CN110116015A - Complete photochemical catalyst for decomposing water and its preparation method and application, photocatalysis decompose the reaction method and catalytic mixing liquid of water completely - Google Patents
Complete photochemical catalyst for decomposing water and its preparation method and application, photocatalysis decompose the reaction method and catalytic mixing liquid of water completely Download PDFInfo
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- CN110116015A CN110116015A CN201810119486.9A CN201810119486A CN110116015A CN 110116015 A CN110116015 A CN 110116015A CN 201810119486 A CN201810119486 A CN 201810119486A CN 110116015 A CN110116015 A CN 110116015A
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- carbon nitride
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 85
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 title claims description 61
- 238000002156 mixing Methods 0.000 title claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 83
- 239000010439 graphite Substances 0.000 claims abstract description 83
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229910002451 CoOx Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 238000005286 illumination Methods 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 abstract description 47
- 238000006555 catalytic reaction Methods 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 16
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 239000010953 base metal Substances 0.000 abstract description 9
- 239000003426 co-catalyst Substances 0.000 abstract description 8
- 239000012071 phase Substances 0.000 abstract 3
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 235000013495 cobalt Nutrition 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000004202 carbamide Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- 229910052724 xenon Inorganic materials 0.000 description 12
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 12
- 239000012279 sodium borohydride Substances 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- -1 3mg3)2·6H2O Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention discloses catalyst and reaction method that water is decomposed in a kind of photocatalysis based on base metal load graphite phase carbon nitride completely.Graphite phase carbon nitride, metallic nickel nano granule and cobalt precursor are added directly into pure water by this method, and cobalt precursor is transformed into CoO by light reactionx, metallic nickel nano granule and CoOxSynergistic effect is used as co-catalyst, realizes the complete hydrogen production by water decomposition of visible light catalytic and oxygen processed of base metal load graphite phase carbon nitride.Operation of the present invention is simple, reproducible, and the material preparation cost related to is cheap, and can recycle solid phase from reaction system after reacting and obtain photochemical catalyst, for decomposing the light-catalyzed reaction of water completely.Catalyst and reaction method provided by the invention do not use noble metal, and constructive system is simple and convenient, can reduce the cost for decomposing the light-catalyzed reaction of water completely.
Description
Technical field
The invention belongs to photocatalysis technology field, in particular to a kind of photochemical catalyst and preparation method thereof for decomposing water completely
Decompose the reaction method and a kind of catalytic mixing liquid of water completely with application, a kind of photocatalysis.
Background technique
The made rapid progress of science and technology and the high speed development of process of industrialization increase the demand to the energy increasingly, conventional
The lasting consumption of the energy and it is non-renewable will lead to new energy crisis, while brought by the development and utilization of fossil energy
Problem of environmental pollution has seriously affected the existence and health of people.In order to solve energy shortage and environmental pollution, this two big threatens people
The exploitation of the problem of class survival and development, cleanliness without any pollution renewable energy arouses great concern.High efficiency, low cost
The basic theory that utilizes with scale of the high-quality conversion of renewable energy and center and hot spot that key technology is research.It gathers around in China
There is renewable energy very rich and potentiality to be exploited is huge, there are many renewable energy of form to be attempted out at present
Hair, including solar energy, water energy, wind energy, ocean energy etc..Wherein, solar energy has unlimitedness, generality, economy and spatter property
The features such as, thus have been a concern.Hydrogen Energy is ideal secondary energy sources, has energy density height, can store, can transport, nothing
The advantages that pollution.Renewable energy especially solar energy is converted into Hydrogen Energy, is the desirable route for solving the problems, such as energy and environment.Too
It is positive can photochemical catalyzing production clean reproducible hydrogen, being capable of energy density is low, intensity distribution geographical diversity at any time
Significant solar energy is converted into energy matter and is stored than high, free of contamination Hydrogen Energy, to realize the effective use of solar energy, is recognized
To be one of the scheme for being most hopeful to solve global energy crisis and problem of environmental pollution, realize efficiently low under visible light conditions
The industrial applications of the complete hydrogen production by water decomposition of the extensive photocatalysis of cost are the final directions of scientific research.
