CN104888829B - The preparation method of CSTON type visible ray complete solution water catalyst - Google Patents
The preparation method of CSTON type visible ray complete solution water catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of CSTON types visible ray complete solution water catalyst, after system fully dissolves soluble calcium salt, soluble scandium salts, soluble tantalum salt and combustion assisting agent in methanol water mixed solution, heated up in Muffle furnace Program and occur combustion reaction, kept for certain time in hot stage, predecessor is formed after natural cooling, CSTON Ca-Ti ore type nitrogen oxides powders are obtained after the predecessor then is carried out into nitridation high-temperature process.Using CSTON as major catalyst, first load cocatalyst after illumination stirring, then coat nitrogen inhibitor, that is, visible light-responded complete solution water catalyst is made.The present invention has the advantages that efficient stable, environment-friendly, raw material are easy to get.This product is visible light-responded complete solution water catalyst, energy fully trans-utilization solar energy, it is easy to application.
Description
Technical field
The invention belongs to the preparing technical field of inorganic non-metallic material, a kind of CSTON types are concretely related to visible
The preparation method of light complete solution water catalyst.
Background technology
During photocatalysis complete solution water (photocatalytic overall water splitting) is photocatalysis field
Hot research problem.Generally using nanostructured photocatalyst granular in solution is dissolved in, in the solution by with these particles
Contact, occur the reaction of a series of chemical catalysis, final the generation hydrogen of decomposition water completely and oxygen.The method is different from using discrete
The electrode of coating catalyst carry out the common method of hydrogen manufacturing and oxygen.The main advantage of photocatalysis complete solution water is its light used
Catalysis material is more less expensive than the material required by optical electro-chemistry (PEC) battery.Therefore, it can more be born when extensive, scale is used
It must rise, industrial prospect is more optimistic.
In numerous semiconductor light-catalysts, TiO2Because its chemical property is stable, catalytic activity is high, nontoxic, price is low
Honest and clean the advantages of, be considered as the photocatalysis material of most DEVELOPMENT PROSPECT in the application field of degradation of contaminant and decontamination system
Material.But, TiO2Energy gap (3.2 eV) it is wider, absorbing wavelength be concentrated mainly on ultraviolet region (<387 nm).To
Up in the solar energy on ground, the energy of this wave band is less than 5%, and 45% that the ratio of visible light part has accounted for solar energy is left
The right side, therefore TiO2Photocatalysis performance it is relatively low to the utilization ratio of solar energy.Further, since its light induced electron and hole is compound
Probability is higher, causes quantum efficiency relatively low, so as to limit TiO2The application of photochemical catalyst in practice.How photocatalysis is improved
Efficiency and it can effectively absorb the focal issue that visible ray is photocatalysis field research.
One of crucial challenge of photocatalysis complete solution water is that most of catalysis material only just has with UV-activated
Activity, and to visible ray then without activity.Exempt from one one-tenth (Kazunari Domen) professor since Tokyo Univ Japan's hall to exist
Gallium nitride (GaN) and zinc oxide (ZnO) solid solution are reported on Nature has very high visible ray complete solution water photocatalytic activity,
Research of the people to the photocatalytic activity of nitrogen oxides solid-solution material is more and more interested（Maeda, K.; Teramura,
K.; Lu, D. L.; Takata, T.; Saito, N.; Inoue, Y.; Domen, K., Photocatalyst
releasing hydrogen from water - Enhancing catalytic performance holds promise
for hydrogen production by water splitting in sunlight. Nature 2006, 440
(7082), 295-295）.The transition metal nitrogen oxides of perovskite structure（Semi-conducting material such as based on niobium and tantalum）As
A kind of photochemical catalyst of new and effective visible ray also increasingly obtains the attention of people.Because nitrogen-atoms participates in the shape of band structure
Into so that energy gap narrows, and can be used as visible light-responded semiconductor light-catalyst（Kudo, A.; Miseki, Y.,
Heterogeneous photocatScyst materiScs for water splitting. Chem Soc Rev,
2009,38 (1): 253-278）.
