CN108993565A - A kind of composite photo-catalyst and preparation method thereof and Photocatalyzed Hydrogen Production method - Google Patents
A kind of composite photo-catalyst and preparation method thereof and Photocatalyzed Hydrogen Production method Download PDFInfo
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- CN108993565A CN108993565A CN201810757430.6A CN201810757430A CN108993565A CN 108993565 A CN108993565 A CN 108993565A CN 201810757430 A CN201810757430 A CN 201810757430A CN 108993565 A CN108993565 A CN 108993565A
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- niobic acid
- carbon nitride
- phase carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002253 acid Substances 0.000 claims abstract description 79
- 229910052788 barium Inorganic materials 0.000 claims abstract description 73
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 61
- 239000010439 graphite Substances 0.000 claims abstract description 61
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 230000036571 hydration Effects 0.000 claims description 9
- 238000006703 hydration reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 7
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims 1
- 229960004756 ethanol Drugs 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000010955 niobium Substances 0.000 abstract description 4
- 229910052758 niobium Inorganic materials 0.000 abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000003574 free electron Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical group O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of composite photo-catalysts and preparation method thereof and Photocatalyzed Hydrogen Production method, modify graphite phase carbon nitride using niobic acid barium nanometer sheet, graphite phase carbon nitride-niobic acid barium composite photo-catalyst is made.The 3d track of niobium takes part in the composition of valence band, its conduction band is made to be enriched with free electron；Niobic acid barium is provided simultaneously with suitable band structure and high photo-generated carrier mobility because of the diversity of its crystal structure and electronic structure；Separately, graphite phase carbon nitride is modified using niobic acid barium nanometer sheet, so as to generate hetero-junctions between niobic acid barium nanometer sheet and graphite phase carbon nitride, graphite phase carbon nitride with heterojunction structure-niobic acid barium composite photo-catalyst band structure and carrier transport characteristic special as caused by hetero-junctions, the compound of photo-generate electron-hole can effectively be inhibited in light-catalyzed reaction, quantum efficiency is improved, makes this graphite phase carbon nitride-niobic acid barium composite photo-catalyst that there is better visible light photocatalysis active.
Description
Technical field
The present invention relates to photocatalysis technology field, in particular to a kind of composite photo-catalyst and preparation method thereof and photocatalysis
Produce hydrogen methods.
Background technique
Photocatalysis technology presents unique potential using value in Environment control problem and in terms of solving energy crisis, special
It is not the very advantageous in terms of efficiently generating clean energy resource.In numerous catalysis materials, graphite phase carbon nitride is with its cost
It is cheap, have many advantages, such as redox ability and high light chemical stability and become the catalysis material that is currently concerned it
One.But common graphite phase carbon nitride photochemical catalyst not fully has the potentiality of sustainable development, wherein important reason
One of be exactly that graphite phase carbon nitride photo-generate electron-hole is easily compound, this causes it very low to the utilization rate of solar energy；In addition, stone
The black lower quantum efficiency of phase carbon nitride also seriously limits its further application.
Summary of the invention
It is an object of the present invention to provide a kind of composite photo-catalysts and preparation method thereof and Photocatalyzed Hydrogen Production method, solve existing
The above problem present in technology.
The technical scheme to solve the above technical problems is that
A kind of composite photo-catalyst, to modify graphite phase carbon nitride using niobic acid barium nanometer sheet, so that niobic acid barium nanometer sheet
Graphite phase carbon nitride-niobic acid barium composite photo-catalyst of hetero-junctions is generated between graphite phase carbon nitride.
The beneficial effects of the present invention are: the 3d track of niobium takes part in the composition of valence band, its conduction band is made to be enriched with free electron；Niobium
Sour barium is provided simultaneously with suitable band structure and high photo-generated carrier is mobile because of the diversity of its crystal structure and electronic structure
Property；In addition, graphite phase carbon nitride is modified using niobic acid barium nanometer sheet, so as to generate between niobic acid barium nanometer sheet and graphite phase carbon nitride
Hetero-junctions, graphite phase carbon nitride-niobic acid barium composite photo-catalyst with heterojunction structure are special as caused by hetero-junctions
Band structure and carrier transport characteristic, can effectively inhibit the compound of photo-generate electron-hole, raising amount in light-catalyzed reaction
Sub- efficiency makes this graphite phase carbon nitride-niobic acid barium composite photo-catalyst have better visible light photocatalysis active.
