CN101254462B - Preparation of nano cadmium tantalite photocatalyst - Google Patents
Preparation of nano cadmium tantalite photocatalyst Download PDFInfo
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- CN101254462B CN101254462B CN2008100177754A CN200810017775A CN101254462B CN 101254462 B CN101254462 B CN 101254462B CN 2008100177754 A CN2008100177754 A CN 2008100177754A CN 200810017775 A CN200810017775 A CN 200810017775A CN 101254462 B CN101254462 B CN 101254462B
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- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 58
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000013019 agitation Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 12
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 5
- 238000003760 magnetic stirring Methods 0.000 abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229940083342 drysol Drugs 0.000 abstract 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 32
- 229910052739 hydrogen Inorganic materials 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- -1 alkoxide Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012418 validation experiment Methods 0.000 description 1
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- 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
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Abstract
The present invention relates to a method for preparing cadmium tantalate nanoparticle catalysts. The method includes the following steps: dissolving tantalum pentachloride and cadmium nitrate tetrahydrate in anhydrous alcohol and then dissolving polyethylene glycol in anhydrous alcohol; mixing the solutions under magnetic stirring, and evaporating solvents in a water bath to obtain a transparent sol; placing the transparent sol in an oven, fan-drying to obtain a dry sol, and grinding to obtain a flavescent precursor powder; calcining the precursor powder in a muffle furnace to obtain a gray powder; calcining the gray powder in the muffle furnace; and naturally cooling down to room temperature to obtain white cadmium tantalate nanoparticle photocatalyst. The invention utilizes the cadmium element instead of alkali metal and alkaline earth metal elements. The energy band structure and state density calculation show that the valence band of the photocatalyst is mainly formed by 0 2p orbital, the conduction band thereof is formed by Ta 5d, 0 2p and Cd 5s5p hybrid orbits, the band gap is minimized, Ta and Cd orbits are used together as reaction points to enhance the photocatalytic activity.
Description
Technical field
The present invention relates to Hydrogen Energy photocatalysis clean technology of preparing, particularly a kind of preparation method of cadmium tantalite photocatalyst of Hydrogen Energy preparation field.
Background technology
The current conventional energy resource that acceleration brought problems such as severe contamination under-supply, that liquid fuel is short, the fossil energy utilization causes along with science and technology and process of industrialization become increasingly conspicuous, and impel people to have to seek new clean alternative energy source.The fundamental research that renewable energy conversion is utilized, the regenerative resource high-quality of development high efficiency, low cost transforms with scale utilizes technology, has become present China energy science and technology field urgent task the most.China has very abundant regenerative resource resource, and potentiality to be exploited is huge.Yet because most regenerative resource energy densities are low, dispersed strong, unstable, discontinuous, in time, season and weather and factors such as variation are seriously restricting the development and utilization of the extensive regenerative resource of high efficiency, low cost.
Solar energy is inexhaustible, the nexhaustible disposable energy, be the photosynthesis by green plants and photosynthetic microorganism, is chemical energy with conversion of solar energy.Seeking alternative new energy field, be conversion of solar energy that storable electric energy, chemical energy are the research topics that people are most interested in.Hydrogen is a kind of storage, transportation and reproducible clean energy resource of being easy to, and decomposing water with solar energy hydrogen manufacturing is one of the best way that utilizes solar energy.Utilize the approach of decomposing water with solar energy to have by photoelectric process: (1) photoelectrochemical method: to absorb luminous energy by the photosemiconductor material and produce electron-hole pair, respectively at two electrolysis water; (2) homogeneous phase light helps complexometry: the redox system of utilizing metal complex to form absorbs the light decomposition water; (3) conductor photocatalysis method: wherein most economical, cleaning, practicality, a kind of promising method of can yet be regarded as with the method for conductor photocatalysis hydrogen production by water decomposition.