The content of the invention
The present invention is intended to provide a kind of preparation method of visible ray complete solution water catalysis material, to solve the full light of current visible ray
Solve water efficiency it is low, using solar energy it is insufficient the problem of.The present invention realizes Low Temperature Solid-Phase calcining by using combustion assisting agent
Produce the technical process of CSTON powders.Pass through multigroup contrast test, it was found that co-catalyst and nitrogen inhibitor are anti-in complete solution water
Played an important role in answering.Preparation method of the present invention can be applied equally to the change of the photocatalytic water catalysis material similar with CSTON
Study on the synthesis is learned, and is had broad application prospects.
To reach above-mentioned purpose, what the present invention was realized in.
A kind of preparation method of CSTON types visible ray complete solution water catalyst, be by soluble calcium salt, soluble scandium salts, can
After dissolubility tantalum salt and combustion assisting agent fully dissolve in methanol water mixed solution, directly fired in the heating of Muffle furnace Program
Reaction is burnt, and predecessor is formed after hot stage keeps certain time, natural cooling, then the predecessor is nitrogenized
After high-temperature process, CaSc is obtained1/4Ta3/4O5/2N1/2Ca-Ti ore type（ABX3）Nitrogen oxides solid solution, it is believed that be 50%
CaTaO2N and 50% CaSc1/2Ta1/2O3The solid-solution material formed, is abbreviated as CSTON；With CaSc1/4Ta3/4O5/2N1/2It is main
Catalyst, after illumination stirring, first load cocatalyst, then coat nitrogen inhibitor, that is, purpose product is made.
It is of the invention by soluble calcium salt, soluble scandium salts, soluble tantalum salt and combustion assisting agent as a kind of preferred scheme
Mol ratio be 4：1：3：20~200.
Further, soluble calcium salt of the present invention is calcium chloride or one kind or its mixture in calcium nitrate.
Further, soluble scandium salts of the present invention is scandium chloride or one kind or its mixture in scandium nitrate.
Further, soluble tantalum salt of the present invention is tantalic chloride or one kind in five ethoxy-tantalums or its mixing
Thing.
Further, combustion assisting agent of the present invention is urea or one kind or its mixture in citric acid.
Further, the heating rate scope of described Muffle furnace Program heating is in 5~20 DEG C/min；Described height
The temperature of thermophase is 600~900 DEG C；Retention time scope is 2~12 h；The nitridation high-temperature process temperature 800~
1000 DEG C, the reaction time is 4~24 h.
Further, the light source of illumination stirring of the present invention is 300 W xenon lamps, 1000 revs/min of mixing speed, illumination
Mixing time 24 hours.
Further, co-catalyst of the present invention is metal oxide RhCrNiOxMixture, based on load capacity
The 0.1~5% of catalyst quality.
Further, nitrogen inhibitor of the present invention is TiO2, load capacity is the 0.5~10% of main catalyst quality.
Compared with prior art, the present invention has following features.
（1）Present invention process route is simple, and preparation cost is low, easy to control, with higher production efficiency.
（2）Purpose product CSTON type visible ray complete solution water catalyst prepared by the present invention, its purity is high, good dispersion, entirely
Water efficiency high is solved, requirement of the photocatalysis field to visible light-responded catalysis material can be met.
（3）The object of the invention product belongs to complete solution water catalyst, under illumination in pure water（Without any sacrifice agent）Can be simultaneously
Decomposition water generates hydrogen and oxygen, and mol ratio is 2:1.
（4）The present invention realizes the technique mistake that CSTON powders are produced in Low Temperature Solid-Phase calcining by using combustion assisting agent
Journey, so as to save mass energy.
（5）CaSc prepared by the present invention1/4Ta3/4O5/2N1/2（CSTON）ABX3Type solid-solution material, the composition of location A
For Ca；The composition of B location is Sc1/4Ta3/4；X3The composition of position is O5/2N1/2It is the photocatalysis that energy gap is about 2.44 eV
Agent material.The wherein difference of B location Sc and Ta ionic radius so that the dipole moment of solid-solution material produces change, is conducive to light
Raw electronics and the separation in hole.
（6）The illumination stirring technique process of the present invention can effectively change the state of charge on major catalyst surface so that main
Catalyst and auxiliary agent can be effectively combined, and be the critical process process for improving catalyst performance.
