CN110449148A - Transient metal doped single layer titanium dioxide nanoplate and preparation method thereof - Google Patents
Transient metal doped single layer titanium dioxide nanoplate and preparation method thereof Download PDFInfo
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- CN110449148A CN110449148A CN201910572067.5A CN201910572067A CN110449148A CN 110449148 A CN110449148 A CN 110449148A CN 201910572067 A CN201910572067 A CN 201910572067A CN 110449148 A CN110449148 A CN 110449148A
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- titanium dioxide
- layer titanium
- dioxide nanoplate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002356 single layer Substances 0.000 title claims abstract description 53
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 239000002055 nanoplate Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 230000001052 transient effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000725 suspension Substances 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000005119 centrifugation Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- 239000011636 chromium(III) chloride Substances 0.000 claims description 5
- 239000011565 manganese chloride Chemical group 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims 2
- 230000007704 transition Effects 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 30
- 239000001257 hydrogen Substances 0.000 abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 30
- 125000004429 atom Chemical group 0.000 abstract description 10
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000227 grinding Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910019426 CoxO4 Inorganic materials 0.000 description 2
- 229910003911 NixO4 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/23—
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- B01J35/39—
-
- B01J35/612—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to photocatalysis liberation of hydrogen technical fields, disclose a kind of transient metal doped single layer titanium dioxide nanoplate and preparation method thereof, the transition metal element of doping is Ni, Mn, Fe, Co, Cr, Cu, and atom content 1-10%, the area of nanometer sheet is 10-100 μm2；Preparation process is first by CsCO3、TiO2It is mixed with the hydrochloride of transition metal element M；Mixture is repeated to two-stage calcining at high temperature；Sample and HCl solution mixing are protonated, is filtered, washed, air-dries later；Sediment is stirred in quaternary ammonium aqueous alkali and forms colloidal nano piece suspension；Water is finally added in colloidal nano piece suspension, centrifugation removal quaternary ammonium aqueous alkali is dried to obtain transient metal doped single layer titanium dioxide nanoplate powder.The present invention influences surface oxygen atoms by the method for containing transition metal to hydrionic adsorption capacity, to improve hydrogen-producing speed.
Description
Technical field
The invention belongs to photocatalysis liberation of hydrogen technical fields, are that a kind of liberation of hydrogen that transition metal is trace doped is urged specifically
Agent and preparation method thereof.
Technical background
A large amount of consumption of traditional energy have had resulted in serious environmental pollution, such as haze, global warming, the salinization of soil
Etc..Accordingly, it is desirable to find clean reproducible energy to replace these traditional energies.It is well known that hydrogen energy source is considered as
21 century most potential clean reproducible energy, currently, most environmentally friendly liberation of hydrogen process is photolysis water hydrogen gas --- it will
Solar energy is converted into the chemical energy of hydrogen form.And for light-catalyzed reaction, an effective catalyst is essential
's.Before, it has been found that metal platinum is expected to there are higher liberation of hydrogen photocatalytic activity as ideal catalyst, but due to
The problems such as content of metal platinum is less in the Nature, and production cost is higher, to limit its extensive use industrially.
From researchers in 1972 in TiO2Photochemical catalyzing is found on Single Crystalline Electrodes and after generating hydrogen, TiO2By
The highest attention of researchers.Recently, researchers successfully separate a kind of novel single layer titanium dioxide nanoplate ---
Lepidocrocite type titanium dioxide nanoplate, since itself energy band is wider, bandedge placement meets the condition of oxidation-reduction potential and higher
Carrier mobility etc., and preparation process is relatively simple, therefore this single layer titanium dioxide nanoplate is expected to become light
Solve the catalyst of water hydrogen manufacturing.But catalytic efficiency it is low the problems such as hinder it in the application of related fields.Therefore, the present invention is uncommon
Prestige sought by the method for material modification the high single layer titanium dioxide nanoplate of catalytic activity with and preparation method thereof.
