CN108144636A - A kind of cobalt titanate doped titanium nitride photochemical catalyst and preparation method for hydrogen manufacturing - Google Patents
A kind of cobalt titanate doped titanium nitride photochemical catalyst and preparation method for hydrogen manufacturing Download PDFInfo
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- CN108144636A CN108144636A CN201810092870.4A CN201810092870A CN108144636A CN 108144636 A CN108144636 A CN 108144636A CN 201810092870 A CN201810092870 A CN 201810092870A CN 108144636 A CN108144636 A CN 108144636A
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000001257 hydrogen Substances 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000725 suspension Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 claims abstract description 25
- 239000008187 granular material Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- 235000019441 ethanol Nutrition 0.000 claims abstract description 13
- 239000002071 nanotube Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000004408 titanium dioxide Substances 0.000 description 17
- 238000004321 preservation Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000002242 deionisation method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- -1 hydroxyl free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to photochemical catalyst fields, provide a kind of cobalt titanate doped titanium nitride photochemical catalyst and preparation method for hydrogen manufacturing, first titania nanotube and metal magnesium granules are placed in reaction kettle high temperature in nitrogen atmosphere is obtained by the reaction titanium nitride, then titanium nitride is added in the aqueous solution of deionized water and ethyl alcohol and forms suspension, finally cobalt titanate is added in suspension, centrifuge, filter after being stirred to react, it is dry it is laser sintered up to cobalt titanate doped titanium nitride composite photo-catalyst.The present invention has relatively narrow band gap using cobalt titanate, there is good optical Response in visible light region, itself and titanium nitride are compounded to form p n heterojunction photocatalysts, widened the optical Response of titanium nitride, improve its photocatalysis efficiency so that hydrogen production efficiency is also improved.
Description
Technical field
The invention belongs to photochemical catalyst fields, and in particular to a kind of cobalt titanate doped titanium nitride photochemical catalyst for hydrogen manufacturing
And preparation method.
Background technology
Traditional hydrogen production process needs to consume huge conventional energy resource, makes the Hydrogen Energy personal value too high, greatly limits Hydrogen Energy
It promotes and applies.Then one during scientists are expected quickly by the use of inexhaustible, cheap solar energy as Hydrogen Energy forming process
The secondary energy makes Hydrogen Energy exploitation show more wide prospect.Scientists are found that using catalysis material as " medium " energy is sharp
Water-splitting it is oxygen and hydrogen necessary to fuel cell with solar energy, scientist claims this only with sunlight and aquatic output hydrogen and oxygen
Technology be " one of desirable technique of the mankind ".
Photocatalysis technology is the basic nanometer technology being born in the 1970s, wherein titanium dioxide (Titanium
Dioxide) because its oxidability is strong, chemical property is stablized nontoxic, becomes nano photocatalyst catalytic material most hot in the world.In morning
It is phase, also once more to use cadmium sulfide (CdS) and zinc oxide (ZnO) as photocatalyst material, but due to the chemistry of the two
Property is unstable, can dissolve out harmful metal ion with certain bio-toxicity light-catalysed while light dissolving occurs, therefore
Developed country has seldom been used them as at present as civilian catalysis material, and the industrial photocatalysis field in part is also using.
Titanium dioxide is a kind of semiconductor, is respectively provided with anatase (Anatase), rutile (Rutile) and brockite
(Brookite) three kinds of crystal structures, wherein only anatase structured and rutile structure has photocatalysis characteristic.
Titanium dioxide is one kind of oxide semiconductor, is the very big a kind of basic chemical industry raw material of yield in the world, general
Logical titanium dioxide is commonly referred to as body phase semiconductor mutually to be distinguished with nano-titanium dioxide.It is tied with Anatase or Rutile
The titanium dioxide of structure [photon excitation principle refer to photocatalyst reaction principle] under the photon excitation with certain energy can make point
Electronics in sub-track leaves valence band (Valence band) and transits to conduction band (conduction band).So as in material valency
Band forms photohole [Hole+], light induced electron [e-] is formed in conduction band, due to titanium dioxide granule in body phase titanic oxide
Very greatly, light induced electron is easy to compound with photohole during reaching conduction band and starting to particle surface activity, thus from
Macroscopically we can not observe the effect of photon excitation.But the titanium dioxide granule of nanometer is due to small-sized, so electric
Son is easier to be diffused into plane of crystal, and leading to 2 different pieces of uncharged plane of crystal originally, polarity occur opposite
2 microcell-light induced electrons and photohole.Since light induced electron and photohole have very strong energy, it is much higher by one
As organic pollution strand intensity, it is possible to organic pollution is resolved into the state of most original easily.The same time
Raw hole can also be formed with the hydrone in air react, generate hydroxyl free radical and also decomposable asymmetric choice net organic pollution and kill carefully
Bacterium virus.This property that 2 microcells are completely contradicted in a region and process for reaching effect jointly is nanometer technology
Typical application, commonly referred to as Manichaeanism.The reaction microcell is referred to as binary collaboration interface.