The principle of the complete hydrogen production by water decomposition of photocatalysis and oxygen processed is: under the irradiation of certain energy light, conductor photocatalysis
Agent light excitation generate electrons and holes pair, then electrons and holes move to catalyst surface respectively with water occur redox
Reaction generates hydrogen and oxygen.Can be realized the photochemical catalyst that water is decomposed in photocatalysis completely must have suitable band structure,
Including band gap size and bandedge placement.For most photochemical catalysts, co-catalyst also plays critical effect, helps and urges
Whether matched between agent and photochemical catalyst and determines that can decomposing aqueous systems completely construct success.Therefore, in order to successfully realize
The complete hydrogen production by water decomposition of photocatalysis and oxygen processed of low cost load matching and cheap, stable, efficient on photochemical catalyst
The research of base metal co-catalyst is most important to the development and application of photocatalysis industry.
Currently, in the catalysis material of numerous types, nonmetallic polymer semiconductor's graphite phase carbon nitride (g-C3N4) material
Material has suitable band structure, and (band gap 2.7eV has visible light-responded；Bandedge placement is capable of providing enough oxidation electricity
Gesture and reduction potential), good physical and chemical stability, unique two-dimensional structure characteristic, can be in different sacrifice agent systems
Photocatalyzed Hydrogen Production is realized respectively and produces oxygen, and photocatalysis may be implemented under certain condition and decompose water completely.And graphite-phase nitrogenizes
The persursor material abundance of carbon is cheap, and preparation method is simple, nontoxic, and environmental-friendly heavy metal free pollution is (containing only two kinds of C, N
Element) the advantages that, meet the prerequisite of inexpensive large-scale application, thus graphite phase carbon nitride be considered as it is optimal can
Light-exposed catalyst and rapidly become research hotspot.However, the high light induced electron and hole of graphite phase carbon nitride itself is compound
Rate makes it be difficult to realize complete hydrogen production by water decomposition and oxygen processed.For this problem, graphite is based on by co-catalyst load building
The complete decomposition aqueous systems of phase carbon nitride are to realize that carbonitride decomposes the important means of water application completely.
Summary of the invention
The purpose of the present invention is to provide a kind of photochemical catalyst and its preparation method and application for decomposing water completely, which is urged
Water can be completely decomposed into hydrogen and oxygen under illumination condition by agent, and base metal loads the visible light of graphite phase carbon nitride
It is catalyzed complete hydrogen production by water decomposition and oxygen processed.
The object of the invention is also to provide the reaction method that water is decomposed in a kind of photocatalysis completely, base metal loads stone
The complete hydrogen production by water decomposition of the visible light catalytic of black phase carbon nitride and oxygen processed.
The object of the invention is also to provide the catalytic mixing liquid that water is decomposed in a kind of photocatalysis completely, can simplify catalysis
Agent introduces the process of reaction system, keeps the active and efficient of catalyst.
The present invention is to be achieved through the following technical solutions:
A kind of complete photochemical catalyst for decomposing water, using graphite phase carbon nitride as carrier, load has nickel in graphite phase carbon nitride
Nano particle and CoOx；Wherein, 1.0≤x≤1.5.
Preferably, according to quality meter, graphite phase carbon nitride: nano nickel particles=1:(0.01~0.1).
Preferably, according to quality meter, graphite phase carbon nitride: CoOx=1:(0.002~0.025).
Preferably, the CoO in graphite phase carbon nitride is loaded toxIt is by the cobalt precursor solution containing graphite phase carbon nitride
It is generated in light reaction.
It is further preferred that cobalt precursor is cobalt nitrate.
The preparation method of the photochemical catalyst: by the mixed liquor of graphite phase carbon nitride, nano nickel particles and cobalt precursor
Light reaction is carried out under the primary condition of anaerobic, separation obtains photochemical catalyst after reaction.
The photochemical catalyst is decomposing the application in the reaction that water prepares oxygen and hydrogen completely.
The catalytic mixing liquid of water, including water are decomposed in a kind of photocatalysis completely, and graphite phase carbon nitride, nickel nanometer are mixed in water
Particle and cobalt precursor, wherein the quality sum of graphite phase carbon nitride, nano nickel particles and cobalt precursor is catalytic mixing liquid matter
The 0.5%~10% of amount.