（7）Co-catalyst among the object of the invention product can be effectively promoted the separation in light induced electron and hole, from
And improve the efficiency of photocatalysis complete solution water.Nitrogen inhibitor can effectively suppress the generation of side reaction, it is suppressed that the production of nitrogen
It is raw, improve the stability of catalyst.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and detailed description.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 schemes for the SEM of the CSTON powders prepared by the present invention.
Fig. 2 schemes for the SEM of the CSTON powders prepared by the present invention.
Fig. 3 schemes for the SEM of the CSTON powders prepared by the present invention.
Fig. 4 schemes for the SEM of the CSTON powders prepared by the present invention.
Fig. 5 is the X-ray diffractogram of the CSTON powders prepared by the present invention.
Fig. 6 is the infrared spectrogram of the CSTON powders prepared by the present invention.
Fig. 7 is the ultraviolet-visible spectrogram of the CSTON powders prepared by the present invention.
Fig. 8 is the energy gap figure of the CSTON powders prepared by the present invention.
Fig. 9-11 is the catalytic activity phenogram of the CSTON type visible ray complete solution water catalyst prepared by the present invention.
Embodiment
The present invention is using soluble calcium salt, scandium salts, tantalum salt and different combustion assisting agents as raw material.Raw material is according to certain mole
Proportioning, in methanol water mixed solution（Volume ratio 1:1）In fully after dissolving, directly occur burning in the heating of Muffle furnace Program anti-
Should, and predecessor is formed after hot stage keeps certain time, natural cooling, predecessor is then nitrogenized into high temperature under ammonia
CSTON powders are obtained after processing.Using CSTON as major catalyst, after illumination stirring, first load cocatalyst, then coat nitrogen suppression
Preparation, that is, be made purpose product CSTON type visible ray complete solution water catalyst（Visible light-responded photocatalytic water catalyst）.
Its preparation process is.
（1）By soluble calcium salt, soluble scandium salts, soluble tantalum salt and different combustion assisting agents according to certain mol ratio
After weighing, methanol water mixed solution is placed in（Volume ratio 1:1）In fully dissolve.
（2）By above-mentioned solution, combustion reaction, the heating rate model of Muffle furnace Program heating directly occur in Muffle furnace
It is trapped among 5~20 DEG C/min.
（3）The temperature of Muffle furnace hot stage is 600~900 DEG C；Retention time scope is 2~12 h, after natural cooling
Predecessor is made.
（4）Predecessor is subjected to high-temperature ammonolysis processing in ammonia atmosphere, nitriding temperature is 800~1000 DEG C, time
For 4~24 hours, that is, CSTON powders are made.
（5）Using CSTON powders as major catalyst, illumination stirring is first carried out, its light source is 300 W xenon lamps, mixing speed
1000 revs/min, illumination mixing time 24 hours.
（6）Load cocatalyst again after illumination stirring.Described co-catalyst is metal oxide RhCrNiOx（Rh、Cr
And Ni mol ratio is 1:1：1 metal oxide）Mixture, load capacity be main catalyst quality 0.1~5%.
（7）After load co-catalyst, then coat nitrogen inhibitor.Described nitrogen inhibitor is TiO2, based on load capacity
The 0.5~10% of catalyst quality.
CaSc of the present invention1/4Ta3/4O5/2N1/2（It is abbreviated as CSTON）It is a kind of important Ca-Ti ore type solid solution material
Material, is mainly used in visible light-responded photocatalysis field.Because CSTON is in response to the photochemical catalyst of visible spectrum, forbidden band is wide
Degree is about 2.44 eV, is increasingly valued by people in recent years.
Referring to shown in Fig. 1 to 11, the CSTON powders obtained by preparation are carried out a series of sign and analysis by the present invention, its
As a result, products obtained therefrom CSTON powders are finely dispersed nano particle, particle diameter between 50-90nm (Fig. 1-4).Gained is produced
Product CSTON powder XRD diffraction patterns are ABX3Type perovskite structure and crystallinity is very strong（Fig. 5）.Fig. 6 is products obtained therefrom CSTON
The infrared spectrogram of powder.The ABSORPTION EDGE of products obtained therefrom CSTON powders is in 510 nm or so（Fig. 7）, the eV of energy gap about 2.44
（Fig. 8）.A certain amount of co-catalyst and nitrogen inhibitor are loaded, under visible light conditions, is had in the reaction model of complete solution water
Very high catalytic activity（Fig. 9-11）.
