CN107827152A - Blue titanium dioxide for carbon dioxide photocatalysis synthesizing methane and preparation method thereof - Google Patents
Blue titanium dioxide for carbon dioxide photocatalysis synthesizing methane and preparation method thereof Download PDFInfo
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- CN107827152A CN107827152A CN201711108369.4A CN201711108369A CN107827152A CN 107827152 A CN107827152 A CN 107827152A CN 201711108369 A CN201711108369 A CN 201711108369A CN 107827152 A CN107827152 A CN 107827152A
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- anatase
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 298
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 120
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 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 20
- 229910000246 schorl Inorganic materials 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910001258 titanium gold Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 96
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000005406 washing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000001548 drop coating Methods 0.000 description 10
- 150000002171 ethylene diamines Chemical class 0.000 description 10
- 239000013049 sediment Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 9
- 238000004088 simulation Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000004087 circulation Effects 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
- 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
- 241001062009 Indigofera Species 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
- 238000006757 chemical reactions by type 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
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 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
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- 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 blue titanium dioxide for carbon dioxide photocatalysis synthesizing methane and preparation method thereof, the preparation method includes：After alkali metal, titanium dioxide and ethylenediamine are mixed blue titanium dioxide is obtained at 100~200 DEG C behind solvent thermal reaction 10~48 hours, then scrubbed, drying.Blue titanium dioxide photochemical catalyst prepared by the present invention has an excellent photocatalysis performance for carbon dioxide and water are converted into methane reaction compared with same type material, and with preparation method is gentle, controllable, low cost and other advantages.
Description
Technical field
The present invention relates to blue titanium dioxide for carbon dioxide photocatalysis synthesizing methane and preparation method thereof, belonging to
Chemical catalyst technical field.
Background technology
As abundant, nontoxic, reproducible carbon resource, CO2Gas can be widely used in producing hydro carbons, alcohols and formic acid etc.
High level chemicals.At present, CO2Photocatalysis synthesizing methane is paid high attention to by domestic and foreign scholars.The realization of the process, not only will
Clean reproducible solar energy and be 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 rings.The research and development of high efficiency photocatalyst turn into CO2Synthesize the key of high level chemicals (such as methane).
It is presently used for CO2The catalyst of synthesizing methane course of reaction mainly has photochemical catalyst, elctro-catalyst and thermocatalyst
Deng.Photochemical catalyst utilizes and cleans reproducible solar energy by CO2It is considered as to solve energy crisis and environment dirt to be reduced into fuel
The desirable route of dye.Titanium dioxide is as a kind of oxide semiconductor material, because its is environment-friendly, chemical property is stable, valency
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 its limited electron hole pair suppresses with transmittability
It is further to apply.People have been working hard attempt to pass through doping metals (Fe, Co, Ni, Mn, Cr etc.) or non-for many years
Metal (N, S, C, I etc.) changes the band structure of titanium dioxide, coloured titanium dioxide is prepared, to realize sunshine
Wide spectrum absorbs.Hydrogenation titanium dioxide obtains due to showing good Photocatalyzed Hydrogen Production and photocatalysis contaminant degradation performance
Extensive concern.Chen et al. is heat-treated titanium dioxide at 200 DEG C using 20bar high-purity hydrogens and obtains within five days hydrogenating black two
Titanium oxide (Science 2011,331,746.).Sun et al. is heat-treated dioxy also with 70bar high-purity hydrogens at 450 DEG C
Change titanium to obtain hydrogenating 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 normal temperature, but Hydrogen Vapor Pressure reaches 35bar, and 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 preparation process is dangerous, power consumption is high, and prepared coloured titanium dioxide is less is successfully applied to
Photocatalysis CO2Synthesizing methane process.
In a word, current all kinds of photocatalysis CO2The coloured titanium dioxide preparation condition of reduction is harsh, and preparation temperature is high, power consumption
Height, hazardous gas hydrogen etc. need to be used.Therefore, it is necessary to develop one kind can compared with temperate condition and possess wide spectrum response have
The preparation method of color titanium dioxide optical catalyst.
The content 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, power consumption is higher, its object is to provide under a kind of temperate condition
High activity, the blue titanium dioxide photochemical catalyst and preparation method thereof of high selectivity and high stability.
On the one hand, the invention provides a kind of preparation method of blue titanium dioxide, by alkali metal, titanium dioxide and second two
After amine mixing blue titanium dioxide is obtained at 100~200 DEG C behind solvent thermal reaction 10~48 hours, then scrubbed, drying.