The reaction method of water is decomposed in a kind of photocatalysis completely, comprising steps of
1) configure reaction mixture, the reaction mixture be include graphite phase carbon nitride and nano nickel particles cobalt before
Drive body aqueous solution；
2) it is stirring and under illumination, is carrying out the reaction that water is decomposed in photocatalysis completely.
Preferably, in reaction mixture, the concentration of graphite phase carbon nitride is 0.1~1mg/mL；According to quality meter, graphite
Phase carbon nitride: nano nickel particles=1:(0.01~0.1), graphite phase carbon nitride: cobalt element=1:(0.002 in cobalt precursor
~0.02).
Preferably, the oxygen in reaction mixture is removed in step 2), before light reaction.
Compared with prior art, the invention has the following beneficial technical effects:
The complete photochemical catalyst for decomposing water provided by the invention, by the supported by cobalt oxide of the nano particle of elemental nickel and cobalt
Onto graphite phase carbon nitride, the photochemical catalyst of base metal load graphite phase carbon nitride is formed, can be realized and decompose water system completely
Standby oxygen and hydrogen, catalyst activity is high and low in cost, and preparation process is simple, reliable, to construct photocatalysis Decomposition aqueous systems
Water cost is decomposed completely with reduction photocatalysis provides a kind of reliable scheme.
The present invention also provides the preparation methods of the photochemical catalyst, and this method is simple and convenient, and material is common and cheap.
The present invention also provides the reaction methods that water is decomposed in a kind of photocatalysis completely, by graphite phase carbon nitride, metallic nickel
Nanometer and cabaltous nitrate hexahydrate are added directly into pure water, and cabaltous nitrate hexahydrate is transformed into CoO by light reactionx, metal
Nano nickel particles and CoOxSynergistic effect is used as co-catalyst, and the visible light for realizing base metal load graphite phase carbon nitride is urged
Change complete hydrogen production by water decomposition and oxygen processed, this method is simple and efficient, and it is low in cost and reproducible, it can also be from reactant after reaction
Photochemical catalyst is recycled in system for decomposing the reaction of water completely.
The catalytic mixing liquid of water is decomposed in photocatalysis provided by the invention completely, and it is dense to be directly diluted to reaction when in use
Degree can directly be reacted, and decompose the reaction solution of water completely convenient for configuration photocatalysis, while avoiding small quality material and matching
Bigger error problem when setting and weighing, convenient precisely configuration catalyst system.
Detailed description of the invention
Fig. 1 is CN-0Ni-0CoOx、CN-Ni、CN-Ni-3.5CoOxAnd CN-3.5CoOxReaction system is carrying out all band
X-ray diffraction (XRD) figure of the sample recycled after light-catalyzed reaction.
Fig. 2 is CN-0Ni-0CoOxAnd CN-Ni-3.5CoOxReaction system recycles after carrying out all band light-catalyzed reaction
Uv-visible absorption spectra (UV-vis) figure of the sample arrived.
Fig. 3 is the transmission electron microscope for the sample that CN-Ni reaction system recycles after carrying out all band light-catalyzed reaction
(TEM) photo.
Fig. 4 is CN-3.5CoOxThe transmission electricity for the sample that reaction system recycles after carrying out all band light-catalyzed reaction
Mirror (TEM) photo.
Fig. 5 is CN-Ni-3.5CoOxThe sample that reaction system recycles after carrying out all band light-catalyzed reaction it is saturating
Radio mirror (TEM) photo.
Fig. 6-1, Fig. 6-2 and Fig. 6-3 are CN-Ni-3.5CoOxReaction system recycles after carrying out all band light-catalyzed reaction
X-ray photoelectron spectroscopy (XPS) figure of obtained sample.
Fig. 7 is CN-0Ni-0CoOxAnd CN-Ni-3.5CoOxReaction system recycles after carrying out all band light-catalyzed reaction
Fluorescence spectrum (PL) figure of the sample arrived.
Fig. 8-1 is CN-Ni-3.5CoOxThe lower photocatalysis hydrogen production of reaction system all band light (not plus optical filter) irradiation with
Oxygen activity figure processed.