Another technical solution of the invention is as follows:
A kind of preparation method of composite photo-catalyst, includes the following steps:
Step A1 disperses niobic acid barium nanometer sheet in the second ultrapure water, and urea is added, and obtains solution D；
Step A2 heats the solution D, and is stirred well to generation dried object；
The dried object is calcined, isolates light yellow precipitate after cooling by step A3；
The light yellow precipitate is successively washed, is dried by step A4, and it is compound to obtain graphite phase carbon nitride-niobic acid barium
Photochemical catalyst.
The beneficial effects of the present invention are: having graphite phase carbon nitride-niobic acid barium of heterojunction structure multiple using calcining preparation
Light combination catalyst, preparation process are simple, safe, at low cost；In addition, raw material sources used by preparing are easy to get extensively.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the mass ratio of the niobic acid barium nanometer sheet and the urea is 1:20.
Beneficial effect using above-mentioned further scheme is: improving graphite phase carbon nitride-niobic acid barium complex light obtained and urges
The visible light photocatalysis active of agent.
Further, the heating is carried out using immersion method, and the bath temperature of the immersion method is 80 DEG C；The calcining is in horse
It is carried out in expense furnace, and continues 2 hours at 500 DEG C.
Beneficial effect using above-mentioned further scheme is: immersion method carries out reaction under constant temperature bad border, is conducive to reaction
Stablize carry out；Another bath temperature is 80 DEG C, avoids continuous heating that bath temperature is caused to reach 100 DEG C, sends out the water in solution D
Raw boiling, influences reaction effect.
Further, the niobic acid barium nanometer sheet is made using following steps:
Barium hydroxide is dissolved in the first ultrapure water by step B1, and solution A is sufficiently stirred to obtain；Columbium pentachloride is dissolved in
In dehydrated alcohol, solution B is sufficiently stirred to obtain；
The solution B is added in the solution A, solution C is sufficiently stirred to obtain by step B2；
The solution C is carried out hydro-thermal reaction, isolates white depositions after cooling by step B3；
The white depositions are successively washed, are dried by step B4, obtain the niobic acid barium nanometer sheet.
Beneficial effect using above-mentioned further scheme is: preparing niobic acid barium nanometer sheet, preparation process using hydro-thermal reaction
Simply, safe, at low cost；In addition, raw material sources used by preparing are easy to get extensively.
Further, the barium hydroxide is barium hydroxide octahydrate.
Further, the mass ratio of the barium hydroxide octahydrate and the columbium pentachloride is 5.85:1, and described first is ultrapure
The volume ratio of water and the dehydrated alcohol is 5:1.
Further, the hydro-thermal reaction continues 48 hours at 180 DEG C.
Another technical solution of the invention is as follows:
A kind of Photocatalyzed Hydrogen Production method of composite photo-catalyst is urged using above-mentioned graphite phase carbon nitride-niobic acid barium complex light
Agent carries out Photocatalyzed Hydrogen Production.
The beneficial effects of the present invention are: utilizing the better visible light light of graphite phase carbon nitride-niobic acid barium composite photo-catalyst
Catalytic activity carries out Photocatalyzed Hydrogen Production, improves Photocatalyzed Hydrogen Production performance.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the Photocatalyzed Hydrogen Production method specifically comprises the following steps:
The graphite phase carbon nitride-niobic acid barium composite photocatalyst is added into the reactor equipped with water to be decomposed in step C1
Agent and oxalic acid aqueous solution and six hydration chloroplatinic acid aqueous solutions, obtain solution E；Wherein, institute in the six hydrations chloroplatinic acid aqueous solution
The quality of platiniferous is the quality of contained graphite phase carbon nitride in the graphite phase carbon nitride-niobic acid barium composite photo-catalyst being added
1%；
Step C2 is passed through nitrogen into the reactor, to remove the oxygen in the reactor；
Step C3 irradiates the solution E using the LED light of Single wavelength 420nm, and using molten described in magnetic stirrer
Liquid E, to carry out Photocatalyzed Hydrogen Production.