Summary of the invention
The present invention put forth effort on solve single layer titanium dioxide nanoplate surface layer oxygen atom hydrophily it is weaker, hydrogen ion is not easy to inhale
It is attached on surface oxygen atoms, the technical problem of hydrogen activity deficiency is produced so as to cause it, a kind of transient metal doped single layer is provided
Titanium dioxide nanoplate and preparation method thereof influences surface oxygen atoms by the method for containing transition metal to hydrionic suction
Attached ability, to improve hydrogen-producing speed.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
A kind of transient metal doped single layer titanium dioxide nanoplate, single layer titanium dioxide nanoplate is doped with transition metal
Element M, the transition metal element M of doping are one of Ni, Mn, Fe, Co, Cr, Cu, the original of the transition metal element
Sub- 100% × M/ of content (Ti+M) is 1-10%；Transition metal element can significantly improve liberation of hydrogen as effective co-catalyst
Rate；And when the atomic percent of transition metal element is less than 1%, foreign atom does not have the effect for improving liberation of hydrogen rate,
When the atomic percent of transition metal element is greater than 2%, liberation of hydrogen efficiency can be declined.
And the transient metal doped single layer titanium dioxide nanoplate is obtained by following preparation method:
(1) by CsCO3、TiO2With the hydrochloride of transition metal element M, water is added to be mixed, is heat-treated steams water later
Hair, obtains Cs0.7Ti1.82-xMxO4, 0 x≤0.2 <；Wherein, the hydrochloride of the transition metal element M is NiCl2、MnCl2、
FeCl3、CoCl2、CrCl3、CuCl2One of；
(2) mixture for again obtaining step (1) is in the environment of containing oxygen in 400 DEG C of -500 DEG C of calcining 55-
65min continues calcining 18-22 hours at 800 DEG C -1000 DEG C after grinding；The above process in this step operates 1-2 times；
(3) HCl solution that the sample for obtaining step (2) and concentration are 0.08-0.12mol/L according to 0.008~
The ratio of 0.012g/mL mixes, and stirring is protonated for 60-75 hours, is filtered, washed later, removes extra acid, and wind
It is dry；
(4) sediment for obtaining step (3) stirs 6-7 days in the quaternary ammonium aqueous alkali of 0.02-0.03mol/L, shape
At colloid nanometer sheet suspension
(5) water is added in the colloidal nano piece suspension that step (4) obtains, the quaternary ammonium in the suspension of centrifugation removal later
Aqueous alkali, then be dried, obtain transient metal doped single layer titanium dioxide nanoplate powder.
Wherein, the area of transient metal doped single layer titanium dioxide nanoplate is 10-100 μm2。
Preferably, the x value in step (1) is 0.02-0.2.
Preferably, in 400 DEG C of -500 DEG C of temperature lower calcination 60min in step (2), in 800 DEG C of -1000 DEG C of temperature lower calcinations
20 hours.
Preferably, the concentration of HCl solution is 0.01g/mL in step (3).
Preferably, the ratio of sample and HCl solution is 1:1mg/L in step (3).
Preferably, the mixing time protonated in step (3) is 72 hours.
Preferably, the quaternary ammonium aqueous alkali in step (4) selects the tetrabutylammonium hydroxide aqueous solution of 0.025mol/L.
A kind of preparation method of above-mentioned transient metal doped single layer titanium dioxide nanoplate carries out in accordance with the following steps:
(1) by CsCO3、TiO2With the hydrochloride of transition metal element M, water is added to be mixed, is heat-treated steams water later
Hair, obtains Cs0.7Ti1.82-xMxO4(0 x≤0.2 <)；Wherein, the hydrochloride of the transition metal element M is NiCl2、MnCl2、
FeCl3、CoCl2、CrCl3、CuCl2One of；
(2) mixture for again obtaining step (1) is in the environment of containing oxygen in 400 DEG C of -500 DEG C of calcining 55-
65min continues calcining 18-22 hours at 800 DEG C -1000 DEG C after grinding；The above process in this step operates 1-2 times；
(3) HCl solution that the sample for obtaining step (2) and concentration are 0.08-0.12mol/L according to 0.008~
The ratio of 0.012g/mL mixes, and stirring is protonated for 60-75 hours, is filtered, washed later, removes extra acid, and wind
It is dry；
(4) sediment for obtaining step (3) stirs 6-7 days in the quaternary ammonium aqueous alkali of 0.02-0.03mol/L, shape
At colloid nanometer sheet suspension
(5) water is added in the colloidal nano piece suspension that step (4) obtains, the quaternary ammonium in the suspension of centrifugation removal later
Aqueous alkali, then be dried, obtain transient metal doped single layer titanium dioxide nanoplate powder.
