CN107827152B - Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane - Google Patents
Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane Download PDFInfo
- Publication number
- CN107827152B CN107827152B CN201711108369.4A CN201711108369A CN107827152B CN 107827152 B CN107827152 B CN 107827152B CN 201711108369 A CN201711108369 A CN 201711108369A CN 107827152 B CN107827152 B CN 107827152B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- phase
- anatase
- tio
- 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.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 305
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 28
- 238000007146 photocatalysis Methods 0.000 title abstract description 12
- 230000001699 photocatalysis Effects 0.000 title abstract description 12
- 239000001569 carbon dioxide Substances 0.000 title abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 8
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 claims description 15
- 229910000246 schorl Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910001258 titanium gold Inorganic materials 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 101
- 239000003054 catalyst Substances 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 238000001548 drop coating Methods 0.000 description 10
- 239000013049 sediment Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 238000004088 simulation Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000004845 hydriding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
-
- 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—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The present invention relates to the blue titanium dioxides and preparation method thereof for carbon dioxide photocatalysis synthesizing methane, the preparation method include: by alkali metal, titanium dioxide and ethylenediamine mix after at 100~200 DEG C solvent thermal reaction 10~48 hours, after washed again, dry, blue titanium dioxide is obtained.Blue titanium dioxide photochemical catalyst prepared by the present invention has many advantages, such as excellent photocatalysis performance for converting methane reaction for carbon dioxide and water compared with same type material, and has preparation method mild, controllable, at low cost.
Description
Technical field
The present invention relates to the blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane, belonging to
Chemical catalyst technical field.
Background technique
As abundant, nontoxic, reproducible carbon resource, CO2Gas can be widely used in producing hydro carbons, alcohols and formic acid etc.
High level chemicals.Currently, CO2Highest attention of the photocatalysis synthesizing methane by domestic and foreign scholars.The realization of the process not only will
It cleans reproducible solar energy and is converted to chemical energy, and be to alleviate the CO such as greenhouse effects, global warming, Ocean acidification2It is negative
The effective way that face is rung.The research and development of high efficiency photocatalyst become CO2Synthesize the key of high level chemicals (such as methane).
Currently, being used for CO2The catalyst of synthesizing methane reaction process mainly has photochemical catalyst, elctro-catalyst and thermocatalyst
Deng.Photochemical catalyst, which utilizes, cleans reproducible solar energy for CO2Being reduced into fuel is considered as solving energy crisis and environment dirt
The desirable route of dye.Titanium dioxide is as a kind of oxide semiconductor material, since its is environmental-friendly, chemical property is stable, valence
The features such as lattice are cheap, preferable charge transport properties, in CO2Photo catalytic reduction field is widely used.However, dioxy
Change titanium greater band gap (~3.2eV), electric conductivity is weaker；Meanwhile the separation of limited electron hole pair and transmittability inhibit
It is further to apply.People, which have been working hard, for many years attempts by doping metals (Fe, Co, Ni, Mn, Cr etc.) or non-
Metal (N, S, C, I etc.) changes the band structure of titanium dioxide, coloured titanium dioxide is prepared, to realize sunlight
Wide spectrum absorbs.Hydrogenation titanium dioxide is obtained due to showing good Photocatalyzed Hydrogen Production and photocatalysis contaminant degradation performance
Extensive concern.Chen et al. is heat-treated at 200 DEG C using 20bar high-purity hydrogen obtains hydrogenation black two for titanium dioxide five days
Titanium oxide (Science 2011,331,746.).Sun et al. is heat-treated dioxy at 450 DEG C also with 70bar high-purity hydrogen
Change titanium and obtains hydrogenation black titanium dioxide (J.Phys.Chem.C 2011,115,25590.).Lu et al. is existed using high-purity hydrogen
Lark or black titanium dioxide are prepared under room temperature, but Hydrogen Vapor Pressure reaches 35bar, the reaction time is up to 20 days (RSC
Adv.2014,4,1128.).But these hydrogenate the preparation process of coloured titanium dioxide mostly under high-purity hydrogen atmosphere, use
High temperature and high pressure reacts for a long time, and the coloured titanium dioxide that preparation process is dangerous, energy consumption is high and prepared is less to be successfully applied to
Photocatalysis CO2Synthesizing methane process.