It can be seen that photocatalysis has important theory value and potential application value, especially in terms of hydrogen manufacturing.But
The catalyzing manufacturing of hydrogen effect of individual photochemical catalyst is often bad, is typically improved by doping or with the compound grade of other materials
Its catalytic efficiency in terms of hydrogen manufacturing.
The patent of Publication No. CN105921153A discloses a kind of composite photo-catalyst and preparation method thereof, by triethylene
Diamines and cobalt source compound are soluble in water；Molybdenum source compound and oxalic acid is soluble in water, and stirring is added dropwise in cobalt ammonium complex compound,
Then titanium source compound and template are added in, adds in triethylene diamine, hydro-thermal process after burin-in process obtains slurries after cooling,
It is filtered, washed, dries, roasts, composite photo-catalyst is obtained after compression molding.
Photochemical catalyst is used for hydrogen manufacturing, and due to poor to photoresponse and sensibility, hydrogen production efficiency is relatively low.
Metal nitride is being catalyzed the research with Material Field, there is important theory value and potential application value,
Especially in terms of hydrogen is added, since metal nitride has eka-platinium metallicity, become the one of catalysis and Material Field
The important semiconducting compound of class.But its synthesis technology is more complicated, specific surface area is smaller, to the absorbability of visible ray compared with
It is weak.
Invention content
The object of the present invention is to provide a kind of cobalt titanate doped titanium nitride photochemical catalyst and preparation method for hydrogen manufacturing, profits
There is relatively narrow band gap with cobalt titanate, have good optical Response in visible light region, itself and titanium nitride are compounded to form p-n
Heterojunction photocatalyst has widened the optical Response of titanium nitride, improves its photocatalysis efficiency so that hydrogen production efficiency is also carried
It is high.
Specific technical solution of the present invention is as follows：
A kind of preparation method of cobalt titanate doped titanium nitride photochemical catalyst for hydrogen manufacturing, receives titanium dioxide in nitrogen atmosphere
Mitron and metal magnesium granules are placed in reaction kettle high temperature and titanium nitride are obtained by the reaction, and titanium nitride then is added in deionized water and ethyl alcohol
Aqueous solution in form suspension, finally by cobalt titanate add in suspension in, centrifuged after being stirred to react, filter, be drying to obtain titanium
Sour cobalt doped titanium nitride composite photo-catalyst, is as follows：
S01：Mass ratio is added in the closed container that nitrogen gas concn is 65%-100% is（1-3）:1 titania nanotube and
Then container is placed in reaction kettle and titanium nitride is obtained by the reaction at a high temperature of 800-1200 DEG C by metal magnesium granules；
S02：The titanium nitride being prepared is added in the solution being made of deionized water and ethyl alcohol and forms suspension, suspension
The mass fraction of middle titanium nitride is 30%-40%, and the mass fraction of ethyl alcohol is 40%-50%；
S03：Cobalt titanate is added in into suspension so that the mass fraction of cobalt titanate is 5%-10% in mixing suspension；
S04：It centrifuges, filter after mixing suspension is stirred to react, is dry, laser sintered compound up to cobalt titanate doped titanium nitride
Photochemical catalyst.
The present invention using cobalt titanate have relatively narrow band gap, have good optical Response in visible light region, by its with
Titanium nitride is compounded to form p-n heterojunction, and hetero-junctions is the formed interface zone that is in contact by two different semiconductors, i.e.,
It is using the compound of cobalt titanate and titanium nitride in the present invention, p-n heterojunction is formed in its intersection, because of semiconductor heterostructure
Electronics and hole can be confined in middle layer, the recombination rate in electronics and hole thus increase, so luminous efficiency is larger, from
And the optical Response of titanium nitride is widened.