Embodiment 1.
By calcium chloride, scandium chloride, tantalic chloride and urea according to mol ratio be 4：1：3：100, first is put into after precise
Alcohol solution（Volume ratio of alcohol to water 1：1）Middle stirring and dissolving.Muffle furnace is directly placed into after above-mentioned mixture is fitted into big crucible
In, the heating rate of temperature programming is 10 DEG C/min, and 800 DEG C of high temperature design temperature, the hot stage retention time is 12 h, from
So after cooling, predecessor is produced.By predecessor under ammonia atmosphere nitrogen treatment, nitriding temperature is 850 DEG C, and the time is 12 small
When, after cooling, produce CSTON powders.Its product purity is not less than 99.80%, impurity content：Carbon is less than 0.04%；Chlorine is less than
0.12%.Using CSTON as major catalyst, after being stirred 24 hours with 300 W Xenon light shinings（1000 revs/min of mixing speed）, first load
Co-catalyst RhCrNiOxMixture, load capacity is the 1.0wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, bear
Carrying capacity is the 2.0wt% of main catalyst quality, that is, CSTON type visible ray complete solution water catalyst is made（Visible light-responded complete solution water
Catalyst）.In pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is about 9.2 μm of ol/h photocatalysis production oxygen
Efficiency be about 4.6 μm of ol/h, production hydrogen and production oxygen mol ratio be 2:1, and activity of preceding 7 hours is almost unattenuated, and light is urged
It is active after changing reaction 24 hours substantially not decay（See Fig. 9）.
Embodiment 2.
By calcium nitrate, scandium nitrate, five ethoxy-tantalums and citric acid according to mol ratio be 4：1：3：60, it is put into after precise
Methanol aqueous solution（Volume ratio of alcohol to water 1：1）Middle stirring and dissolving.Muffle is directly placed into after above-mentioned mixture is fitted into big crucible
In stove, the heating rate of temperature programming is 10 DEG C/min, and 800 DEG C of high temperature design temperature, the hot stage retention time is 4 h,
After natural cooling, predecessor is produced.By predecessor under ammonia atmosphere nitrogen treatment, nitriding temperature is 850 DEG C, and the time is 7 small
When, after cooling, produce CSTON powders.Its product purity is not less than 99.93%, impurity content：Carbon is less than 0.06%；Chlorine is less than
0.02%.Using CSTON as major catalyst, after being stirred 24 hours with 300 W Xenon light shinings（1000 revs/min of mixing speed）, first load
Co-catalyst RhCrNiOxMixture, load capacity is 0.8 wt% of main catalyst quality, then coats nitrogen inhibitor TiO2's
Mixture, load capacity is the 1.0wt% of main catalyst quality, that is, CSTON type visible ray complete solution water catalyst is made（Visible ray rings
The complete solution water catalyst answered）.In pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is about 16.4 μm of ol/h
The efficiency of photocatalysis production oxygen is about 8.2 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1, and activity of preceding 7 hours is almost
Unattenuated, activity does not substantially decay after light-catalyzed reaction 24 hours（See Figure 10）.
Embodiment 3.
By calcium nitrate, scandium nitrate, tantalic chloride and citric acid according to mol ratio be 4：1：3：80, first is put into after precise
Alcohol solution（Volume ratio of alcohol to water 1：1）Middle stirring and dissolving.Muffle furnace is directly placed into after above-mentioned mixture is fitted into big crucible
In, the heating rate of temperature programming is 10 DEG C/min, and 800 DEG C of high temperature design temperature, the hot stage retention time is 6 h, from
So after cooling, predecessor is produced.By predecessor under ammonia atmosphere nitrogen treatment, nitriding temperature is 900 DEG C, and the time is 7 small
When, after cooling, produce CSTON powders.Its product purity is not less than 99.90%, impurity content：Carbon is less than 0.04%；Chlorine is less than
0.04%.Using CSTON as major catalyst, after being stirred 24 hours with 300 W Xenon light shinings（1000 revs/min of mixing speed）, first load
Co-catalyst RhCrNiOxMixture, load capacity is 1.5 wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, bear
Carrying capacity is the 2.5wt% of main catalyst quality, that is, CSTON type visible ray complete solution water catalyst is made（Visible light-responded complete solution water
Catalyst）.In pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is about 12.2 μm of ol/h photocatalysis production oxygen
Efficiency be about 6.1 μm of ol/h, production hydrogen and production oxygen mol ratio be 2:1, and activity of preceding 7 hours is almost unattenuated, and light is urged
It is active after changing reaction 24 hours substantially not decay（See Figure 11）.