In short, current all kinds of photocatalysis CO2The coloured titanium dioxide preparation condition of reduction is harsh, and preparation temperature is high, consumes energy
Height need to use hazardous gas hydrogen etc..Therefore, it is necessary to develop one kind can compared under temperate condition and have wide spectrum response have
The preparation method of color titanium dioxide optical catalyst.
Summary of the invention
The present invention is low to sun light utilization efficiency for ordinary titanium dioxide, and difficulty is adsorbed and activated to reactant molecule, and
It has been reported that the deficiencies of preparation method of color titanium dioxide is dangerous, energy consumption is higher, its purpose is to provide under a kind of temperate condition
High activity, highly selective and high stability blue titanium dioxide photochemical catalyst and preparation method thereof.
On the one hand, the present invention provides a kind of preparation methods of blue titanium dioxide, by alkali metal, titanium dioxide and second two
Blue titanium dioxide is obtained behind solvent thermal reaction 10~48 hours, then washed, drying at 100~200 DEG C after amine mixing.
Alkali metal is introduced into the ethylenediamine solution containing titanium dioxide by the present invention, then the solvent at 100~200 DEG C
Thermal response 10~48 hours, then by washing and drying, obtain blue titanium dioxide.
Preferably, the titanium dioxide is anatase phase titanium dioxide, red schorl phase titanium dioxide, brookite titanium dioxide
At least one of titanium, preferably anatase phase titanium dioxide, red schorl phase titanium dioxide, brookite titanium dioxide or rutile titania
The mixed phase of mine titanium dioxide phase and red schorl phase titanium dioxide.
Also, preferably, when titanium dioxide is the mixed phase of anatase phase titanium dioxide and red schorl phase titanium dioxide, it is described
The mass ratio of anatase phase titanium dioxide and red schorl phase titanium dioxide is (0.1~9): 1.
Preferably, the alkali metal is at least one of lithium, sodium, potassium.
Preferably, the ratio of the titanium dioxide and ethylenediamine is (100~900) mg:(10~60) ml, it can more preferably promote shell
Nuclear structure and the decrystallized formation of surface hydriding.
Preferably, the mass ratio of the alkali metal and titanium dioxide is 1:(1~10), preferred 1:(3~8), can more preferably promote
Into the decrystallized formation of core-shell structure and surface.
Preferably, it is 0.01~0.5mol L that the washing, which is with concentration,–1Hydrochloric acid solution washing, then washed with water and alcohol
It washs.
Preferably, the temperature of the drying is -10~150 DEG C, the time is 10~30 hours.
On the other hand, the present invention also provides a kind of blue titanium dioxide prepared according to above-mentioned preparation method, the indigo plants
Color titanium dioxide include titanium dioxide crystal core and be coated on titanium dioxide crystal core surface containing Lacking oxygen and H atom
Titanium oxide amorphous shell.Heretofore described blue titanium dioxide photochemical catalyst is represented by H-X-TiO2-δ(y), wherein X
Indicate different crystal phase titanium dioxide (Anatase A, Rutile Type R, brookite B or anatase and rutile mixed phase P), y is
The alkali metal quality (unit mg) being added in preparation process.Prepared blue titanium dioxide (the modified H-X-TiO in surface2-δ(y))
A kind of unique nucleocapsid structure is shown, internal is titanium dioxide crystal core, and outside is to contain a large amount of Lacking oxygens and H atom
Titanium oxide TiO2-δAmorphous shell.Its H atom adulterated and nucleocapsid structure can lead to the change of titanium dioxide color, significantly
Increase the absorption and utilization to sunlight.The formation of unformed amorphous shell and a large amount of Lacking oxygens has also effectively facilitated reactant
The absorption and activation of carbon dioxide, and then significantly improve the overall performance of catalyst.
In another aspect, the present invention also provides a kind of above-mentioned blue titanium dioxides in carbon dioxide photocatalysis synthesizing methane
Application.
Blue titanium dioxide photochemical catalyst prepared by the present invention is and same for converting methane reaction for carbon dioxide and water
Types of material, which is compared, has many advantages, such as excellent photocatalysis performance, and has preparation method mild, controllable, at low cost.Complete
Under spectral illumination, the selectivity of methane is up to 89%, and the reachable generating rate of methane is 16.2 μm of ol g–1h–1, after six times recycle
Still maintain 15 μm of ol g–1h–1More than.