Beneficial effect using above-mentioned further scheme is: oxalic acid aqueous solution further increases photocatalysis as sacrifice agent
H2-producing capacity；The quality of six hydration chloroplatinic acid aqueous solutions and platinum contained therein is that graphite phase carbon nitride-niobic acid barium of addition is compound
The 1% of the quality of contained graphite phase carbon nitride in photochemical catalyst makes to be formed on graphite phase carbon nitride-niobic acid barium composite photo-catalyst
The load of metal platinum, graphite phase carbon nitride-niobic acid barium composite photo-catalyst is as composite semiconductor, metal platinum and composite semiconductor
With different fermi levels, the work function of metal platinum is higher than the work function of composite semiconductor, and after the two combines, electronics is continuous
It is migrated from composite semiconductor to metal platinum, contacts metal platinum surface in the space charge layer to be formed in the two and obtain extra negative electricity
Lotus, composite semiconductor negative surface charge largely disappears, so that accelerating light induced electron passes to hydrionic migration rate, promotees
Into the separation of electrons and holes；In addition, the energy band of composite semiconductor bends towards Surface Creation depletion layer, partly led in metal platinum with compound
The shallow gesture Schottky energy barrier that energy trapped electron is formed on body interface effectively serves as electron trap and prevents answering for electron hole
It closes, therefore, metal platinum load further increases Photocatalyzed Hydrogen Production performance；It is produced using the LED light of Single wavelength 420nm as photocatalysis
The light source of hydrogen, the visible light of Single wavelength 420nm are conducive to improve Photocatalyzed Hydrogen Production performance, and LED light energy conservation and environmental protection.
Detailed description of the invention
Fig. 1 is composite photo-catalyst -1 of the present invention to 3 and the XRD spectra of graphite phase carbon nitride；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph (a) and TEM transmission electron microscope picture (b) of composite photo-catalyst -2 of the present invention；
Fig. 3 is the hydrogen output curve that composite photo-catalyst -1 of the present invention carries out Photocatalyzed Hydrogen Production to 3 and graphite phase carbon nitride
Figure.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
A kind of composite photo-catalyst of the embodiment of the present invention 1, to modify graphite phase carbon nitride using niobic acid barium nanometer sheet, so that
Graphite phase carbon nitride-niobic acid barium composite photo-catalyst of hetero-junctions is generated between niobic acid barium nanometer sheet and graphite phase carbon nitride.
A kind of preparation method of the composite photo-catalyst of the embodiment of the present invention 2, includes the following steps:
Step A1 disperses niobic acid barium nanometer sheet in the second ultrapure water, and urea is added, and obtains solution D；
Step A2 heats the solution D, and is stirred well to generation dried object；
The dried object is calcined, isolates light yellow precipitate after cooling by step A3；
The light yellow precipitate is successively washed, is dried by step A4, and it is compound to obtain graphite phase carbon nitride-niobic acid barium
Photochemical catalyst.
A kind of preparation method of the composite photo-catalyst of the embodiment of the present invention 3, on the basis of embodiment 2, the niobic acid barium
The mass ratio of nanometer sheet and the urea is 1:20.
A kind of preparation method of the composite photo-catalyst of the embodiment of the present invention 4, on the basis of embodiment 2 or 3, the heating
It is carried out using immersion method, the bath temperature of the immersion method is 80 DEG C；The calcining carries out in horse expense furnace, and at 500 DEG C
Continue 2 hours.
The preparation method of a kind of composite photo-catalyst of the embodiment of the present invention 5, on the basis of 2 to 4 any embodiment of embodiment
On, the niobic acid barium nanometer sheet is made using following steps:
Barium hydroxide is dissolved in the first ultrapure water by step B1, and solution A is sufficiently stirred to obtain；Columbium pentachloride is dissolved in
In dehydrated alcohol, solution B is sufficiently stirred to obtain；
The solution B is added in the solution A, solution C is sufficiently stirred to obtain by step B2；
The solution C is carried out hydro-thermal reaction, isolates white depositions after cooling by step B3；
The white depositions are successively washed, are dried by step B4, obtain the niobic acid barium nanometer sheet.