Embodiment 4.
By calcium nitrate, scandium nitrate, tantalic chloride and citric acid according to mol ratio be 4：1：3：100, it is put into after precise
Methanol aqueous solution（Volume ratio of alcohol to water 1：1）Middle stirring and dissolving.Muffle is directly placed into after above-mentioned mixture is fitted into big crucible
In stove, the heating rate of temperature programming is 10 DEG C/min, and 900 DEG C of high temperature design temperature, the hot stage retention time is 12 h,
After natural cooling, predecessor is produced.By predecessor under ammonia atmosphere nitrogen treatment, nitriding temperature be 1000 DEG C, the time is 4
Hour, after cooling, produce CSTON powders.Its product purity is not less than 99.94%, impurity content：Carbon is less than 0.03%；Chlorine is less than
0.03%.Using CSTON as major catalyst, after being stirred 24 hours with 300 W Xenon light shinings（1000 revs/min of mixing speed）, first load
Co-catalyst RhCrNiOxMixture, load capacity is the 1.2wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, bear
Carrying capacity is the 1.5wt% of main catalyst quality, that is, CSTON type visible ray complete solution water catalyst is made（Visible light-responded complete solution water
Catalyst）.In pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is about 15.6 μm of ol/h, photocatalysis production
The efficiency of oxygen is about 7.8 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1.
Embodiment 5.
By calcium nitrate, scandium nitrate, tantalic chloride and citric acid according to mol ratio be 4：1：3：100, it is put into after precise
Methanol aqueous solution（Volume ratio of alcohol to water 1：1）Middle stirring and dissolving.Muffle is directly placed into after above-mentioned mixture is fitted into big crucible
In stove, the heating rate of temperature programming is 10 DEG C/min, and 900 DEG C of high temperature design temperature, the hot stage retention time is 12 h,
After natural cooling, predecessor is produced.By predecessor under ammonia atmosphere nitrogen treatment, nitriding temperature be 1000 DEG C, the time is 24
Hour, after cooling, produce CSTON powders.Its product purity is not less than 99.97%, impurity content：Carbon is less than 0.02%；Chlorine is less than
0.01%.Using CSTON as major catalyst, after being stirred 24 hours with 300 W Xenon light shinings（1000 revs/min of mixing speed）, first load
Co-catalyst RhCrNiOxMixture, load capacity is the 0.5wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, bear
Carrying capacity is the 1.0wt% of main catalyst quality, that is, CSTON type visible ray complete solution water catalyst is made（Visible light-responded complete solution water
Catalyst）.In pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is about 26.2 μm of ol/h, photocatalysis production
The efficiency of oxygen is about 13.1 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1.
Comparative example 1.
Remaining preparation condition is same as Example 5, has only been the absence of after being stirred 24 hours with 300 W Xenon light shinings（Stirring
1000 revs/min of speed）The crucial preparation technology of this step.The experimental result of its photocatalytic water is, in pure water, with 300w xenon lamp
For light source, the efficiency of Photocatalyzed Hydrogen Production is about 0.3 μm of ol/h, and the efficiency of photocatalysis production oxygen is about 0.03 μm of ol/h.And have
Nitrogen accessory substance is about 1.1 μm of ol/h.
Comparative example 2.
Remaining preparation condition is same as Example 5, is only the absence of load cocatalyst this step preparation technology.Its photocatalytic water
Experimental result be that in pure water, using 300w xenon lamp as light source, the efficiency of Photocatalyzed Hydrogen Production is almost 0 μm of ol/h, and light is urged
The efficiency for changing production oxygen is almost 0 μm of ol/h.
Comparative example 3.
Remaining preparation condition is same as Example 5, has only been the absence of coating the preparation work of nitrogen inhibitor this step key
Skill.The experimental result of its photocatalytic water is, in pure water, using 300w xenon lamp as light source, and the efficiency of Photocatalyzed Hydrogen Production is about 30.3
μm ol/h, the efficiency of photocatalysis production oxygen is about 8.6 μm of ol/h.And it is about 33.8 μm of ol/h to have nitrogen accessory substance.