The photolysis water hydrogen principle is: when semiconductor light-catalyst is equal to or greater than the light radiation of its energy gap at energy, electronics from the highest electronics occupied molecular orbital (valence band) induced transition to minimum electronics occupied molecular orbital (being conduction band) not, thereby stayed photohole in valence band, introduced light induced electron in the conduction band, photohole and light induced electron have oxidation and reducing power respectively.Realize solar photolysis water hydrogen and oxygen, the reducing power of light induced electron must be able to be reduced H
2O produces H
2, and the oxidability of photohole must oxidation H
2O produces O
2, promptly will be at the bottom of the conduction band of semiconductor light-catalyst at H
2O/H
2Current potential (EO=OV, top (the conduction band position is high more, and current potential is negative more, and reducing power is strong more) pH=O); And top of valence band is at O
2/ H
2The O current potential (ENHE=+1.23V, pH=0) following (valence band location is low more, current potential more just, oxidability is strong more).
The key that realizes the solar energy photocatalytic decomposition water is to seek the high activity and high stability photochemical catalyst with appropriate bandgap.Studying at present maximum in the world is the transition metal composite oxide catalytic agent, mainly concentrates on Ti
4+, Ta
5+And Nb
5+Alkali metal and titanates of alkali-earth metals, tantalates and niobates semi-conducting material, for example CaTiO for core
3, SrTiO
3, A
2TiO
13(A=Na, K, Rb), Sr
2Nb
2O
7, ATaO
3(A=Na, K), MTa
2O
6(M=Ca, Sr, Ba) and Sr
2Ta
2O
7Deng all successively being reported.The design feature of such catalyst is by TaO
6, NbO
6, TiO
6Octahedra with rib altogether or altogether form such as angle constituted laminate, and alkali metal ion, alkaline-earth metal ions etc. intert and form Ca-Ti ore type and quasi-perovskite structure at interlayer.Wherein tantalates is studied more extensive because higher Ta5d track makes such catalyst activity higher relatively.The compound of pyrochlore constitution also has a small amount of report, Ca
2Ta
2O
7And A
2Ta
2O
6(A=Na, K) grade all shows certain photocatalytic activity.But, the common shortcoming that these catalyst exist be exactly band gap than broad, all more than 4.0eV, this has just determined the light absorption interval of material to be positioned at below the 300nm, greatly reduces efficiency of light absorption.
The preparation of oxide semiconductor photochemical catalyst at present mainly contains following two kinds of methods:
1, solid reaction process preparation: this method is to select for use corresponding metal carbonate or metal oxide to mix by certain stoichiometric proportion, through grinding, mixing, adopts high-temperature electric resistance furnace to calcine under long period, higher temperature and forms.Its advantage is simple to operate, and cost is lower, and the properties of sample of preparation is good, the mechanical strength height, and have good activity and anti-poisoning capability.But relatively poor with product cut size and uniformity that the method makes, and easily introduce impurity, too high sintering and the reunion that causes catalyst easily of temperature in the calcination process, thus catalytic performance reduced.
2, sol-gel process: this method is present more common a kind of preparation method.With a certain proportion of inorganic metal salt or organo-metallic compound such as alkoxide, adding a certain amount of organic coordination compound matter (citric acid etc.) adds thermal agitation and fully cooperates, chemical reactions such as hydrolysis, polymerization take place, form colloidal sol (Sol), colloidal sol can be transformed into the gel with certain space structure (Gel) of ceramic form or glassy state by modes such as dryings, and calcining at a certain temperature just can obtain target product.Advantages such as this method has that synthesis temperature is low, easy control of reaction system, product purity height, particle diameter are little, good dispersion more help the raising of photocatalysis performance, so be widely adopted, become one of important method of preparation nano material.
Brisse, people such as F. and N.N.Kolpakova once reported tantalic acid cadmium Cd
2Ta
2O
7As a kind of research of ferroelectric, all be to adopt the high temperature solid-state method preparation, and analyzed its structure and dielectric property etc.