A kind of preparation method of the composite photo-catalyst of the embodiment of the present invention 6, on the basis of embodiment 5, the hydroxide
Barium is barium hydroxide octahydrate.
A kind of preparation method of the composite photo-catalyst of the embodiment of the present invention 7, on the basis of embodiment 6, eight hydration
The mass ratio of barium hydroxide and the columbium pentachloride is 5.85:1, and the volume ratio of first ultrapure water and the dehydrated alcohol is
5:1。
The preparation method of a kind of composite photo-catalyst of the embodiment of the present invention 8, on the basis of 5 to 7 any embodiment of embodiment
On, the hydro-thermal reaction continues 48 hours at 180 DEG C.
The Photocatalyzed Hydrogen Production method of a kind of composite photo-catalyst of the embodiment of the present invention 9, using above-mentioned graphite phase carbon nitride-niobium
Sour barium composite photo-catalyst carries out Photocatalyzed Hydrogen Production.
A kind of Photocatalyzed Hydrogen Production method of the composite photo-catalyst of the embodiment of the present invention 10, it is described on the basis of embodiment 9
Photocatalyzed Hydrogen Production method specifically comprises the following steps:
The graphite phase carbon nitride-niobic acid barium composite photocatalyst is added into the reactor equipped with water to be decomposed in step C1
Agent and oxalic acid aqueous solution and six hydration chloroplatinic acid aqueous solutions, obtain solution E；Wherein, institute in the six hydrations chloroplatinic acid aqueous solution
The quality of platiniferous is the quality of contained graphite phase carbon nitride in the graphite phase carbon nitride-niobic acid barium composite photo-catalyst being added
1%；
Step C2 is passed through nitrogen into the reactor, to remove the oxygen in the reactor；
Step C3 irradiates the solution E using the LED light of Single wavelength 420nm, and using molten described in magnetic stirrer
Liquid E, to carry out Photocatalyzed Hydrogen Production.
Specific embodiment 1
Make composite photo-catalyst:
Step 1,1.58g barium hydroxide octahydrate is dissolved in 50mL ultrapure water, solution A is sufficiently stirred to obtain；By 0.27g
Columbium pentachloride is dissolved in 10mL dehydrated alcohol, and solution B is sufficiently stirred to obtain；
Step 2, solution B is added in solution A, and solution C is sufficiently stirred to obtain；
Step 3, by solution C at 180 DEG C hydro-thermal reaction 48 hours, isolate white depositions after cooling；
Step 4, white depositions successively washed, dried, obtain niobic acid barium nanometer sheet；
Step 5, it disperses 0.2g niobic acid barium nanometer sheet in 100mL ultrapure water, and 2g urea is added, obtain solution D；
Step 6, by solution D be 80 DEG C in bath temperature at heating water bath, and be stirred well to generation dried object；
Step 7, dried object is taken in furnace in horse and is calcined 2 hours at 500 DEG C, isolate light yellow precipitate after cooling；
Step 8, light yellow precipitate successively washed, dried, obtain graphite phase carbon nitride-niobic acid barium composite photocatalyst
Agent is labeled as composite photo-catalyst -1.
As shown in Figure 1, the XRD base peak (JCPDS of the XRD diffraction maximum position of -1 sample of composite photo-catalyst and niobic acid barium
14-0028) position is identical, shows that niobic acid barium object does not change mutually in composite catalyst -1；But -1 sample of composite photo-catalyst
XRD diffraction maximum in do not occur the XRD diffraction maximum of graphite phase carbon nitride, show that complex light is urged since the amount of the urea of addition is few
Graphite phase carbon nitride content is few in agent -1, i.e., this composite photo-catalyst -1 is mainly niobic acid barium.
Photocatalyzed Hydrogen Production:
Composite photo-catalyst -1 is added into the reactor equipped with water to be decomposed, 0.025mM is added in dosage 0.5g/L
Oxalic acid aqueous solution as sacrifice agent, six hydration chloroplatinic acid aqueous solutions are added, obtain solution E；Wherein, six hydration chloroplatinic acid aqueous solution
The quality of middle institute's platiniferous is 1% of the quality of contained graphite phase carbon nitride in the composite photo-catalyst -1 being added；Into reactor
It is passed through nitrogen, to remove the oxygen in reactor；It is irradiated solution E 4 hours using the LED light of power 3W Single wavelength 420nm, and
Magnetic stirrer solution E is used, simultaneously to carry out Photocatalyzed Hydrogen Production；Its hydrogen output is as shown in figure 3, hydrogen output after 4 hours
About 176 μm of ol.