The beneficial effects of the present invention are:
(1) transient metal doped single layer titanium dioxide nanoplate and preparation method thereof of the invention, may be implemented larger
The doping of concentration, up to 1-10%, the doping of high concentration can swash the atom content of the transition metal element concentration of doping
More surface oxygen atoms living, to provide more active sites.
(2) transient metal doped single layer titanium dioxide nanoplate and preparation method thereof of the invention, can prepare larger face
Long-pending nanometer sheet, area is up to 10-100 μm2, be conducive to the nanometer sheet for preparing high-crystallinity in this way, reduce lacking in sample
Fall into concentration.
(3) to titanium dioxide nanoplate produced by the present invention carry out liberation of hydrogen rate test, and with undoped single layer two
TiOx nano piece is compared.Test result shows that the liberation of hydrogen rate of undoped single layer titanium dioxide nanoplate is about 5
μm ol/h, the liberation of hydrogen rate of transient metal doped single layer titanium dioxide nanoplate have clear improvement, for the system containing Cr,
Liberation of hydrogen rate has reached highest, is 10-12 times undoped with system.Meanwhile micro transient metal doped preparation process is more
Simply, the content of transition metal is also compared with horn of plenty and on the earth, therefore, regardless of in terms of liberation of hydrogen efficiency, or in preparation work
In terms of skill, the present invention is of great significance.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail:
Embodiment 1
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Cr doping, chemical formula Cs0.7Ti1.82-xCrxO4(x
=0.018,0.027,0.07,0.145).
By CsCO3, TiO2And CrCl3·6H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xCrxO4.Mixture is carried out to the calcining of 60min in air, temperature controls at 400 DEG C, exists again after grinding
20h is calcined at 800 DEG C.After repeating above-mentioned calcination process twice twice, obtained sample 0.5g is immersed in 0.1mol/L's
72h (ratio of sample and HCl solution is mg/L) is stirred in HCl solution 50mL, is filtered, washed later, is removed extra acid, and
And it air-dries；It is finally stirred 7 days in the tetrabutylammonium hydroxide aqueous solution of 0.025mol/L, the sediment that can will be obtained in this way
Removing forms colloidal nano piece suspension to single layer；Water finally is added in obtained colloidal nano piece suspension, is centrifuged later
The tetrabutylammonium hydroxide aqueous solution in suspension is removed, then is dried, the single layer titanium dioxide nanoplate of Cr doping is obtained
Powder.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Cr element is about 0.9%~7.8%.The sample that doping concentration is about 1.5% is chosen, is measured by microscope
The diameter of sample is about 8.2 μm, and the area of nanometer sheet is about 52.78 μm2, be conducive to good crystallinity, lesser defect is dense
Degree.Sample about 20mg is taken later, using methanol solution (percent by volume 20%) as reaction solution, is carried out in quartz reaction pond
Light source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate has reached 51
μm ol/h or so, for 10~12 times undoped with system.
Embodiment 2
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Mn doping, chemical formula Cs0.7Ti1.82-xMnxO4(x
=0.02,0.033,0.089,0.18).