Alkali metal is incorporated 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.
It is preferred that 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 ore deposit titanium dioxide phase and red schorl phase titanium dioxide.
Also, it is preferred that 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.
It is preferred that the alkali metal is at least one of lithium, sodium, potassium.
It is preferred that the ratio of the titanium dioxide and ethylenediamine is (100~900) mg：(10~60) ml, can more preferably promote shell
Nuclear structure and the decrystallized formation of surface hydriding.
It is preferred that the mass ratio of the alkali metal and titanium dioxide is 1：(1~10), preferably 1：(3~8), can more preferably it promote
Enter the decrystallized formation of core-shell structure and surface.
It is preferred that described wash to be 0.01~0.5mol L with concentration–1Hydrochloric acid solution washing, then washed with water and alcohol
Wash.
It is preferred that the temperature of the drying is -10~150 DEG C, the time is 10~30 hours.
On the other hand, present invention also offers a kind of blue titanium dioxide prepared according to above-mentioned preparation method, the indigo plant
Color titanium dioxide includes titanium dioxide crystal core and be coated on the titanium dioxide crystal core surface contain 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
Different crystalline phase titanium dioxide (Anatase A, Rutile Type R, brookite B or anatase and rutile mixed phase P) are represented, y is
The alkali metal quality (unit mg) added in preparation process.(surface is modified H-X-TiO to prepared blue titanium dioxide2-δ(y))
A kind of unique nucleocapsid structure is shown, it is titanium dioxide crystal core that it is internal, 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 cause the change of titanium dioxide color, significantly
Increase the absorption and utilization to sunshine.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.
Another further aspect, present invention also offers a kind of above-mentioned blue titanium dioxide in carbon dioxide photocatalysis synthesizing methane
Application.
Blue titanium dioxide photochemical catalyst prepared by the present invention is and same for carbon dioxide and water are converted into methane reaction
Types of material has that preparation method is gentle, controllable, low cost and other advantages compared to having an excellent photocatalysis performance.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 circulations
Still maintain 15 μm of ol g–1h–1More than.
Brief description of the drawings
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.
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 represents different crystalline 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) added in preparation process.Wherein, prepared surface is modified H-X-
TiO2-δ(y) a kind of unique nucleocapsid structure is shown, it is titanium dioxide crystal core that it is internal, 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 scrubbed, 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, such as can be alkali metal to 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), preferably 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 ore deposit phase titanic oxide (B), preferably can be anatase phase titanium dioxide, red schorl phase titanium dioxide, brockite
Phase titanic oxide or the mixed phase of anatase titania phase and red schorl phase titanium dioxide (P).And when titanium dioxide is anatase
During 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.
It is described to wash as that be 0.01~0.5mol L with concentration in the present invention–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, including：(1) by 100~900mg
Titanium dioxide is scattered in 10~60mL ethylenediamines, stirs 0.1~5h, adds 0~400mg alkali metal；(2) by step
(1) mixed system 10~48h of solvent heat at 100~200 DEG C in；(3) material after solvent heat in step (2) is filtered and be used in combination
Concentration is 0.01~0.5mol L–1Hydrochloric acid solution fully wash, then fully washed with water and alcohol；(4) by step (3)
Sediment dries 10~30h at -10~150 DEG C, obtains blue titanium dioxide H-X-TiO2-δ(y) catalyst.
In the present invention, all catalytic reactions of the blue titanium dioxide are 100mL in volume and top is equipped with saturating
Carried out in the tank reactor of light quartz plate.A certain amount of catalyst fines is 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 react 1~10h under simulated solar light irradiation, product directly with mass spectrograph and
Gas chromatograph carries out qualitative and quantitative analysis.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope 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 this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1：
By 500mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 7：3) it is scattered in 30mL ethylenediamines, stirs 0.5h, 200mg lithium metal is added, then by the mixed system
24h is incubated at 180 DEG C, after cooling filter and be 0.1mol L with concentration–1Hydrochloric acid solution fully wash, then with water and alcohol
Fully washing, gained sediment dry 20h at -10 DEG C, that is, obtain H-P-TiO2-δ(200) catalyst；
By 50mg H-P-TiO2-δ(200) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 4mL water, kettle, then it is passed through 2bar CO2, under the irradiation of room temperature simulation sunshine
5h is reacted, the results are shown in Table 1.