Comparative example 4.
Remaining preparation condition is same as Example 5, is only the absence of load cocatalyst and the step system of cladding nitrogen inhibitor two
Standby technique.The experimental result of its photocatalytic water is, in pure water, using 300w xenon lamp as light source, and the efficiency of Photocatalyzed Hydrogen Production is almost
For 0 μm of ol/h, the efficiency of photocatalysis production oxygen is almost 0 μm of ol/h.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (5)
1. a kind of preparation method of CSTON types visible ray complete solution water catalyst, it is characterised in that by calcium chloride, scandium chloride, pentachloro-
It is 4 to change tantalum and urea according to mol ratio：1：3：100, volume ratio of alcohol to water 1 is put into after precise：Stir molten in 1 methanol aqueous solution
Solution；Be directly placed into after above-mentioned mixture is fitted into big crucible in Muffle furnace, the heating rate of temperature programming for 10 DEG C/
Min, 800 DEG C of high temperature design temperature, the hot stage retention time is 12 h, after natural cooling, produces predecessor；By predecessor
The nitrogen treatment under ammonia atmosphere, nitriding temperature is 850 DEG C, and the time is 12 hours, after cooling, produces CSTON powders；
Its product purity is not less than 99.80%, impurity content：Carbon is less than 0.04%；Chlorine is less than 0.12%；Using CSTON as main catalytic
Agent, uses 300W Xenon light shinings, 1000 revs/min of mixing speed, after stirring 24 hours, first load cocatalyst RhCrNiOxMixing
Thing, load capacity is the 1.0wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, load capacity is main catalyst quality
2.0wt%, that is, be made CSTON type visible ray complete solution water catalyst；In pure water, using 300w xenon lamp as light source, Photocatalyzed Hydrogen Production
Efficiency be 9.2 μm of ol/h, the efficiency of photocatalysis production oxygen is 4.6 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1.
2. a kind of preparation method of CSTON types visible ray complete solution water catalyst, it is characterised in that by calcium nitrate, scandium nitrate, five second
Epoxide tantalum and citric acid are 4 according to mol ratio：1：3：60, volume ratio of alcohol to water 1 is put into after precise：Stirred in 1 methanol aqueous solution
Mix dissolving；It is directly placed into after above-mentioned mixture is fitted into big crucible in Muffle furnace, the heating rate of temperature programming is 10
DEG C/min, 800 DEG C of high temperature design temperature, the hot stage retention time is 4 h, after natural cooling, produces predecessor；By forerunner
Thing nitrogen treatment under ammonia atmosphere, nitriding temperature is 850 DEG C, and the time is 7 hours, after cooling, produces CSTON powders；
Its product purity is not less than 99.93%, impurity content：Carbon is less than 0.06%；Chlorine is less than 0.02%；Using CSTON as main catalytic
Agent, with 300 W Xenon light shinings, after the stirring 24 hours of 1000 revs/min of mixing speed, first load cocatalyst RhCrNiOxMixing
Thing, load capacity is 0.8 wt% of main catalyst quality, then coats nitrogen inhibitor TiO2Mixture, load capacity is main catalytic
The 1.0wt% of agent quality, that is, be made CSTON type visible ray complete solution water catalyst；In pure water, using 300w xenon lamp as light source, light
It is 16.4 μm of ol/h that the efficiency of hydrogen is produced in catalysis, and the efficiency of photocatalysis production oxygen is 8.2 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is
2:1。
3. a kind of preparation method of CSTON types visible ray complete solution water catalyst, it is characterised in that by calcium nitrate, scandium nitrate, pentachloro-
It is 4 to change tantalum and citric acid according to mol ratio：1：3：80, volume ratio of alcohol to water 1 is put into after precise：Stirred in 1 methanol aqueous solution
Dissolving；Be directly placed into after above-mentioned mixture is fitted into big crucible in Muffle furnace, the heating rate of temperature programming for 10 DEG C/
Min, 800 DEG C of high temperature design temperature, the hot stage retention time is 6 h, after natural cooling, produces predecessor；Predecessor is existed
Nitrogen treatment under ammonia atmosphere, nitriding temperature is 900 DEG C, and the time is 7 hours, after cooling, produces CSTON powders；
Its product purity is not less than 99.90%, impurity content：Carbon is less than 0.04%；Chlorine is less than 0.04%；Using CSTON as main catalytic
Agent, with 300 W Xenon light shinings, after the stirring 24 hours of 1000 revs/min of mixing speed, first load cocatalyst RhCrNiOxMixing
Thing, load capacity is 1.5 wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, load capacity is main catalyst quality
2.5wt%, that is, be made CSTON type visible ray complete solution water catalyst；In pure water, using 300w xenon lamp as light source, Photocatalyzed Hydrogen Production
Efficiency be 12.2 μm of ol/h, the efficiency of oxygen is produced in photocatalysis
For 6.1 μm of ol/h, the mol ratio of production hydrogen and production oxygen is 2:1.