For traditional hetero-junctions, it is by the semiconductive thin film of different materials, same pedestal is deposited on according to precedence
On.And be then to carry out that Nano titanium nitride is obtained by the reaction using the metallic particles sword gas of nanostructured in the present invention, then suspending
Cobalt titanate is added in liquid so that titanium nitride and cobalt titanate are adsorbed each other in aaerosol solution so that nitridation titanium molecule and cobalt titanate
Molecule contacts with each other, and condense together the microstructure to be formed and adulterated each other, a large amount of nitridation titanium molecules and cobalt titanate molecule aggregation
Cobalt titanate doped titanium nitride composite photo-catalyst is formed together, is equivalent to and is formd one new " mixture ", this " mixing
The contact point of several nitridation titanium molecules and cobalt titanate molecule, the nitridation titanium molecule and metatitanic acid of continuous adjacent are formed in the structure of object "
Contact surface is then formed between cobalt molecule, so as to form p-n heterojunction face, that is to say, that the metatitanic acid being finally prepared in the present invention
Its internal light sound that there are multiple p-n heterojunctions, therefore be greatly improved titanium nitride of cobalt doped titanium nitride composite photo-catalyst
Ying Xing improves its photocatalysis efficiency, and the efficiency for being applied to hydrogen manufacturing is also improved.
As being further improved for this programme, the nano particle diameter of the titania nanotube composition is 20-50nm.
Titanium oxide nanotubes because its prepare it is simple, cheap, there is higher specific surface area etc., in the dye sensitization sun
Energy battery, photolysis water hydrogen, ultraviolet light detector and photochemical catalyst etc. are widely used, but titanium dioxide is that N-type is wide
Bandgap semiconductor material, energy gap reach 3.2eV, the only absorbable ultraviolet light for accounting for about sunlight 5%, to visible ray almost without
It absorbs, and its electron-hole pair for generating under light illumination（electron-hole pairs）It is easily compound, thus limit
Its application range.It is placed in reaction kettle high temperature with metal magnesium granules in the present invention, titanium nitride is obtained by the reaction so that titanium nitride
Also there is the characteristic, then using metatitanic acid cobalt doped, significantly expand its light abstraction width to visible region and inhibit light induced electron
Hole pair it is compound.
As being further improved for this programme, the grain size of the metal magnesium granules is 0.1-0.3mm.
As being further improved for this programme, the suspension is kept the temperature, and the temperature of heat preservation is 80-100 DEG C.
As being further improved for this programme, the suspension is 3-5 hours a length of when keeping the temperature.
As being further improved for this programme, the drying temperature is 500-800 DEG C.
As being further improved for this programme, the drying time is 5-8 hours.
A kind of cobalt titanate doped titanium nitride photochemical catalyst for hydrogen manufacturing being prepared by the above method.
Compared with prior art, the present invention the characteristics of its protrusion and excellent effect are：Have using cobalt titanate relatively narrow
Band gap, have good optical Response in visible light region, itself and titanium nitride be compounded to form p-n heterojunction photochemical catalyst,
The optical Response of titanium nitride has been widened, has improved its photocatalysis efficiency so that hydrogen production efficiency is also improved.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 80%
Interior by titania nanotube and metal magnesium granules is 2 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 30nm, and the grain size of metal magnesium granules is 0.2mm, then the pyroreaction at 900 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 35% in liquid, and the mass fraction of ethyl alcohol is 50%, and suspension is carried out heat preservation 3 hours, heat preservation
Temperature is 90 DEG C, and cobalt titanate is added in most backward suspension so that the mass fraction of cobalt titanate is 6% in mixing suspension, will be mixed
It closes after suspension is stirred to react and centrifuges, permeation filtration is finally 5 hours dry, laser sintered up to cobalt titanate at a temperature of 600 DEG C
Doped titanium nitride photochemical catalyst.