Summary of the invention
Purpose of the present invention just provides a kind of photocatalytic activity height, and Stability Analysis of Structures, the preparation method of the nano cadmium tantalite photocatalyst that anti-photoetch ability is strong.
For achieving the above object, the technical solution used in the present invention is:
1) at first, in 50-70 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 20-40g, then, the polyethylene glycol (6000) with 15-25g is dissolved in the absolute ethyl alcohol of 20-40g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 70-100 ℃ of water-bath evaporating solvent obtains vitreosol;
3) colloidal sol that obtains is placed in 80-150 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 300-500 ℃ of calcining 4-6 hour;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 1-5 hour.
Because the present invention adopts cadmium element to replace the alkali metal and the alkali earth metal of present extensive use, the band structure and the density of states are calculated and are shown, the valence band of catalyst mainly is made of O 2p track, conduction band is by Ta 5d, O 2p and Cd 5s5p hybridized orbit constitute, dwindled band gap on the degree very much, Ta and Cd are common as the reaction position, have improved the light-catalyzed reaction activity.Therefore photochemical catalyst of the present invention has good photochemical catalyzing performance.
Description of drawings
Fig. 1 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The X-ray diffractogram of catalyst; Wherein a is the XRD figure of nano cadmium tantalite catalyst before the light-catalyzed reaction, and b is the XRD figure of nano cadmium tantalite catalyst after the light-catalyzed reaction;
Fig. 2 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The UV-vis figure of catalyst;
Fig. 3 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The SEM figure of catalyst;
Fig. 4 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The transmission electron microscope picture of catalyst;
Fig. 5 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The EDS figure of catalyst;
Fig. 6 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The band structure of catalyst and density of states calculating chart;
Fig. 7 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7The photocatalysis of catalyst decomposes methanol/water solution is produced hydrogen activity and is characterized schematic diagram, and abscissa is represented the time, and ordinate is represented hydrogen output;
Fig. 8 is by the synthetic nano cadmium tantalite Cd of method of the present invention
2Ta
2O
7Catalyst decomposes pure water hydrogen produces oxygen activity and characterizes schematic diagram, and abscissa is represented the time, and ordinate represents to produce the hydrogen oxygen-producing amount: ■ represents hydrogen, ● represent oxygen.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
2) secondly, above two kinds of solution are mixed under magnetic agitation, 90 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 150 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 450 ℃ of calcinings 5 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 2 hours.
2) secondly, above two kinds of solution are mixed under magnetic agitation, 70 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 120 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 300 ℃ of calcinings 6 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 5 hours.
2) secondly, above two kinds of solution are mixed under magnetic agitation, 100 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 100 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 500 ℃ of calcinings 4 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 3 hours.
2) secondly, above two kinds of solution are mixed under magnetic agitation, 80 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 130 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 370 ℃ of calcinings 5 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 1 hour.
2) secondly, above two kinds of solution are mixed under magnetic agitation, 75 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 80 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 400 ℃ of calcinings 6 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 4 hours.
Cadmium tantalite photocatalyst particle diameter by method preparation of the present invention is 80-100nm, has the pyrochlore constitution of cubic system, satisfies space group Fd-3m, and lattice parameter is a=b=c=10.37
And α=β=γ=90, include many TaO
6, CdO
8The tridimensional network that polyhedron constitutes.The UV, visible light ABSORPTION EDGE is positioned at about 370nm, and the calculating band gap is 3.35eV, and the oxidation photocatalyst band gap of report is obviously dwindled both at home and abroad at present, and the light utilization ratio is greatly improved.The catalyst that the SEM test shows makes is a nanometer particle size, and the EDS elementary analysis shows that Cd in the catalyst: Ta: O is 2: 2: 7.Show that by the BET test result this specific surface area of catalyst reaches 5.09m
2g
-1, be far longer than the specific area of the catalyst of solid reaction process preparation.The light-catalyzed reaction of on this breadboard photocatalytic reaction device, carrying out, the result is as follows:
1, nanometer Cd
2Ta
2O
7Supporting Pt (0.2wt%) produces H in methanol/water solution
2Be by 2.47mmol/h (in the 0.3g catalyst) that quantum yield and energy conversion efficiency are respectively 16.74% and 6.15%;
2, nanometer Cd
2Ta
2O
7Produce hydrogen product oxygen activity behind load 0.2 (wt) %NiO and bring up to 173.04 and 86.34 μ mol/h (in the 0.3g catalyst), quantum efficiency reaches 1.17%, and light energy use efficiency reaches 0.43%.