Embodiment 2：
400mg anatase phase titanium dioxides (A) are scattered in 20mL ethylenediamines, stir 2h, add 300mg metallic sodium,
Then the mixed system is incubated 32h at 160 DEG C, after cooling filter and be 0.2mol L with concentration–1Hydrochloric acid solution it is abundant
Washing, then fully washed with water and alcohol, gained sediment dries 30h at 10 DEG C, that is, obtains H-A-TiO2-δ(300) it is catalyzed
Agent；
By 30mg H-A-TiO2-δ(300) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 6mL water, kettle, then it is passed through 5bar CO2, under the irradiation of room temperature simulation sunshine
3h is reacted, the results are shown in Table 1.
Embodiment 3：
600mg red schorl phase titanium dioxides (R) are scattered in 15mL ethylenediamines, stir 5h, add 100mg metallic potassium,
Then the mixed system is incubated 12h at 200 DEG C, after cooling filter and be 0.5mol L with concentration–1Hydrochloric acid solution it is abundant
Washing, then fully washed with water and alcohol, gained sediment dries 15h at 100 DEG C, that is, obtains H-R-TiO2-δ(100) it is catalyzed
Agent；
By 60mg H-R-TiO2-δ(100) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 2mL water, kettle, then it is passed through 10bar CO2, the irradiation of room temperature simulation sunshine
Lower reaction 10h, the results are shown in Table 1.
Embodiment 4：
900mg brookites titanium dioxide (B) is scattered in 25mL ethylenediamines, stirs 0.5h, adds 400mg metal
Sodium, the mixed system is then incubated 48h at 150 DEG C, after cooling filter and be 0.01mol L with concentration–1Hydrochloric acid solution
Fully washing, then fully washed with water and alcohol, gained sediment dries 10h at 150 DEG C, that is, obtains H-B-TiO2-δ(400)
Catalyst；
By 90mg H-B-TiO2-δ(400) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 8mL water, kettle, then it is passed through 6bar CO2, under the irradiation of room temperature simulation sunshine
4h is reacted, the results are shown in Table 1.
Embodiment 5：
By 600mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 6：4) it is scattered in 20mL ethylenediamines, stirs 0.1h, 400mg lithium metal is added, then by the mixed system
36h is incubated at 170 DEG C, after cooling filter and be 0.05mol L with concentration–1Hydrochloric acid solution fully wash, then with water and wine
Smart fully washing, gained sediment dry 25h at 80 DEG C, that is, obtain H-P-TiO2-δ(400) catalyst；
By 70mg H-P-TiO2-δ(400) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 8mL water, kettle, then it is passed through 20bar CO2, the irradiation of room temperature simulation sunshine
Lower reaction 1h, the results are shown in Table 1.
Embodiment 6：
By 700mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 8：2) it is scattered in 30mL ethylenediamines, stirs 0.2h, 300mg lithium metal is added, then by the mixed system
48h is incubated at 140 DEG C, after cooling filter and be 0.1mol L with concentration–1Hydrochloric acid solution fully wash, then with water and alcohol
Fully washing, gained sediment dry 30h at 50 DEG C, that is, obtain H-P-TiO2-δ(300) catalyst；
By 100mg H-P-TiO2-δ(300) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 4mL water, kettle, then it is passed through 3bar CO2, under the irradiation of room temperature simulation sunshine
6h is reacted, the results are shown in Table 1.
Embodiment 7：
By 500mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 7：3) it is scattered in 30mL ethylenediamines, stirs 2h, add 100mg lithium metal, then the mixed system exists
40h is incubated at 130 DEG C, after cooling filter and be 0.1mol L with concentration–1Hydrochloric acid solution fully wash, then filled with water and alcohol
Divide washing, gained sediment dries 30h at 25 DEG C, that is, obtains H-P-TiO2-δ(100) catalyst；
By 80mg H-P-TiO2-δ(100) catalyst fines is dispersed in water, then drop coating is placed in reactor in sheet glass
Top, after air drains in reactor bottom addition 5mL water, kettle, then it is passed through 6bar CO2, under the irradiation of room temperature simulation sunshine
8h is reacted, the results are shown in Table 1.