Embodiment 2
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 65%
Interior by titania nanotube and metal magnesium granules is 1 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 20nm, and the grain size of metal magnesium granules is 0.1mm, and then the pyroreaction at 800 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 30% in liquid, and the mass fraction of ethyl alcohol is 40%, and suspension is carried out heat preservation 3 hours, heat preservation
Temperature is 80 DEG C, and cobalt titanate is added in most backward suspension so that the mass fraction of cobalt titanate is 5% in mixing suspension, will be mixed
It closes after suspension is stirred to react and centrifuges, permeation filtration is finally 5 hours dry at a temperature of 500 DEG C, laser sintered up to cobalt titanate
Doped titanium nitride photochemical catalyst.
Embodiment 3
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 70%
Interior by titania nanotube and metal magnesium granules is 1 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 25nm, and the grain size of metal magnesium granules is 0.2mm, and then the pyroreaction at 1000 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 35% in liquid, and the mass fraction of ethyl alcohol is 50%, and suspension is carried out heat preservation 4 hours, heat preservation
Temperature is 85 DEG C so that the mass fraction of cobalt titanate is 6% in mixed solution, is centrifuged after mixing suspension is stirred to react, and is permeated
Filtering, it is finally 8 hours dry at a temperature of 800 DEG C, it is laser sintered up to cobalt titanate doped titanium nitride photochemical catalyst.
It is measured through experiment, cobalt titanate doped titanium nitride composite photo-catalyst its catalytic efficiency that this programme is prepared is to pass
1.62 times of system titanium dioxide optical catalyst.
Embodiment 4
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 75%
Interior by titania nanotube and metal magnesium granules is 2 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 35nm, and the grain size of metal magnesium granules is 0.2mm, and then the pyroreaction at 1000 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 35% in liquid, and the mass fraction of ethyl alcohol is 50%, and suspension is carried out heat preservation 4 hours, heat preservation
Temperature is 90 DEG C, and cobalt titanate is added in most backward suspension so that the mass fraction of cobalt titanate is 5% in mixed solution, will be mixed
Solution centrifuges after being stirred to react, permeation filtration, finally dry 5 small, the laser sintered metatitanic acid cobalt doped nitrogen to obtain the final product at a temperature of 600 DEG C
Change titanium composite photo-catalyst.
Embodiment 5
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 90%
Interior by titania nanotube and metal magnesium granules is 3 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 45nm, and the grain size of metal magnesium granules is 0.2mm, and then the pyroreaction at 1100 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 38% in liquid, and the mass fraction of ethyl alcohol is 45%, and suspension is carried out heat preservation 4 hours, heat preservation
Temperature is 95 DEG C, and cobalt titanate is added in most backward suspension so that the mass fraction of cobalt titanate is 8% in mixed solution, will be mixed
Solution centrifuges after being stirred to react, permeation filtration, finally 8 hours dry at a temperature of 800 DEG C, laser sintered up to metatitanic acid cobalt doped
Titanium nitride composite photo-catalyst.
Comparative example 1
For the cobalt titanate doped titanium nitride composite photo-catalyst preparation method of hydrogen manufacturing, in the closed container that nitrogen gas concn is 90%
Interior by titania nanotube and metal magnesium granules is 3 in mass ratio:1 ratio is placed in reaction kettle, and wherein titanium dioxide is received
The nano particle diameter of mitron composition is 45nm, and the grain size of metal magnesium granules is 0.2mm, and then the pyroreaction at 1100 DEG C obtains
To titanium nitride, by the titanium nitride being prepared be added to by deionization be hydrated ethanol group into solution in form suspension, suspend
The mass fraction of titanium nitride is 38% in liquid, and the mass fraction of ethyl alcohol is 45%, and suspension is carried out heat preservation 4 hours, heat preservation
Temperature is 95 DEG C, and cobalt titanate is added in most backward suspension so that the mass fraction of cobalt titanate is 8% in mixed solution, will be mixed
Solution centrifuges after being stirred to react, permeation filtration, is answered to get cobalt titanate doped titanium nitride within finally dry 8 hours at a temperature of 800 DEG C
Closing light catalyst.
Comparative example 2
Commercially available titanium nitride photochemical catalyst.
The photochemical catalyst that embodiment 1-5, comparative example 1-2 are obtained is under the conditions of equal natural light for hydrolytic hydrogen production, system
Hydrogen efficiency is as shown in table 1.