Above catalyst is through long-time continuous reaction experiment catalyst testing structure no change, and is active undamped.Therefore the prepared nano cadmium tantalite photocatalyst of this method has characteristics such as active height, good stability.
Fig. 1 (a) and (b) have provided synthetic nano cadmium tantalite Cd
2Ta
2O
7Photochemical catalyst is at 10-100 ° XRD figure, the synthetic catalyst crystal structure of this method is a cube phase pyrochlore constitution as can be seen, have good purity and degree of crystallinity, the position at each peak after the light-catalyzed reaction and intensity all do not have to change, and its structural having good stability is described.
Fig. 2 is the nano cadmium tantalite Cd that is synthesized
2Ta
2O
7The UV-vis figure of catalyst material, ABSORPTION EDGE is about 370nm as can be seen, and the band gap of calculating is 3.35eV.Than alkali metal and alkaline earth metal tantalate obvious red shift is arranged, enlarged the photoresponse interval to a great extent.
That Fig. 3 provides is synthetic tantalic acid cadmium Cd
2Ta
2O
7The SEM figure of photochemical catalyst, the particle that can find out gained intuitively is a nanometer particle size, size is even, good dispersion, no agglomeration phenomenon.
Fig. 4 is prepared tantalic acid cadmium Cd
2Ta
2O
7The TEM figure of catalyst has further verified the SEM characterization result, the tantalic acid cadmium Cd of nanometer particle size from figure
2Ta
2O
7The particle homogeneous, favorable dispersibility.
Fig. 5 is prepared tantalic acid cadmium Cd
2Ta
2O
7The EDS figure of catalyst, the element mol ratio is consistent with rate of charge in the visible gained catalyst, because the reduction of synthesis temperature, the situation of having avoided cadmium at high temperature to volatilize takes place.
Fig. 6 is the tantalic acid cadmium Cd that utilizes algorithm from the beginning to obtain
2Ta
2O
7The band structure of catalyst and density of states figure, the conduction band of this catalyst with high degree of dispersion as can be seen therefrom, the contribution of cadmium atom makes the catalyst conduction band by Ta 5d, O 2p and Cd 5s5p hybridized orbit constitute, dwindled band gap on the degree very much, therefore Ta and Cd are common has improved the light-catalyzed reaction activity as the reaction position, and this is one of improvement aspect of more present alkali metal of reporting and alkaline earth metal tantalate catalyst.
It below is the concrete confirmatory experiment that the present invention provides.
Hydrogen performance evaluation is produced in photocatalysis
Built-in quartz reactor is all adopted in the test and validation experiment of all relevant photochemical catalyzing performances of the present invention, adopts the 300W high-pressure sodium lamp to do light source, magnetic stirring apparatus.300W mercury lamp device mainly comprises a mercury lamp control cabinet and a 300W mercury lamp.Owing to can follow a large amount of heat to emit in the mercury lamp irradiation process, adopt circulating condensing water device, the temperature constant of reaction system is at 25 ± 2 ℃.Producing gas adopts on-line gas chromatography to carry out gas composition and quantitative analysis (the SP-2100 type gas chromatograph that the BeiFen Instrument Techogy Co., Ltd., BeiJing City produces, TCD detector, 5
Molecular sieve column).