By CsCO3, TiO2And MnCl2·4H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xMnxO4.Mixture is carried out to the calcining of 55min in air, temperature controls at 450 DEG C, exists again after grinding
19h is calcined at 900 DEG C.After repeating above-mentioned calcination process twice twice, obtained sample 0.45g is immersed in 0.12mol/L
HCl solution 50mL in stir 65h, be filtered, washed later, remove extra acid, and air-dry；Finally 0.02mol/L's
It is stirred in tetrabutylammonium hydroxide aqueous solution 7 days, obtained sediment can be removed in this way to single layer, form colloidal nano piece
Suspension；Water finally is added in obtained colloidal nano piece suspension, the tetrabutyl hydrogen-oxygen in the suspension of centrifugation removal later
Change aqueous ammonium, then be dried, obtains the single layer titanium dioxide nanoplate powder of Mn doping.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Mn element is about 1%~10%.The sample that doping concentration is about 1.8% is chosen, by being measured microscopically sample
Diameter be about 10.2 μm, the area of nanometer sheet is about 81.67 μm2, be conducive to good crystallinity, lesser defect density.
Sample about 22mg is taken later, and using methanol solution (percent by volume 20%) as reaction solution, light is carried out in quartz reaction pond
Source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate has reached 45 μ
Mol/h or so, for 9~10 times undoped with system.
Embodiment 3
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Fe doping, chemical formula Cs0.7Ti1.82-xFexO4(x
=0.018,0.024,0.055,0.112).
By CsCO3, TiO2And MnCl3·6H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xFexO4.Mixture is carried out to the calcining of 65min in air, temperature controls at 400 DEG C, exists again after grinding
20h is calcined at 850 DEG C.Later, obtained sample 0.5g is immersed in the HCl solution 50mL of 0.08mol/L and stirs 75h, it
After be filtered, washed, remove extra acid, and air-dry；Finally stirred in the tetrabutylammonium hydroxide aqueous solution of 0.03mol/L
6 days, obtained sediment can be removed in this way to single layer, form colloidal nano piece suspension；Finally received in obtained colloid
Water is added in rice piece suspension, the tetrabutylammonium hydroxide aqueous solution in the suspension of centrifugation removal later, then be dried, it obtains
The single layer titanium dioxide nanoplate powder of Fe doping.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Fe element is about 1%~6.2%.It is chosen at the sample that doping concentration is about 1.3%, is measured by microscope
The diameter of sample is about 11.2 μm, and the area of nanometer sheet is about 98.47 μm2, be conducive to good crystallinity, lesser defect is dense
Degree.Sample about 19mg is taken later, using methanol solution (percent by volume 20%) as reaction solution, is carried out in quartz reaction pond
Light source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate has reached 40
μm ol/h or so, for 7~8 times undoped with system.
Embodiment 4
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Co doping, chemical formula Cs0.7Ti1.82-xCoxO4(x
=0.022,0.055,0.123,0.165).
By CsCO3, TiO2And CoCl2·6H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xCoxO4.Mixture is carried out to the calcining of 55min in air, temperature controls at 500 DEG C, exists again after grinding
18h is calcined at 950 DEG C.After repeating above-mentioned calcination process twice twice, obtained sample 0.5g is immersed in 0.11mol/L's
68h is stirred in HCl solution 60mL, is filtered, washed later, removes extra acid, and air-dry；Finally the four of 0.03mol/L
It is stirred in butyl ammonium hydroxide aqueous solution 6 days, obtained sediment can be removed in this way to single layer, it is outstanding to form colloidal nano piece
Turbid；Water finally is added in obtained colloidal nano piece suspension, the tetrabutylammonium hydroxide in the suspension of centrifugation removal later
Aqueous ammonium, then be dried, obtain the single layer titanium dioxide nanoplate powder of Co doping.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Co element is about 1.2%~8.9%.The sample that doping concentration is about 1.2% is chosen, then by being surveyed with microscope
The diameter for measuring sample is about 3.8 μm, and the area of nanometer sheet is about 11.33 μm2, be conducive to good crystallinity, lesser defect
Concentration.Sample about 20mg is taken later, using methanol solution (percent by volume 20%) as reaction solution, in quartz reaction Chi Zhongjin
Line light source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate reaches
28 μm of ol/h or so, for 5~7 times undoped with system.
Embodiment 5
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Ni doping, chemical formula Cs0.7Ti1.82-xNixO4(x
=0.027,0.055,0.112,0.166).