Detailed description of the invention
Fig. 1 is H-P-TiO prepared by embodiment 12-δ(200) high resolution transmission electron microscopy photo；
Fig. 2 is H-P-TiO prepared by embodiment 12-δ(200) hydrogen nuclear magnetic resonance spectrogram；
Fig. 3 is H-P-TiO prepared by embodiment 12-δ(200) cycle performance figure of catalyst.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
H-X-TiO is expressed as provided by the present invention for the blue titanium dioxide of carbon dioxide photocatalysis synthesizing methane2-δ
(y), wherein X indicates different crystal phase titanium dioxide (for example, Anatase A, Rutile Type R, brookite B or anatase and gold
Red stone mixed phase P), y is the alkali metal quality (unit mg) being added in preparation process.Wherein, the modified H-X- in prepared surface
TiO2-δ(y) a kind of unique nucleocapsid structure is shown, internal is titanium dioxide crystal core, and outside is to contain a large amount of Lacking oxygens
With the TiO of H atom2-δAmorphous shell (titanium oxide amorphous shell).Wherein, the TiO containing Lacking oxygen and H atom2-δAmorphous shell
The thickness of layer is generally 2~5 nanometers.
The present invention arrives blue titanium dioxide by prepared by simple solvent-thermal method, and solvent is dissolved with a certain amount of alkali metal
Ethylenediamine solution.Illustrate to following exemplary the preparation method of blue titanium dioxide provided by the invention.
By alkali metal, titanium dioxide and ethylenediamine mix after at 100~200 DEG C solvent thermal reaction 10~48 hours, then
After washed, dry, blue titanium dioxide is obtained.It should be noted that the addition of alkali metal, titanium dioxide and ethylenediamine is suitable in the present invention
Sequence and without concrete restriction may be, for example, and alkali metal be added in the ethylenediamine solution containing titanium dioxide or by titanium dioxide
It is added in the ethylenediamine solution containing alkali metal and all may be used.The alkali metal can be at least one of lithium, sodium, potassium.Described two
The ratio of titanium oxide and ethylenediamine can be (100~900) mg:(10~60) ml.The mass ratio of the alkali metal and titanium dioxide can
For 1:(1~10), preferred 1:(3~8).
In the present invention, the titanium dioxide can be anatase phase titanium dioxide (A), red schorl phase titanium dioxide (R), plate titanium
At least one of mine phase titanic oxide (B) preferably can be anatase phase titanium dioxide, red schorl phase titanium dioxide, brockite
The mixed phase (P) of phase titanic oxide or anatase titania phase and red schorl phase titanium dioxide.And when titanium dioxide is anatase
When the mixed phase of phase titanic oxide and red schorl phase titanium dioxide, the anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio can be (0.1~9): 1.
In the present invention, it can be 0.01~0.5mol L that the washing, which is with concentration,–1Acid solution (for example, hydrochloric acid solution etc.)
Washing, then with water and ethanol wash.
In the present invention, the temperature of the drying can be -10~150 DEG C, and the time can be 10~30 hours.
As a blue titanium dioxide H-X-TiO2-δ(y) example of preparation method, comprising: (1) by 100~900mg
Titanium dioxide is scattered in 10~60mL ethylenediamine, is stirred 0.1~5h, is added the alkali metal of 0~400mg；(2) by step
(1) mixed system 10~48h of solvent heat at 100~200 DEG C in；(3) substance after solvent heat in step (2) is filtered and is used in combination
Concentration is 0.01~0.5mol L–1Hydrochloric acid solution sufficiently wash, then sufficiently washed with water and alcohol；It (4) will be in step (3)
Sediment dry 10~30h at -10~150 DEG C, obtains blue titanium dioxide H-X-TiO2-δ(y) catalyst.
