in step (1) the titanium source is one of titanium chloride, titanyl sulfate, tetrabutyl titanate, or titanium fluoride.
3. The method of claim 1, wherein in step (1), the acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, oxalic acid, citric acid, ascorbic acid or oleic acid.
4. The method of claim 1, wherein in step (2), the acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, oxalic acid, citric acid, ascorbic acid or oleic acid.
5. The method for preparing a high-index-surface-exposed titanium oxide polyhedral nano/micro photocatalyst as claimed in claim 1, wherein the drying temperature in the steps (1) and (2) is 60-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011468135.2A CN112573567B (en) | 2020-12-15 | 2020-12-15 | Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011468135.2A CN112573567B (en) | 2020-12-15 | 2020-12-15 | Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112573567A true CN112573567A (en) | 2021-03-30 |
| CN112573567B CN112573567B (en) | 2022-05-17 |
Family
ID=75134949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011468135.2A Active CN112573567B (en) | 2020-12-15 | 2020-12-15 | Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112573567B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215001A (en) * | 2008-01-16 | 2008-07-09 | 中山大学 | Method for preparing rutile-type titanium dioxide micro-sphere |
| CN102941076A (en) * | 2012-11-21 | 2013-02-27 | 华东理工大学 | {110} surface exposed titanium dioxide photocatalysis material and preparation method thereof |
| CN103230787A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of {001} surface-exposed anatase-phase titanium dioxide microsphere photocatalyst |
| CN103331153A (en) * | 2013-06-07 | 2013-10-02 | 南京信息工程大学 | Synthesis method of high-activity TiO2 nanodisk photocatalyst |
| CN103708544A (en) * | 2013-12-13 | 2014-04-09 | 天津大学 | One-step preparation method of mono-dispersed decahedral anatase titanium dioxide powder |
| CN104722289A (en) * | 2015-03-19 | 2015-06-24 | 中国科学院电工研究所 | Method for preparing ultrafine powder in nano titanium dioxide structure |
| CN105347393A (en) * | 2015-11-11 | 2016-02-24 | 湘潭大学 | Anatase titanium dioxide nanoribbons exposing {010} crystal face and preparation method thereof |
| CN110252353A (en) * | 2019-07-02 | 2019-09-20 | 汕头大学 | A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application |
| CN110743522A (en) * | 2019-09-24 | 2020-02-04 | 浙江工业大学 | High-index crystal face titanium dioxide nano catalyst and preparation method thereof |
| CN111056568A (en) * | 2018-10-17 | 2020-04-24 | 南京理工大学 | F ion hydrothermal regulation and control TiO2Method of crystal face |
-
2020
- 2020-12-15 CN CN202011468135.2A patent/CN112573567B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215001A (en) * | 2008-01-16 | 2008-07-09 | 中山大学 | Method for preparing rutile-type titanium dioxide micro-sphere |
| CN102941076A (en) * | 2012-11-21 | 2013-02-27 | 华东理工大学 | {110} surface exposed titanium dioxide photocatalysis material and preparation method thereof |
| CN103230787A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of {001} surface-exposed anatase-phase titanium dioxide microsphere photocatalyst |
| CN103331153A (en) * | 2013-06-07 | 2013-10-02 | 南京信息工程大学 | Synthesis method of high-activity TiO2 nanodisk photocatalyst |
| CN103708544A (en) * | 2013-12-13 | 2014-04-09 | 天津大学 | One-step preparation method of mono-dispersed decahedral anatase titanium dioxide powder |
| CN104722289A (en) * | 2015-03-19 | 2015-06-24 | 中国科学院电工研究所 | Method for preparing ultrafine powder in nano titanium dioxide structure |
| CN105347393A (en) * | 2015-11-11 | 2016-02-24 | 湘潭大学 | Anatase titanium dioxide nanoribbons exposing {010} crystal face and preparation method thereof |
| CN111056568A (en) * | 2018-10-17 | 2020-04-24 | 南京理工大学 | F ion hydrothermal regulation and control TiO2Method of crystal face |
| CN110252353A (en) * | 2019-07-02 | 2019-09-20 | 汕头大学 | A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application |
| CN110743522A (en) * | 2019-09-24 | 2020-02-04 | 浙江工业大学 | High-index crystal face titanium dioxide nano catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112573567B (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Duan et al. | TiO2 faceted nanocrystals on the nanofibers: Homojunction TiO2 based Z-scheme photocatalyst for air purification | |
| JP2020033250A (en) | Linear porous titanium dioxide material, and preparation method and application thereof | |
| WO2017118223A1 (en) | Spherical cadmium sulfide crystal and method for preparing same | |
| CN105236491B (en) | A kind of thread W18O49The preparation method of material | |
| Bi et al. | Constructing anatase TiO2/Amorphous Nb2O5 heterostructures to enhance photocatalytic degradation of acetaminophen and nitrogen oxide | |
| CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
| CN106622201A (en) | Preparation method and application of graphene and titanium dioxide photo-catalysis nano-crystals | |
| CN105618021B (en) | A kind of H2O2Modified anatase/rutile titanium dioxide nano-crystal composite material | |
| CN110540238A (en) | Method for preparing anatase type nano titanium dioxide powder by improved hydrothermal method | |
| CN107311227A (en) | The preparation method and product of a kind of titanium dioxide nanoplate for mixing crystal formation | |
| CN109326790B (en) | One-dimensional nano linear sodium titanate and preparation method and application thereof | |
| CN103626225A (en) | Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof | |
| CN111701583A (en) | Ultrathin hexagonal BiO2-x platelet photocatalyst and preparation method thereof | |
| CN103657625A (en) | Preparation method of rutile type boron-doped titania (B-TiO2) microsphere with exposed high energy crystal face {001} | |
| CN111686770A (en) | Metal ion co-doped BiOBr microsphere, preparation method and application thereof | |
| CN107227511B (en) | A kind of preparation method and product of the titania fiber mixing crystal form | |
| CN112573567B (en) | Preparation method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {114} surface | |
| Liu et al. | Hierarchical TiO 2 spheres: Facile fabrication and enhanced photocatalysis | |
| CN104001489A (en) | High-photocatalytic-activity flower-shaped porous titanium dioxide nano material and preparation method thereof | |
| CN112892514B (en) | Synthesis method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {136} surface | |
| CN105561969A (en) | Preparation and application of porous TixSn1-xO2 solid solution microspheres | |
| CN112439429B (en) | Cadmium sulfide particles with cage-shaped structure and preparation method and application thereof | |
| CN113751027A (en) | Ultrathin MgIn2S4Nano-sheet sterilization photocatalytic material and preparation method thereof | |
| CN108295831A (en) | Modifying titanium dioxide nanometer sheet and amorphous carbon composite material powder and preparation method | |
| CN103721701B (en) | A kind of novel nido bismuth oxide photocatalyst and preparation method thereof |
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 |