Table 1：
By test, the present invention has good optical Response in visible light region, incites somebody to action by using the relatively narrow band gap of cobalt titanate
It is compounded to form p-n heterojunction photochemical catalyst with the laser sintered connection of titanium nitride, has widened the optical Response of titanium nitride, has improved it
Photocatalysis efficiency so that hydrogen production efficiency is also improved.And duration is good.
Claims (6)
1. a kind of preparation method of cobalt titanate doped titanium nitride photochemical catalyst for hydrogen manufacturing, it is characterised in that：In nitrogen atmosphere
It is middle titania nanotube and metal magnesium granules to be placed in reaction kettle high temperature titanium nitride is obtained by the reaction, then titanium nitride is added in
Suspension is formed in the aqueous solution of deionized water and ethyl alcohol, finally adds in cobalt titanate in suspension, centrifugation, mistake after being stirred to react
Filter, dry, laser sintered cobalt titanate doped titanium nitride composite photo-catalyst to obtain the final product, are as follows：
S01：Mass ratio is added in the closed container that nitrogen gas concn is 65%-100% is（1-3）:1 titania nanotube and
Then container is placed in reaction kettle and titanium nitride is obtained by the reaction at a high temperature of 800-1200 DEG C by metal magnesium granules；
S02：The titanium nitride being prepared is added in the solution being made of deionized water and ethyl alcohol and forms suspension, suspension
The mass fraction of middle titanium nitride is 30%-40%, and the mass fraction of ethyl alcohol is 40%-50%；
S03：Cobalt titanate is added in into suspension so that the mass fraction of cobalt titanate is 5%-10% in mixing suspension；
S04：It centrifuges, filter after mixing suspension is stirred to react, is dry, laser sintered compound up to cobalt titanate doped titanium nitride
Photochemical catalyst.
It is 2. special according to claim 1 for the preparation method of the cobalt titanate doped titanium nitride composite photo-catalyst of hydrogen manufacturing
Sign is：The nano particle diameter of the titania nanotube composition is 20-50nm.
It is 3. special according to claim 2 for the preparation method of the cobalt titanate doped titanium nitride composite photo-catalyst of hydrogen manufacturing
Sign is：The grain size of the metal magnesium granules is 0.1-0.3mm.
It is 4. special according to claim 1 for the preparation method of the cobalt titanate doped titanium nitride composite photo-catalyst of hydrogen manufacturing
Sign is：The drying temperature is 500-800 DEG C.
It is 5. special according to claim 1 for the preparation method of the cobalt titanate doped titanium nitride composite photo-catalyst of hydrogen manufacturing
Sign is：The drying time is 5-8 hours.
6. the cobalt titanate doped titanium nitride photochemical catalyst for hydrogen manufacturing that any one of Claims 1 to 5 the method is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111939912A (en) * | 2019-05-15 | 2020-11-17 | 国家纳米科学中心 | Cobalt-based catalyst and preparation method and application thereof |
| CN113697891A (en) * | 2021-09-18 | 2021-11-26 | 海南聚能科技创新研究院有限公司 | Photo-anode material and preparation method thereof |
| CN114231996A (en) * | 2022-02-28 | 2022-03-25 | 青岛理工大学 | Zinc molybdate-cobalt titanate coaxial fiber photo-anode film and preparation method and application thereof |
| CN115999614A (en) * | 2023-02-16 | 2023-04-25 | 福州大学 | Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst |
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2018
- 2018-01-31 CN CN201810092870.4A patent/CN108144636A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111939912A (en) * | 2019-05-15 | 2020-11-17 | 国家纳米科学中心 | Cobalt-based catalyst and preparation method and application thereof |
| CN111939912B (en) * | 2019-05-15 | 2023-05-23 | 国家纳米科学中心 | Cobalt-based catalyst and preparation method and application thereof |
| CN113697891A (en) * | 2021-09-18 | 2021-11-26 | 海南聚能科技创新研究院有限公司 | Photo-anode material and preparation method thereof |
| CN113697891B (en) * | 2021-09-18 | 2023-10-03 | 海南聚能科技创新研究院有限公司 | Photo-anode material and preparation method thereof |
| CN114231996A (en) * | 2022-02-28 | 2022-03-25 | 青岛理工大学 | Zinc molybdate-cobalt titanate coaxial fiber photo-anode film and preparation method and application thereof |
| CN115999614A (en) * | 2023-02-16 | 2023-04-25 | 福州大学 | Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst |
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