In the present invention, all catalysis reactions of the blue titanium dioxide are 100mL in volume and top is equipped with saturating
It is carried out in the tank reactor of light quartz plate.A certain amount of catalyst fines are dispersed in water, then drop coating is in 4cm2Glass
Glass piece is placed in reactor top, and 2~10mL water is added in reactor bottom.After air drains in kettle, then it is passed through 2~
20barCO2, uniform stirring (800rpm) at room temperature, simulated solar irradiation irradiation is lower to react 1~10h, product directly use mass spectrograph and
Gas chromatograph carries out qualitative and quantitative analysis.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
By 500mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 7:3) it is scattered in 30mL ethylenediamine, 0.5h is stirred, the lithium metal of 200mg is added, then by the mixing
System is kept the temperature for 24 hours at 180 DEG C, is filtered after cooling and is 0.1mol L with concentration–1Hydrochloric acid solution sufficiently wash, then with water and
Alcohol sufficiently washs, and gained sediment dries 20h at -10 DEG C to get H-P-TiO is arrived2-δ(200) catalyst；
By 50mg H-P-TiO2-δ(200) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 4mL water is added in reactor bottom, after air drains in kettle, then is passed through 2bar CO2, room temperature simulation solar irradiation
Lower reaction 5h is penetrated, the results are shown in Table 1.
Embodiment 2:
It disperses 400mg anatase phase titanium dioxide (A) in 20mL ethylenediamine, stirs 2h, add the metal of 300mg
Then the mixed system is kept the temperature at 160 DEG C 32h, filters after cooling and be 0.2mol L with concentration by sodium–1Hydrochloric acid solution fill
Divide washing, then sufficiently washed with water and alcohol, gained sediment dries 30h at 10 DEG C to get H-A-TiO is arrived2-δ(300) it urges
Agent；
By 30mg H-A-TiO2-δ(300) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 6mL water is added in reactor bottom, after air drains in kettle, then is passed through 5bar CO2, room temperature simulation solar irradiation
Lower reaction 3h is penetrated, the results are shown in Table 1.
Embodiment 3:
It disperses 600mg red schorl phase titanium dioxide (R) in 15mL ethylenediamine, stirs 5h, add the metal of 100mg
Then the mixed system is kept the temperature at 200 DEG C 12h, filters after cooling and be 0.5mol L with concentration by potassium–1Hydrochloric acid solution fill
Divide washing, then sufficiently washed with water and alcohol, gained sediment dries 15h at 100 DEG C to get H-R-TiO is arrived2-δ(100) it urges
Agent；
By 60mg H-R-TiO2-δ(100) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 2mL water is added in reactor bottom, after air drains in kettle, then is passed through 10bar CO2, room temperature simulation sunlight
Irradiation is lower to react 10h, the results are shown in Table 1.
Embodiment 4:
It disperses 900mg brookite titanium dioxide (B) in 25mL ethylenediamine, stirs 0.5h, add the gold of 400mg
Belong to sodium, then the mixed system is kept the temperature into 48h at 150 DEG C, filtered after cooling and be 0.01mol L with concentration–1Hydrochloric acid it is molten
Liquid sufficiently washs, then is sufficiently washed with water and alcohol, and gained sediment dries 10h at 150 DEG C to get H-B-TiO is arrived2-δ
(400) catalyst；
By 90mg H-B-TiO2-δ(400) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 8mL water is added in reactor bottom, after air drains in kettle, then is passed through 6bar CO2, room temperature simulation solar irradiation
Lower reaction 4h is penetrated, the results are shown in Table 1.
Embodiment 5:
By 600mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 6:4) it is scattered in 20mL ethylenediamine, 0.1h is stirred, the lithium metal of 400mg is added, then by the mixing
System keeps the temperature 36h at 170 DEG C, filters after cooling and is 0.05mol L with concentration–1Hydrochloric acid solution sufficiently wash, then use water
It is sufficiently washed with alcohol, gained sediment dries 25h at 80 DEG C to get H-P-TiO is arrived2-δ(400) catalyst；
By 70mg H-P-TiO2-δ(400) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 8mL water is added in reactor bottom, after air drains in kettle, then is passed through 20bar CO2, room temperature simulation sunlight
Irradiation is lower to react 1h, the results are shown in Table 1.