Specific embodiment 2
Make composite photo-catalyst:
Using method identical with specific embodiment 1, the dosage of wherein urea is only changed to 4g, graphite-phase nitridation is made
Carbon-niobic acid barium composite photo-catalyst is labeled as composite photo-catalyst -2.
As shown in Figure 1, the XRD base peak (JCPDS of the XRD diffraction maximum position of -2 sample of composite photo-catalyst and niobic acid barium
14-0028) position is identical, shows that niobic acid barium object does not change mutually in composite catalyst -2；Since the dosage of urea increases to
There is the very weak XRD base peak (JCPDS with graphite phase carbon nitride in the XRD diffraction maximum of -2 sample of composite photo-catalyst in 4g
87-1526) identical diffraction maximum, and as indicated with 2, the SEM scanning electron microscope (SEM) photograph (a) and TEM transmission electron microscope of composite photo-catalyst -2
Figure (b) shows that niobic acid barium nanometer sheet surface is coated with uniform Multi-layer graphite phase carbon nitride.
Photocatalyzed Hydrogen Production:
Using method identical with specific embodiment 1, Photocatalyzed Hydrogen Production is carried out using composite photo-catalyst -2；Its hydrogen output
As shown in figure 3, hydrogen output is about 534.6 μm of ol after 4 hours.
Specific embodiment 3
Make composite photo-catalyst:
Using method identical with specific embodiment 1, the dosage of wherein urea is only changed to 8g, graphite-phase nitridation is made
Carbon-niobic acid barium composite photo-catalyst is labeled as composite photo-catalyst -3.
As shown in Figure 1, the XRD base peak (JCPDS of the XRD diffraction maximum position of -3 sample of composite photo-catalyst and niobic acid barium
14-0028) position is identical, shows that niobic acid barium object does not change mutually in composite catalyst -3；Since the dosage of urea is further
Increase to 8g, occurs the XRD base peak significantly with graphite phase carbon nitride in the XRD diffraction maximum of -3 sample of composite photo-catalyst
(JCPDS 87-1526) identical diffraction maximum, shows compared with composite photo-catalyst -2, graphite-phase nitrogen in composite photo-catalyst -3
Change carbon content to increase.
Photocatalyzed Hydrogen Production:
Using method identical with specific embodiment 1, Photocatalyzed Hydrogen Production is carried out using composite photo-catalyst -3；Its hydrogen output
As shown in figure 3, hydrogen output is about 332.4 μm of ol after 4 hours.
Specific embodiment 4
Photocatalyzed Hydrogen Production:
Using method identical with specific embodiment 1, Photocatalyzed Hydrogen Production is carried out using graphite phase carbon nitride photochemical catalyst；Its
Hydrogen output is as shown in figure 3, hydrogen output is about 225 μm of ol after 4 hours.
By embodiments above 1 to 4 it is found that Photocatalyzed Hydrogen Production performance height successively are as follows: -2 > of composite photo-catalyst
- 3 > graphite phase carbon nitride photochemical catalyst > composite photo-catalyst -1 of composite photo-catalyst；Show graphite phase carbon nitride photochemical catalyst
All there is preferable visible light photocatalysis active with niobic acid barium photochemical catalyst (composite photo-catalyst -1)；The two is carried out compound
(composite photo-catalyst -2, composite photo-catalyst -3), so as to hetero-junctions is generated between niobic acid barium nanometer sheet and graphite phase carbon nitride,
Graphite phase carbon nitride with heterojunction structure-niobic acid barium composite photo-catalyst energy band knot special as caused by hetero-junctions
Structure and carrier transport characteristic can effectively inhibit the compound of photo-generate electron-hole in light-catalyzed reaction, improve quantum efficiency, make
This graphite phase carbon nitride-niobic acid barium composite photo-catalyst is compared to be used alone with the two, has better visible light photocatalysis living
Property；And when the mass ratio of niobic acid barium nanometer sheet and urea is 1:20, graphite phase carbon nitride obtained-niobic acid barium composite photocatalyst
The visible light photocatalysis active of agent (composite photo-catalyst -2) is best.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of composite photo-catalyst, which is characterized in that modify graphite phase carbon nitride using niobic acid barium nanometer sheet, so that niobic acid
Graphite phase carbon nitride-niobic acid barium composite photo-catalyst of hetero-junctions is generated between barium nanometer sheet and graphite phase carbon nitride.