Fig. 8-2 is CN-Ni-3.5CoOxPhotocatalysis hydrogen production and oxygen processed under reaction system visible light (λ >=420nm) irradiation
Activity figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Case study on implementation 1:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: graphite phase carbon nitride powder prepared by step 1 is added in pure water (CN-0Ni-0CoOx), it is surveyed
Examination.Specific step is as follows:
1) graphite phase carbon nitride of 50.0mg is added in the reactor that volume is 100mL, and deionized water is added to make light
The total volume for being catalyzed reaction solution is 80mL；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 2:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
It is added in pure water (CN-Ni), is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Liquid, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 3:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3mg3)2·6H2O is added in pure water (CN-Ni-3.0CoOx), it is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Co (the NO of liquid, 3mg3)2·6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 4:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water (CN-Ni-3.5CoOx), it is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Co (the NO of liquid, 3.5mg3)2·6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 5:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water, is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Co (the NO of liquid, 3.5mg3)2·6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply (λ >=420nm) is opened.
Case study on implementation 6:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 4mg3)2·6H2O is added in pure water (CN-Ni-4.0CoOx), it is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Co (the NO of liquid, 4mg3)2·6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 7:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 4.5mg3)2·6H2O is added in pure water (CN-Ni-4.5CoOx), it is tested.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 50.0mg are added in the reactor that volume is 100mL
Co (the NO of liquid, 4.5mg3)2·6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 8:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: the Co (NO of graphite phase carbon nitride powder and 3.5mg prepared by step 13)2·6H2O is added in pure water
(CN-3.5CoOx), it is tested.Specific step is as follows:
1) graphite phase carbon nitride of 50.0mg, the Co (NO of 3.5mg are added in the reactor that volume is 100mL3)2·
6H2O, and deionized water is added makes the total volume 80mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 9:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water (CN-Ni-4.0CoOx), it carries out photocatalysis and decomposes the anti-of water completely
It answers.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 35.0mg are added in the reactor that volume is 250mL
Co (the NO of liquid, 3.5mg3)2·6H2O, and deionized water is added makes the total volume 200mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 10:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water (CN-Ni-4.0CoOx), it carries out photocatalysis and decomposes the anti-of water completely
It answers.Specific step is as follows:
1) graphite phase carbon nitride, the 2.0mL metallic nickel nano granule of 35.0mg are added in the reactor that volume is 50mL
Co (the NO of dispersion liquid, 3.5mg3)2·6H2O, and deionized water is added makes the total volume 35mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 11:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water (CN-Ni-4.0CoOx), it carries out photocatalysis and decomposes the anti-of water completely
It answers.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule point of 100.0mg are added in the reactor that volume is 1000mL
Co (the NO of dispersion liquid, 1.0mg3)2·6H2O, and deionized water is added makes the total volume 800mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.
Case study on implementation 12:
Step 1: 10g urea being placed in alumina crucible, graphite phase carbon nitride is made in 600 DEG C of roasting 3h after capping.
Step 2: preparing metallic nickel nano granule dispersion liquid.By the Ni (NO of 17.5mg3)2·6H2O, the PVP of 100.0mg
The ethylene glycol of K30 and 20mL is added in 125mL three-neck flask and is completely dissolved, and three-neck flask is then placed in 120 DEG C of oil baths
It heats and stirs in pot, the NaBH of 63.0mg is added into solution after temperature is stablized4(NaBH4Quality be metallic nickel quality
18 times), it reheats and obtains transparent solution i.e. metallic nickel nano granule dispersion liquid after stirring 2h, theoretically metal in dispersion liquid
The quality of nano nickel particles is 3.5mg.
Step 3: by graphite phase carbon nitride powder prepared by step 1 and metallic nickel nano granule dispersion liquid prepared by step 2
And Co (the NO of 3.5mg3)2·6H2O is added in pure water (CN-Ni-4.0CoOx), it carries out photocatalysis and decomposes the anti-of water completely
It answers.Specific step is as follows:
1) graphite phase carbon nitride, the metallic nickel nano granule dispersion of 40.0mg are added in the reactor that volume is 500mL
Co (the NO of liquid, 4.0mg3)2·6H2O, and deionized water is added makes the total volume 400mL of light-catalyzed reaction solution；
2) lead to argon gas in illumination forward reaction device and purge 30min, to remove the oxygen in reaction system；
3) magnetic stirring apparatus is opened, xenon lamp power supply is opened.Wherein, case study on implementation 1,2,3,4,6,7 and 8 provided by the invention is distinguished
That obtain is CN-0Ni-0CoOx、CN-Ni、CN-Ni-3.0CoOx、CN-Ni-3.5CoOx、CN-Ni-4.0CoOxAnd CN-Ni-
4.5CoOxAnd CN-3.5CoOxReaction system, and carry out all band photocatalysis and decompose water active testing completely；Case study on implementation 4 and 5
That obtain is CN-Ni-3.5CoOxReaction system, and progress all band and visible light photocatalysis decompose the survey of water activity completely respectively
Examination.After the completion of decomposing water active testing, recycling photochemical catalyst (solid fraction) obtains respective sample.