Embodiment 6:
By 700mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 8:2) it is scattered in 30mL ethylenediamine, 0.2h is stirred, the lithium metal of 300mg is added, then by the mixing
System keeps the temperature 48h at 140 DEG C, filters after cooling and is 0.1mol L with concentration–1Hydrochloric acid solution sufficiently wash, then with water and
Alcohol sufficiently washs, and gained sediment dries 30h at 50 DEG C to get H-P-TiO is arrived2-δ(300) catalyst；
By 100mg H-P-TiO2-δ(300) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 4mL water is added in reactor bottom, after air drains in kettle, then is passed through 3bar CO2, room temperature simulation solar irradiation
Lower reaction 6h is penetrated, the results are shown in Table 1.
Embodiment 7:
By 500mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 7:3) it is scattered in 30mL ethylenediamine, 2h is stirred, the lithium metal of 100mg is added, then by the mixture
It ties up at 130 DEG C and keeps the temperature 40h, filtered after cooling and be 0.1mol L with concentration–1Hydrochloric acid solution sufficiently wash, then with water and wine
Smart sufficiently washing, gained sediment at 25 DEG C dry 30h to get arriving H-P-TiO2-δ(100) catalyst；
By 80mg H-P-TiO2-δ(100) catalyst fines are dispersed in water, then drop coating is placed in instead in sheet glass
Device top is answered, 5mL water is added in reactor bottom, after air drains in kettle, then is passed through 6bar CO2, room temperature simulation solar irradiation
Lower reaction 8h is penetrated, the results are shown in Table 1.
Embodiment 8:
By 200mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 7:3) it is scattered in 15mL ethylenediamine, 4h is stirred, the lithium metal of 50mg is added, then by the mixed system
18h is kept the temperature at 190 DEG C, is filtered after cooling and is 0.2mol L with concentration–1Hydrochloric acid solution sufficiently wash, then with water and alcohol
Sufficiently washing, gained sediment dry 25h at 0 DEG C to get H-P-TiO is arrived2-δ(50) catalyst；
By 60mg H-P-TiO2-δ(50) catalyst fines are dispersed in water, then drop coating is placed in reaction in sheet glass
Device top is added 3mL water in reactor bottom, after air drains in kettle, then is passed through 8bar CO2, the irradiation of room temperature simulation sunlight
Lower reaction 4h, the results are shown in Table 1.
Embodiment 9:
By 500mg anatase and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and Rutile Type titanium dioxide
The mass ratio of titanium is 7:3) it is scattered in 30mL ethylenediamine, 5h is stirred, any alkali metal is added without, then the mixed system exists
It is kept the temperature at 180 DEG C for 24 hours, is filtered after cooling and be 0.05mol L with concentration–1Hydrochloric acid solution sufficiently wash, then with water and alcohol
Sufficiently washing, gained sediment dry 30h at 60 DEG C to get H-P-TiO is arrived2-δ(0) catalyst；
By 40mg H-P-TiO2-δ(0) catalyst fines are dispersed in water, then drop coating is placed in reaction in sheet glass
Device top is added 4mL water in reactor bottom, after air drains in kettle, then is passed through 4bar CO2, the irradiation of room temperature simulation sunlight
Lower reaction 5h, the results are shown in Table 1.
Table 1 is that the blue titanium dioxide catalyst of embodiment 1-9 preparation is the performance parameter of methane to carbon dioxide conversion:
The photochemical catalyst as made from the above method will be for that can will contain a small amount of H under the irradiation of room temperature simulated solar irradiation2The CO of O2
It is converted into CH4, show higher activity, CH4Selectivity and stability, and it is mild, low in cost etc. excellent with preparation method
Point.From the figure 3, it may be seen that in simulated solar irradiation illumination 5h, room temperature, 2bar CO2Under a small amount of aqueous vapor existence condition, H-P-TiO2-δ
(200) 79% is up to the selectivity of methane, the generating rate of methane is 16.2 μm of ol g-1h-1, six times circulation after still maintain
In 15 μm of ol g-1h-1More than.Fig. 1 is H-P-TiO prepared by the embodiment of the present invention 12-δ(200) high-resolution transmission electron microscopy
Mirror photo, as can be seen from the figure prepared surface is modified H-X-TiO2-δ(200) a kind of unique nucleocapsid structure is shown,
It is TiO that it is internal2The nuclei of crystallization, outside are the TiO containing a large amount of Lacking oxygens2-δAmorphous shell (with a thickness of 2~3nm).Fig. 2 is this
H-P-TiO prepared by inventive embodiments 12-δ(200) hydrogen nuclear magnetic resonance spectrogram, as can be seen from the figure prepared surface changes
Property H-X-TiO2-δ(200) contain a large amount of H atoms in surface.