Experimental procedure:
Tantalic acid cadmium Cd
2Ta
2O
7Loaded Pt catalyst decomposes the experiment of methanol/water solution to carry out according to the following steps:
1, be the catalyst fines that adds the 0.3g supporting Pt in the 450mL reactor at volume, 45ml methyl alcohol and 405ml deionized water ultrasonic (99%) 15 minute, are dispersed in the water catalyst fines;
2, reactor is fixed on the magnetic stirring apparatus, opens magnetic agitation, rotating speed is 300-500rpm, connects good relevant apparatus, opens recirculated water, and setting circulating water temperature is 25 ℃;
3, open sweep gas nitrogen, treat that it purged upward 10-20 minute, to remove the oxygen in the reactor, measured the flow (ml/min) in gas-chromatography exit simultaneously;
4, open the high-pressure sodium lamp source, regulate transformer, make that mercury lamp power is 300W to 225V.
5, open chromatographic work station, write related parameter, open automatic sampler, begin to measure hydrogen-producing speed (mmol/h).
Fig. 7 is that catalyst photocatalysis Decomposition methanol/water solution is produced the hydrogen result, and it is tantalic acid cadmium Cd
2Ta
2O
7Produce hydrogen and time relation.Experiment condition: catalyst 0.3g, methyl alcohol 45ml, deionized water 405mL, 300W Hg lamp is a light source.As seen from the figure, the prepared nano cadmium tantalite Cd of the present invention
2Ta
2O
7Have higher decomposition methanol/water solution behind the photochemical catalyst carried noble metal platinum and produce hydrogen activity under this experiment condition, hydrogen-producing speed can reach 2.47mmol/h (in the 0.3g catalyst), and successive reaction 8h activity is not seen decay; And do not change on the structure, from XRD figure, can be verified, referring to Fig. 1.This catalyst that proves absolutely that method proposed by the invention prepares can efficiently decompose methanol/water solution and produce hydrogen, and has good stable.
Tantalic acid cadmium Cd
2Ta
2O
7The experiment of load NiO catalyst decomposes pure water is carried out according to the following steps:
1, is catalyst fines and the 450ml deionized water that adds 0.3g load NiO in the 450mL reactor at volume, ultrasonic (99%) 15 minute, catalyst fines is dispersed in the water;
2, reactor is fixed on the magnetic stirring apparatus, opens magnetic agitation, rotating speed is 300-500rpm, connects good relevant apparatus, opens recirculated water, and setting circulating water temperature is 25 ℃.
3, open sweep gas nitrogen, treat that it purged upward 10-20 minute, to remove the oxygen in the reactor, measured the flow (ml/min) in gas-chromatography exit simultaneously
4, open the high-pressure sodium lamp source, regulate transformer, make that mercury lamp power is 300W to 225V.
5, open chromatographic work station, write related parameter, open automatic sampler, begin to measure hydrogen-producing speed (mmol/h).
Fig. 8 is that catalyst photocatalysis Decomposition pure water produces hydrogen product oxygen result, and ■ represents hydrogen, ● represent oxygen.Experiment condition: catalyst 0.3g, deionized water 450mL, 300W Hg lamp is a light source.As seen from the figure, the prepared nanometer Cd of the present invention
2Ta
2O
7: the NiO photochemical catalyst has higher product hydrogen and produces oxygen activity under this experiment condition.The hydrogen-producing speed of this catalyst can reach 173.04 μ mol/h, the 86.34 μ mol/h (in the 0.3g catalyst) that produce oxygen simultaneously, and successive reaction 9h activity is not seen decay.This proves absolutely the tantalic acid cadmium Cd that method proposed by the invention prepares
2Ta
2O
7Catalyst can efficiently decompose pure water and produce hydrogen and oxygen, and has good stable.