Wherein, the photochemical catalyst recycled is added to the water progress photocatalysis and decomposes water test completely, the results show that recycling
There is sample good photocatalysis to decompose water activity completely.
Wherein, the method for recycling photochemical catalyst is conventional method in that art, such as centrifugation.
Wherein, the photochemical catalyst recycled under certain conditions may face the loss of material in terms of certain, such as lose part cobalt
Oxide or loss part nano nickel particles etc., but under normal circumstances, these losses do not influence the activity of photochemical catalyst,
Under necessary condition, the photochemical catalyst of recycling can be detected in advance, and supplements the material of partial loss accordingly in application, such as sent out
Existing nano nickel particles lose, and corresponding nano nickel particles can be supplemented in the reaction system, if the oxide of cobalt occurs
Loss, then can directly supplement the presoma of cobalt in the reaction system.
In reaction mixture provided by the invention, the presoma of cobalt uses Co (NO3)2·6H2O, mass concentration are stone
0.01~0.1 times of black phase carbon nitride, after completion of the reaction, the CoO of generationxQuality be graphite phase carbon nitride 0.002~
0.025 times, the variation in quality is mainly due to CoOx(mixture of cobalt oxide, three cobalt of titanium dioxide and three four cobalts of oxidation)
It is different and different, but the catalyst that these differences have no effect on institute's return water has the energy for decomposing that water is hydrogen and oxygen completely
Power.
Embodiment provided by the invention is the specific embodiment of application, since catalyst system of the invention can interim structure
It builds, and photochemical catalyst can be obtained during the reaction, therefore, in order to construct the convenience of reaction system, especially weigh material
Convenience and precisely, can be fixed with three kinds of components of pre-production (graphite phase carbon nitride, nano nickel particles and cobalt precursor) ratio,
Catalytic mixing liquid with high concentration, especially, the quality sum of graphite phase carbon nitride, nano nickel particles and cobalt precursor are to urge
Change the 0.5%~10% of mixed liquor quality；In this way, in use, directly the catalytic mixing liquid can be diluted to using concentration,
Or it draws part mixed liquor under stiring and is diluted to the configuration for realizing reaction solution using concentration.
CN-0Ni-0CoOx、CN-Ni、CN-Ni-3.5CoOxAnd CN-3.5CoOxReaction system is carrying out all band photocatalysis
The sample recycled after reaction carries out X-ray diffraction analysis to gained sample, and X-ray diffraction (XRD) figure is shown in Fig. 1.
According to Fig. 1 as can be seen that it is observed that two apparent characteristic peaks, correspond respectively to graphite phase carbon nitride in all samples
(100) and (002) crystal face；It is not observed in all samples and significantly belongs to Ni or CoOxCharacteristic peak, this is primarily due to
Ni or CoOxContent it is low and size is small.
CN-0Ni-0CoOxAnd CN-Ni-3.5CoOxReaction system, which recycles after carrying out all band light-catalyzed reaction, to be obtained
Sample carries out uv-visible absorption spectra (UV-vis) analysis, and acquired results are shown in Fig. 2.It is according to fig. 2 as can be seen that negative
Carry metallic nickel nano granule and CoOxAfter co-catalyst, sample light absorpting ability is remarkably reinforced.
The sample that CN-Ni reaction system recycles after carrying out all band light-catalyzed reaction carries out transmission electron microscopy,
Transmission electron microscope (TEM) photo is obtained, as shown in Figure 3.The results show that nano nickle granules dispersion loads in graphite phase carbon nitride.