By CsCO3, TiO2And NiCl2·6H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xNixO4.Mixture is carried out to the calcining of 60min in air, temperature controls at 400 DEG C, exists again after grinding
18h is calcined at 1000 DEG C.Later, obtained sample 0.6g is immersed in the HCl solution 50mL of 0.12mol/L and stirs 60h, it
After be filtered, washed, remove extra acid, and air-dry；Finally stirred in the tetrabutylammonium hydroxide aqueous solution of 0.025mol/L
It mixes 6 days, obtained sediment can be removed in this way to single layer, form colloidal nano piece suspension；Finally in obtained colloid
Water is added in nanometer sheet suspension, the tetrabutylammonium hydroxide aqueous solution in the suspension of centrifugation removal later, then be dried, it obtains
The single layer titanium dioxide nanoplate powder adulterated to Ni.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Ni element is about 1.5%~8.9%.The sample that doping concentration is about 1.5% is chosen, by being measured microscopically sample
The diameter of product is about 5.6 μm, and the area of nanometer sheet is about 24.62 μm2, be conducive to good crystallinity, lesser defect density.
Sample about 21mg is taken later, and using methanol solution (percent by volume 20%) as reaction solution, light is carried out in quartz reaction pond
Source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate has reached 12 μ
Mol/h or so, for 2~3 times undoped with system.
Embodiment 6
The present embodiment prepares a kind of single layer titanium dioxide nanoplate of Cu doping, chemical formula Cs0.7Ti1.82-xCuxO4(x
=0.018,0.027,0.089,0.182).
By CsCO3, TiO2And CuCl2·2H2O is mixed in the water of 50mL, is heat-treated later by water evaporation, is obtained
Cs0.7Ti1.82-xCuxO4.Mixture is carried out to the calcining of 55min in air, temperature controls at 500 DEG C, exists again after grinding
18h is calcined at 1000 DEG C.Later, obtained sample 0.5g is immersed in the HCl solution 45mL of 0.12mol/L and stirs 64h, it
After be filtered, washed, remove extra acid, and air-dry；Finally stirred in the tetrabutylammonium hydroxide aqueous solution of 0.025mol/L
It mixes 7 days, obtained sediment can be removed in this way to single layer, form colloidal nano piece suspension；Finally in obtained colloid
Water is added in nanometer sheet suspension, the tetrabutylammonium hydroxide aqueous solution in the suspension of centrifugation removal later, then be dried, it obtains
The single layer titanium dioxide nanoplate powder adulterated to Cu.
Sample obtained by the present embodiment analyzes the atomic ratio of sample using X-ray energy spectrum analysis first, obtains
The atom content of Cu element is about 0.9%~10%.The sample that doping concentration is about 1.3% is chosen, by being measured microscopically sample
The diameter of product is about 7.8 μm, and the area of nanometer sheet is about 47.76 μm2, be conducive to good crystallinity, lesser defect density.
Sample about 19mg is taken later, and using methanol solution (percent by volume 20%) as reaction solution, light is carried out in quartz reaction pond
Source (xenon lamp of 500W) irradiation, passes through gas-chromatography standard measure H2Generation.Test result shows that liberation of hydrogen rate has reached 8 μ
Mol/h or so, for 1~2 times undoped with system.
As it can be seen that the micro transition metal in above embodiments is mixed under the premise of guaranteeing that catalyst possesses better stability
Miscellaneous, liberation of hydrogen rate is generally improved；And in numerous transient metal doped samples, the shadow of the doping of Cr to liberation of hydrogen rate
It rings maximum；Optimum foreign atom ratio is 1-2% simultaneously.For photocatalysis liberation of hydrogen field, a high liberation of hydrogen rate, simply
Preparation process and good stability the characteristics of being ideal catalyst, the trace doped single layer titanium dioxide of transition metal of the invention
Nanometer sheet exactly possesses these features, is expected to become ideal photocatalysis liberation of hydrogen catalyst.
Although the preferred embodiment of the present invention is described above, the invention is not limited to above-mentioned specific
Embodiment, the above mentioned embodiment is only schematical, is not restrictive, those skilled in the art
Under the inspiration of the present invention, it when not departing from invention objective and scope of the claimed protection, can also make very much
The specific transformation of form, within these are all belonged to the scope of protection of the present invention.