4. a kind of preparation method of CSTON types visible ray complete solution water catalyst, it is characterised in that by calcium nitrate, scandium nitrate, pentachloro-
It is 4 to change tantalum and citric acid according to mol ratio：1：3：100, volume ratio of alcohol to water 1 is put into after precise：Stirred in 1 methanol aqueous solution
Dissolving；Be directly placed into after above-mentioned mixture is fitted into big crucible in Muffle furnace, the heating rate of temperature programming for 10 DEG C/
Min, 900 DEG C of high temperature design temperature, the hot stage retention time is 12 h, after natural cooling, produces predecessor；By predecessor
The nitrogen treatment under ammonia atmosphere, nitriding temperature is 1000 DEG C, and the time is 4 hours, after cooling, produces CSTON powders；
Its product purity is not less than 99.94%, impurity content：Carbon is less than 0.03%；Chlorine is less than 0.03%；Using CSTON as main catalytic
Agent, with 300 W Xenon light shinings, after the stirring 24 hours of 1000 revs/min of mixing speed, first load cocatalyst RhCrNiOxMixing
Thing, load capacity is the 1.2wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, load capacity is main catalyst quality
1.5wt%, that is, be made CSTON type visible ray complete solution water catalyst；In pure water, using 300w xenon lamp as light source, Photocatalyzed Hydrogen Production
Efficiency be 15.6 μm of ol/h, the efficiency of photocatalysis production oxygen is 7.8 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1.
5. a kind of preparation method of CSTON types visible ray complete solution water catalyst, it is characterised in that by calcium nitrate, scandium nitrate, pentachloro-
It is 4 to change tantalum and citric acid according to mol ratio：1：3：100, volume ratio of alcohol to water 1 is put into after precise：Stirred in 1 methanol aqueous solution
Dissolving；Be directly placed into after above-mentioned mixture is fitted into big crucible in Muffle furnace, the heating rate of temperature programming for 10 DEG C/
Min, 900 DEG C of high temperature design temperature, the hot stage retention time is 12 h, after natural cooling, produces predecessor；By predecessor
The nitrogen treatment under ammonia atmosphere, nitriding temperature is 1000 DEG C, and the time is 24 hours, after cooling, produces CSTON powders；
Its product purity is not less than 99.97%, impurity content：Carbon is less than 0.02%；Chlorine is less than 0.01%；Using CSTON as main catalytic
Agent, with 300 W Xenon light shinings, after the stirring 24 hours of 1000 revs/min of mixing speed, first load cocatalyst RhCrNiOxMixing
Thing, load capacity is the 0.5wt% of main catalyst quality, then coats nitrogen inhibitor TiO2, load capacity is main catalyst quality
1.0wt%, that is, be made CSTON type visible ray complete solution water catalyst；In pure water, using 300w xenon lamp as light source, Photocatalyzed Hydrogen Production
Efficiency be 26.2 μm of ol/h, the efficiency of photocatalysis production oxygen is 13.1 μm of ol/h, and the mol ratio of production hydrogen and production oxygen is 2:1.
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| CN104190461A (en) * | 2014-08-29 | 2014-12-10 | 渤海大学 | Preparation method of CLSTON catalyst for catalyzing visual light to decompose water to prepare hydrogen |
| CN104249993A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for producing hydrogen and oxygen through solar photocatalysis of water based on metal oxide photocatalyst |
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