Embodiment 8：
By 200mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 7：3) it is scattered in 15mL ethylenediamines, stirs 4h, add 50mg lithium metal, then the mixed system exists
18h is incubated at 190 DEG C, after cooling filter and be 0.2mol L with concentration–1Hydrochloric acid solution fully wash, then filled with water and alcohol
Divide washing, gained sediment dries 25h at 0 DEG C, that is, obtains H-P-TiO2-δ(50) catalyst；
By 60mg H-P-TiO2-δ(50) catalyst fines is dispersed in water, then drop coating is placed on reactor in sheet glass
Portion, after air drains in reactor bottom addition 3mL water, kettle, then it is passed through 8bar CO2, it is anti-under the irradiation of room temperature simulation sunshine
4h is answered, the results are shown in Table 1.
Embodiment 9：
By 500mg anatases and rutile mixed phase titanium dioxide (P) (anatase phase titanium dioxide and red schorl phase titanium dioxide
Mass ratio is 7：3) it is scattered in 30mL ethylenediamines, stirs 5h, any alkali metal is added without, then by the mixed system 180
24h is incubated at DEG C, after cooling filter and be 0.05mol L with concentration–1Hydrochloric acid solution fully wash, it is then abundant with water and alcohol
Washing, gained sediment dry 30h at 60 DEG C, that is, obtain H-P-TiO2-δ(0) catalyst；
By 40mg H-P-TiO2-δ(0) catalyst fines is dispersed in water, then drop coating is placed on reactor in sheet glass
Portion, after air drains in reactor bottom addition 4mL water, kettle, then it is passed through 4bar CO2, it is anti-under the irradiation of room temperature simulation sunshine
5h is answered, the results are shown in Table 1.
Table 1 is the performance parameter that blue titanium dioxide catalyst prepared by embodiment 1-9 is methane to carbon dioxide conversion：
It is used to that under normal temperature simulated solar light irradiation a small amount of H can will be contained by photochemical catalyst made from the above method2O CO2
It is converted into CH4, show higher activity, CH4Selectivity and stability, and with that preparation method is gentle, cost is cheap etc. is excellent
Point.From the figure 3, it may be seen that in simulated solar irradiation illumination 5h, normal 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, still maintained after six circulations
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 be 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 is the TiO containing a large amount of Lacking oxygens2-δAmorphous shell (thickness is 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 change
Property H-X-TiO2-δ(200) a large amount of H atoms are contained in surface.
Claims (10)
- A kind of 1. preparation method of blue titanium dioxide, it is characterised in that by alkali metal, titanium dioxide and ethylenediamine mix after Behind solvent thermal reaction 10~48 hours at 100~200 DEG C, then scrubbed, drying, blue titanium dioxide is obtained.
- 2. preparation method according to claim 1, it is characterised in that the titanium dioxide be anatase phase titanium dioxide, At least one of red schorl phase titanium dioxide, brookite titanium dioxide, preferably anatase phase titanium dioxide, Rutile Type Titanium dioxide, brookite titanium dioxide or the mixed phase of anatase titania phase and red schorl phase titanium dioxide.
- 3. preparation method according to claim 2, it is characterised in that when titanium dioxide is anatase phase titanium dioxide and gold During the mixed phase of red stone phase titanic oxide, the mass ratio of the anatase phase titanium dioxide and red schorl phase titanium dioxide is（0.1~ 9）：1.
- 4. according to the preparation method any one of claim 1-3, it is characterised in that the alkali metal is in lithium, sodium, potassium At least one.
- 5. according to the preparation method any one of claim 1-4, it is characterised in that the titanium dioxide and ethylenediamine Than for（100~900）mg：（10~60）ml.
- 6. according to the preparation method any one of claim 1-5, it is characterised in that the alkali metal and titanium dioxide Mass ratio is 1：（1~10）, preferably 1：（3~8）.
- 7. according to the preparation method any one of claim 1-6, it is characterised in that described to wash to be 0.01 with concentration ~0.5 mol L–1Acid solution wash, then with water and ethanol wash.
- 8. according to the preparation method any one of claim 1-7, it is characterised in that the temperature of the drying be -10~ 150 DEG C, the time is 10~30 hours.
- A kind of 9. blue titanium dioxide prepared by preparation method according to any one of claim 1-8, it is characterised in that institute State that blue titanium dioxide includes titanium dioxide crystal core and be coated on the titanium dioxide crystal core surface contain Lacking oxygen and H The titanium oxide amorphous shell of atom.
- A kind of 10. application of the blue titanium dioxide in carbon dioxide photocatalysis synthesizing methane as claimed in claim 9.
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