Claims (10)
1. a kind of preparation method of blue titanium dioxide, which is characterized in that by alkali metal, titanium dioxide and ethylenediamine mix after
Behind solvent thermal reaction 10~48 hours at 100~200 DEG C, then washed, drying, blue titanium dioxide is obtained.
2. preparation method according to claim 1, which is characterized in that the titanium dioxide be anatase phase titanium dioxide,
At least one of red schorl phase titanium dioxide, brookite titanium dioxide.
3. preparation method according to claim 2, which is characterized in that the titanium dioxide be anatase phase titanium dioxide,
The mixed phase of red schorl phase titanium dioxide, brookite titanium dioxide or anatase titania phase and red schorl phase titanium dioxide.
4. preparation method according to claim 2, which is characterized in that when titanium dioxide is anatase phase titanium dioxide and gold
When the mixed phase of red stone phase titanic oxide, the mass ratio of the anatase phase titanium dioxide and red schorl phase titanium dioxide be (0.1~
9): 1.
5. preparation method according to claim 1, which is characterized in that the alkali metal is lithium, sodium, at least one in potassium
Kind.
6. preparation method according to claim 1, which is characterized in that the ratio of the titanium dioxide and ethylenediamine be (100~
900) mg:(10~60) ml.
7. preparation method according to claim 1, which is characterized in that the mass ratio of the alkali metal and titanium dioxide is 1:
(1~10).
8. preparation method according to claim 7, which is characterized in that the mass ratio of the alkali metal and titanium dioxide is 1:
(3~8).
9. preparation method according to claim 1, which is characterized in that it is 0.01~0.5 mol that the washing, which is with concentration,
L–1Acid solution wash, then with water and ethanol wash.
10. preparation method according to claim 1 to 9, which is characterized in that the temperature of the drying be -10~
150 DEG C, the time is 10~30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108369.4A CN107827152B (en) | 2017-11-09 | 2017-11-09 | Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108369.4A CN107827152B (en) | 2017-11-09 | 2017-11-09 | Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107827152A CN107827152A (en) | 2018-03-23 |
| CN107827152B true CN107827152B (en) | 2019-07-16 |
Family
ID=61655097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711108369.4A Active CN107827152B (en) | 2017-11-09 | 2017-11-09 | Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107827152B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939053B (en) * | 2021-01-29 | 2022-11-11 | 浙江大学 | Method for preparing transition metal oxide material containing oxygen vacancy |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895964A (en) * | 2012-10-18 | 2013-01-30 | 南京工业大学 | Preparation method for blue sheet-like titanium dioxide nanomaterial |
| CN103482698A (en) * | 2013-09-10 | 2014-01-01 | 中国科学院合肥物质科学研究院 | Nanometer blue titanium dioxide colloid and preparation method and application thereof |
| CN103553124A (en) * | 2013-11-08 | 2014-02-05 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN104437449A (en) * | 2014-12-09 | 2015-03-25 | 黑龙江大学 | Preparation method of black titanium dioxide visible light photocatalyst |
| CN106582595A (en) * | 2016-12-28 | 2017-04-26 | 上海应用技术大学 | Preparation method for blue TiO2 catalyst |
| CN107244695A (en) * | 2017-07-17 | 2017-10-13 | 河南师范大学 | The method of controlledly synthesis diverse microcosmic appearance blue titanium dioxide nano-powder |
| CN107686129A (en) * | 2017-08-01 | 2018-02-13 | 中国科学院合肥物质科学研究院 | A kind of TiO2The solvent process for thermosynthesizing of flower-shaped hierarchy sub-micron ball |
-
2017
- 2017-11-09 CN CN201711108369.4A patent/CN107827152B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895964A (en) * | 2012-10-18 | 2013-01-30 | 南京工业大学 | Preparation method for blue sheet-like titanium dioxide nanomaterial |
| CN103482698A (en) * | 2013-09-10 | 2014-01-01 | 中国科学院合肥物质科学研究院 | Nanometer blue titanium dioxide colloid and preparation method and application thereof |
| CN103553124A (en) * | 2013-11-08 | 2014-02-05 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN104437449A (en) * | 2014-12-09 | 2015-03-25 | 黑龙江大学 | Preparation method of black titanium dioxide visible light photocatalyst |