CN-3.5CoOxThe sample that reaction system recycles after carrying out all band light-catalyzed reaction carries out transmission electron microscope
Scanning, obtains transmission electron microscope (TEM) photo, as shown in Figure 4.The result shows that Co (NO in light reaction procedure3)2·6H2O gradually turns
Become CoOxAnd it loads in graphite phase carbon nitride.
CN-Ni-3.5CoOxThe sample that reaction system recycles after carrying out all band light-catalyzed reaction carries out transmission electricity
Scarnning mirror obtains transmission electron microscope (TEM) photo, as shown in Figure 5.The results show that nano nickle granules and CoOxDispersion loads to stone
On black phase carbon nitride, without apparent agglomeration.
CN-Ni-3.5CoOxThe sample that reaction system recycles after carrying out all band light-catalyzed reaction carries out X-ray
Photoelectron spectroscopy (XPS) analysis, obtains x-ray photoelectron spectroscopy (XPS) figure, as a result shows in Fig. 6-1, Fig. 6-2 and Fig. 6-3
In.(especially Fig. 6-2) as the result is shown, the 2p of Ni 2p1/2And 2p3/2The energy level difference of track is about 17.5eV, it was demonstrated that Ni is with metal
State exists.
CN-0Ni-0CoOxAnd CN-Ni-3.5CoOxReaction system, which recycles after carrying out all band light-catalyzed reaction, to be obtained
Sample carries out spectrofluorimetry respectively, obtains corresponding fluorescence spectrum (PL) figure, as shown in Figure 7.The result shows that showing metallic nickel
Nano particle and CoOxThe compound of light induced electron and hole can effectively be inhibited as co-catalyst, and then improve photocatalysis effect
Rate.
CN-Ni-3.5CoOxThe Experimental results show of the photocatalysis hydrogen production of reaction system and oxygen activity processed is in Fig. 8-1 and figure
In 8-2, wherein Fig. 8-1 is the photocatalysis hydrogen production and oxygen activity figure processed under all band light (not plus optical filter) irradiation, hydrogen production rate
For 10.16 μm of ol/h, oxygen rate processed is 5.20 μm of ol/h, speed ratio 1.95:1；Fig. 8-2 is visible light (λ >=420nm) irradiation
Under photocatalysis hydrogen production and oxygen activity figure processed, hydrogen production rate is 1.03 μm of ol/h, and oxygen rate processed is 0.52 μm of ol/h, and speed ratio is
1.98:1.Hydrogen manufacturing and oxygen speed ratio processed under all band light and visible light conditions is each about 2:1, it was demonstrated that the reaction is photocatalysis
Water reaction is decomposed completely.
The invention discloses a kind of photocatalysis based on base metal load graphite phase carbon nitride to decompose aqueous systems completely
Construction method.This method is received according to the metallic nickel that reported method prepares graphite phase carbon nitride and good dispersion property first
Then graphite phase carbon nitride, metallic nickel nano granule dispersion liquid and cabaltous nitrate hexahydrate are added directly into pure water by rice grain,
Cabaltous nitrate hexahydrate is transformed into CoO by light reactionx, metallic nickel nano granule and CoOxSynergistic effect is used as co-catalyst, real
The complete hydrogen production by water decomposition of visible light catalytic and oxygen processed of base metal load graphite phase carbon nitride are showed.Operation of the present invention is simple,
Reproducible, the material preparation cost related to is cheap, to reduce photochemical catalyzing cost and building photochemical catalyzing
System and reduction photocatalysis decompose water cost completely and provide a kind of reliable scheme.
Claims (10)
1. a kind of photochemical catalyst for decomposing water completely, which is characterized in that using graphite phase carbon nitride as carrier, in graphite phase carbon nitride
Load has nano nickel particles and CoOx；Wherein, 1.0≤x≤1.5.
2. photochemical catalyst as described in claim 1, which is characterized in that according to quality meter, graphite phase carbon nitride: nano nickel particles
=1:(0.01~0.1).
3. photochemical catalyst as described in claim 1, which is characterized in that according to quality meter, graphite phase carbon nitride: CoOx=1:
(0.002~0.025).
4. photochemical catalyst as described in claim 1, which is characterized in that load to the CoO in graphite phase carbon nitridexIt is by containing
There is the cobalt precursor solution of graphite phase carbon nitride to generate in light reaction.