2. a kind of preparation method of composite photo-catalyst, which comprises the steps of:
Step A1 disperses niobic acid barium nanometer sheet in the second ultrapure water, and urea is added, and obtains solution D；
Step A2 heats the solution D, and is stirred well to generation dried object；
The dried object is calcined, isolates light yellow precipitate after cooling by step A3；
The light yellow precipitate is successively washed, is dried by step A4, is obtained graphite phase carbon nitride-niobic acid barium complex light and is urged
Agent.
3. a kind of preparation method of composite photo-catalyst according to claim 2, which is characterized in that the niobic acid barium nanometer sheet
Mass ratio with the urea is 1:20.
4. a kind of preparation method of composite photo-catalyst according to claim 2, which is characterized in that the heating uses water-bath
Method carries out, and the bath temperature of the immersion method is 80 DEG C；The calcining carries out in horse expense furnace, and it is small at 500 DEG C to continue 2
When.
5. a kind of preparation method of composite photo-catalyst according to claim 2, which is characterized in that the niobic acid barium nanometer sheet
It is made using following steps:
Barium hydroxide is dissolved in the first ultrapure water by step B1, and solution A is sufficiently stirred to obtain；Columbium pentachloride is dissolved in anhydrous
In ethyl alcohol, solution B is sufficiently stirred to obtain；
The solution B is added in the solution A, solution C is sufficiently stirred to obtain by step B2；
The solution C is carried out hydro-thermal reaction, isolates white depositions after cooling by step B3；
The white depositions are successively washed, are dried by step B4, obtain the niobic acid barium nanometer sheet.
6. a kind of preparation method of composite photo-catalyst according to claim 5, which is characterized in that the barium hydroxide is eight
Hydronium(ion) barium monoxide.
7. a kind of preparation method of composite photo-catalyst according to claim 6, which is characterized in that the eight hydronium(ion)s oxidation
The mass ratio of barium and the columbium pentachloride is 5.85:1, and the volume ratio of first ultrapure water and the dehydrated alcohol is 5:1.
8. a kind of preparation method of composite photo-catalyst according to claim 5, which is characterized in that the hydro-thermal reaction exists
Continue 48 hours at 180 DEG C.
9. a kind of Photocatalyzed Hydrogen Production method of composite photo-catalyst, which is characterized in that using a kind of complex light described in claim 1
Any a kind of complex light of graphite phase carbon nitride-niobic acid barium composite photo-catalyst or claim 2 to 8 in catalyst is urged
Graphite phase carbon nitride obtained by the preparation method of agent-niobic acid barium composite photo-catalyst carries out Photocatalyzed Hydrogen Production.
10. a kind of Photocatalyzed Hydrogen Production method of composite photo-catalyst according to claim 9, which is characterized in that the light is urged
Change production hydrogen methods to specifically comprise the following steps:
The graphite phase carbon nitride-niobic acid barium composite photo-catalyst is added into the reactor equipped with water to be decomposed in step C1, with
And oxalic acid aqueous solution and six is hydrated chloroplatinic acid aqueous solutions, obtains solution E；Wherein, institute's platiniferous in the six hydrations chloroplatinic acid aqueous solution
Quality be added the graphite phase carbon nitride-niobic acid barium composite photo-catalyst in contained graphite phase carbon nitride quality
1%；
Step C2 is passed through nitrogen into the reactor, to remove the oxygen in the reactor；
Step C3 irradiates the solution E using the LED light of Single wavelength 420nm, and uses solution E described in magnetic stirrer,
To carry out Photocatalyzed Hydrogen Production.
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