2. catalyst efficiency evaluation
Catalyst quantum efficient and light energy use efficiency computing formula are as follows:
The product hydrogen meter of light-catalyzed reaction is seen quantum efficiency and is calculated by following formula:
Energy conversion efficiency can be estimated with following formula:
Δ G in the formula (2)
P 0Expression produces the standard Gibbs free energy of the reaction of hydrogen, R
PBe the speed that produces standard conditions hydrogen, E
sBe incident intensity, A is the raying area.In the decomposition reaction of water, every generation a part hydrogen will shift two electronics, and the standard Gibbs that reacts when 298K can Δ G
H2 0=237kJ/mol.
By formula (1) calculate Cd
2Ta
2O
7: Pt (0.2wt%) catalyst produces hydrogen in methanol/water solution quantum efficiency is 16.74%, Cd
2Ta
2O
7: NiO (0.2wt%) catalyst produces hydrogen in methanol/water solution quantum efficiency is 1.17%.For employed 300W mercury lamp, by formula (2) calculate Cd
2Ta
2O
7: the light energy use efficiency of Pt (0.2wt%) catalyst is 6.15%, Cd
2Ta
2O
7: NiO (0.2wt%) catalyst decomposes pure water light energy use efficiency is 0.43%.
Claims (6)
1. nano cadmium tantalite Preparation of catalysts method is characterized in that:
1) at first, in 50-70 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 20-40g, then, the polyethylene glycol (6000) with 15-25g is dissolved in the absolute ethyl alcohol of 20-40g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 70-100 ℃ of water-bath evaporating solvent obtains vitreosol;
3) colloidal sol that obtains is placed in 80-150 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 300-500 ℃ of calcining 4-6 hour;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 1-5 hour.
2. the preparation method of nano cadmium tantalite photocatalyst according to claim 1 is characterized in that:
1) at first, in 50 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 40g, then, the polyethylene glycol (6000) with 20g is dissolved in the absolute ethyl alcohol of 40g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 90 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 150 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 450 ℃ of calcinings 5 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 2 hours.
3. the preparation method of nano cadmium tantalite photocatalyst according to claim 1 is characterized in that:
1) at first, in 70 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 30g, then, the polyethylene glycol (6000) with 18g is dissolved in the absolute ethyl alcohol of 30g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 70 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 120 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 300 ℃ of calcinings 6 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 5 hours.
4. the preparation method of nano cadmium tantalite photocatalyst according to claim 1 is characterized in that:
1) at first, in 60 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 25g, then, the polyethylene glycol (6000) with 25g is dissolved in the absolute ethyl alcohol of 25g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 100 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 100 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 500 ℃ of calcinings 4 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 3 hours.
5. the preparation method of nano cadmium tantalite photocatalyst according to claim 1 is characterized in that:
1) at first, in 55 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 35g, then, the polyethylene glycol (6000) with 23g is dissolved in the absolute ethyl alcohol of 35g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 80 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 130 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 370 ℃ of calcinings 5 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 1 hour.
6. the preparation method of nano cadmium tantalite photocatalyst according to claim 1 is characterized in that:
1) at first, in 65 ℃ water-bath, the tantalic chloride of 0.01mol and the four water cadmium nitrates of 0.01mol are dissolved in the absolute ethyl alcohol of 20g, then, the polyethylene glycol (6000) with 15g is dissolved in the absolute ethyl alcohol of 20g again;
2) secondly, above two kinds of solution are mixed under magnetic agitation, 75 ℃ of water-bath evaporating solvents obtain vitreosol;
3) colloidal sol that obtains is placed in 80 ℃ the baking oven, forced air drying obtains xerogel, grinds then and obtains flaxen precursor powder;
4) this precursor powder is placed Muffle furnace,, remove the dispersant polyethylene glycol, reduce to room temperature, take out and grind, obtain the grey powder 400 ℃ of calcinings 6 hours;
5) this grey powder is placed Muffle furnace,, reduce to room temperature naturally, promptly obtain the nano cadmium tantalite photocatalyst of white 900 ℃ of calcinings 4 hours.
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