5. the preparation method of the described in any item photochemical catalysts of Claims 1 to 4, which is characterized in that by graphite phase carbon nitride, nickel
Nano particle and the mixed liquor of cobalt precursor carry out light reaction under the primary condition of anaerobic, and separation obtains photocatalysis after reaction
Agent.
6. the described in any item photochemical catalysts of Claims 1 to 4 are decomposing answering in the reaction that water prepares oxygen and hydrogen completely
With.
7. the catalytic mixing liquid that water is decomposed in a kind of photocatalysis completely, which is characterized in that including water, graphite-phase nitridation is mixed in water
Carbon, nano nickel particles and cobalt precursor, wherein the quality sum of graphite phase carbon nitride, nano nickel particles and cobalt precursor is to urge
Change the 0.5%~10% of mixed liquor quality.
8. the reaction method that water is decomposed in a kind of photocatalysis completely, which is characterized in that comprising steps of
1) reaction mixture is configured, the reaction mixture is the cobalt precursor for including graphite phase carbon nitride and nano nickel particles
Aqueous solution；
2) it is stirring and under illumination, is carrying out the reaction that water is decomposed in photocatalysis completely.
9. the reaction method that water is decomposed in photocatalysis as claimed in claim 8 completely, which is characterized in that in reaction mixture,
The concentration of graphite phase carbon nitride is 0.1~1mg/mL；According to quality meter, graphite phase carbon nitride: nano nickel particles=1:(0.01~
0.1), graphite phase carbon nitride: cobalt element=1:(0.002~0.02 in cobalt precursor).
10. the reaction method that water is decomposed in photocatalysis as claimed in claim 8 completely, which is characterized in that in step 2), light is anti-
The oxygen in reaction mixture is removed before answering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138702A (en) * | 2020-10-20 | 2020-12-29 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN113060771A (en) * | 2021-03-10 | 2021-07-02 | 华东理工大学 | Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride |
| CN113457696A (en) * | 2021-06-29 | 2021-10-01 | 西安交通大学 | Preparation method of phosphorus and sulfur co-modified cobaltous oxide and application of cobalt oxide in photocatalytic decomposition of water |
| CN114956004A (en) * | 2022-05-17 | 2022-08-30 | 宝武清洁能源鄂州有限公司 | Oxygen generator for producing oxygen by photosynthesis |
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| JP2007125496A (en) * | 2005-11-04 | 2007-05-24 | Nagaoka Univ Of Technology | Optical water decomposition catalyst and its manufacturing method |
| CN107159176A (en) * | 2017-06-14 | 2017-09-15 | 西安交通大学 | A kind of construction method of the photocatalytic system based on nano nickel particles co-catalyst |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007125496A (en) * | 2005-11-04 | 2007-05-24 | Nagaoka Univ Of Technology | Optical water decomposition catalyst and its manufacturing method |
| CN107159176A (en) * | 2017-06-14 | 2017-09-15 | 西安交通大学 | A kind of construction method of the photocatalytic system based on nano nickel particles co-catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138702A (en) * | 2020-10-20 | 2020-12-29 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN112138702B (en) * | 2020-10-20 | 2022-06-07 | 苏州大学 | Three-dimensional/two-dimensional Ni-Co bimetallic oxide/g-C3N4Nano composite material and preparation method and application thereof |
| CN113060771A (en) * | 2021-03-10 | 2021-07-02 | 华东理工大学 | Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride |
| CN113060771B (en) * | 2021-03-10 | 2023-11-03 | 华东理工大学 | Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride |
| CN113457696A (en) * | 2021-06-29 | 2021-10-01 | 西安交通大学 | Preparation method of phosphorus and sulfur co-modified cobaltous oxide and application of cobalt oxide in photocatalytic decomposition of water |
| CN113457696B (en) * | 2021-06-29 | 2022-04-22 | 西安交通大学 | Preparation method of phosphorus and sulfur co-modified cobaltous oxide and application of cobalt oxide in photocatalytic decomposition of water |
| CN114956004A (en) * | 2022-05-17 | 2022-08-30 | 宝武清洁能源鄂州有限公司 | Oxygen generator for producing oxygen by photosynthesis |
| CN114956004B (en) * | 2022-05-17 | 2023-12-05 | 宝武清洁能源鄂州有限公司 | Oxygenerator for producing oxygen by photosynthesis |
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