| CN106582595A (en) * | 2016-12-28 | 2017-04-26 | 上海应用技术大学 | Preparation method for blue TiO2 catalyst |
| CN107244695A (en) * | 2017-07-17 | 2017-10-13 | 河南师范大学 | The method of controlledly synthesis diverse microcosmic appearance blue titanium dioxide nano-powder |
| CN107686129A (en) * | 2017-08-01 | 2018-02-13 | 中国科学院合肥物质科学研究院 | A kind of TiO2The solvent process for thermosynthesizing of flower-shaped hierarchy sub-micron ball |
Non-Patent Citations (3)
| Title |
|---|
| Guilian Zhu等.Hydrogenated blue titania with high solar absorption and greatly improved photocatalysis.《Nanoscale》.2016,第2016卷(第8期),第47055-4711页. * |
| Hydrogenated blue titania with high solar absorption and greatly improved photocatalysis;Guilian Zhu等;《Nanoscale》;20160128;第2016卷(第8期);第4705-4712页 * |
| Photocatalytic CO2 conversion over alkali modified TiO2 without loading noble metal cocatalyst;Xianguang Meng等;《ChemComm》;20140806;第2014卷(第50期);第11517-11519页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107827152A (en) | 2018-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106914264B (en) | The preparation method of composite visible light catalyst | |
| CN106238086B (en) | A kind of phenyl ring modification class graphite phase carbon nitride photochemical catalyst and preparation method and application | |
| CN105771948B (en) | The preparation method of bivalve titanium deoxide catalyst with high photocatalysis hydrogen production performance | |
| CN106745226B (en) | Micro-nano titanium dioxide and preparation method and application based on eutectic solvent synthesis | |
| CN104707542B (en) | A kind of photochemical catalyst/SiO2aerogel composite and preparation method thereof | |
| CN104324733B (en) | The preparation method of non precious metal high activity photolytic hydrogen production catalyst | |
| CN101811044A (en) | Potassium niobate nanotube photocatalyst and preparation method and application thereof | |
| CN100396373C (en) | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst | |
| CN102658180A (en) | Core-shell TiO2-BiOCl heterojunction photocatalyst with large specific surface area and preparation method thereof | |
| CN106268902B (en) | A kind of preparation method of g-C3N4 quantum dot, the quantum dot sensitized BiVO4 photochemical catalyst of Ag | |
| CN103130267A (en) | Preparation method for visible-light response black titanium dioxide photocatalyst | |
| CN109985618A (en) | A kind of H occupies BiVO4The catalysis material of-OVs, preparation method and applications | |
| CN106475127A (en) | A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof | |
| CN108452805B (en) | NiTiO for photolyzing water to produce hydrogen3/TiO2Catalyst, preparation method and application thereof | |
| Khusnun et al. | Influence of TiO2 dispersion on silica support toward enhanced amine assisted CO2 photoconversion to methanol | |
| CN107827152B (en) | Blue titanium dioxide and preparation method thereof for carbon dioxide photocatalysis synthesizing methane | |
| Yue et al. | A facile synthesis method of TiO2@ SiO2 porous core shell structure for photocatalytic hydrogen evolution | |
| CN110026224A (en) | A kind of cobaltosic oxide modifies the preparation method of mesoporous azotized carbon nano composite material | |
| CN104043463A (en) | Preparation method of photocatalyst capable of degrading polyacrylamide under response of visible light and application of photocatalyst | |
| Wu et al. | Preparation of N-TiO2/SiO2 composites by solvothermal method and their photocatalytic properties | |
| CN101947459B (en) | Visible light active boron nitrogen codope titanium dioxide hollow sphere catalyst and preparation method thereof | |
| CN113856702A (en) | Cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst and preparation method and application thereof | |
| CN102527421A (en) | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof | |
| CN103418394B (en) | Method for synthesizing nickel-doped indium vanadate nanocrystalline photocatalyst by adopting microwave heating method and application thereof for water decomposition under visible light | |
| CN109174123A (en) | A kind of Z-type CdS-Ag-TiO2Composite photocatalyst material and its preparation method and application |
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 |