Claims (9)
1. a kind of transient metal doped single layer titanium dioxide nanoplate, which is characterized in that the doping of single layer titanium dioxide nanoplate
Having transition metal element M, the transition metal element M of doping is one of Ni, Mn, Fe, Co, Cr, Cu, the transition gold
100% × the M/ of atom content (Ti+M) for belonging to element is 1-10%；And it is obtained by following preparation method:
(1) by CsCO3、TiO2With the hydrochloride of transition metal element M, water is added to be mixed, is heat-treated later by water evaporation, is obtained
To Cs0.7Ti1.82-xMxO4, 0 x≤0.2 <；Wherein, the hydrochloride of the transition metal element M is NiCl2、MnCl2、FeCl3、
CoCl2、CrCl3、CuCl2One of；
(2) mixture for again obtaining step (1) is ground in 400 DEG C of -500 DEG C of calcining 55-65min in the environment of containing oxygen
Continue calcining 18-22 hours after mill at 800 DEG C -1000 DEG C；The above process in this step operates 1-2 times；
(3) sample for obtaining step (2) and concentration are the HCl solution of 0.08-0.12mol/L according to 0.008~0.012g/mL
Ratio mixing, stirring protonated, is filtered, washed later, removes extra acid, and air-dry for 60-75 hours；
(4) sediment for obtaining step (3) stirs 6-7 days in the quaternary ammonium aqueous alkali of 0.02-0.03mol/L, forms glue
Body nanometer sheet suspension；
(5) water is added in the colloidal nano piece suspension that step (4) obtains, the quaternary ammonium buck in the suspension of centrifugation removal later
Solution, then be dried, obtain transient metal doped single layer titanium dioxide nanoplate powder.
2. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that transition
The area of metal-doped single layer titanium dioxide nanoplate is 10-100 μm2。
3. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(1) the x value in is 0.02-0.2.
4. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(2) in 400 DEG C of -500 DEG C of temperature lower calcination 60min in, 800 DEG C -1000 DEG C of temperature lower calcinations 20 hours.
5. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(3) concentration of HCl solution is 0.1mol/L in.
6. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(3) ratio of sample and HCl solution is 0.01g/mL in.
7. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(3) mixing time protonated in is 72 hours.
8. the transient metal doped single layer titanium dioxide nanoplate of one kind according to claim 1, which is characterized in that step
(4) the quaternary ammonium aqueous alkali in selects the tetrabutylammonium hydroxide aqueous solution of 0.025mol/L.
9. a kind of preparation side of transient metal doped single layer titanium dioxide nanoplate as described in any one of claim 1-8
Method, which is characterized in that carry out in accordance with the following steps:
(1) by CsCO3、TiO2With the hydrochloride of transition metal element M, water is added to be mixed, is heat-treated later by water evaporation, is obtained
To Cs0.7Ti1.82-xMxO4, 0 x≤0.2 <；Wherein, the hydrochloride of the transition metal element M is NiCl2、MnCl2、FeCl3、
CoCl2、CrCl3、CuCl2One of；
(2) mixture for again obtaining step (1) is ground in 400 DEG C of -500 DEG C of calcining 55-65min in the environment of containing oxygen
Continue calcining 18-22 hours after mill at 800 DEG C -1000 DEG C；The above process in this step operates 1-2 times；
(3) sample for obtaining step (2) and concentration are the HCl solution of 0.08-0.12mol/L according to 0.008~0.012g/mL
Ratio mixing, stirring protonated, is filtered, washed later, removes extra acid, and air-dry for 60-75 hours；
(4) sediment for obtaining step (3) stirs 6-7 days in the quaternary ammonium aqueous alkali of 0.02-0.03mol/L, forms glue
Body nanometer sheet suspension
(5) water is added in the colloidal nano piece suspension that step (4) obtains, the quaternary ammonium buck in the suspension of centrifugation removal later
Solution, then be dried, obtain transient metal doped single layer titanium dioxide nanoplate powder.
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