CN106902859A - A kind of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst and its preparation method and application - Google Patents
A kind of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010439 graphite Substances 0.000 title claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical class NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- AUFJTVGCSJNQIF-UHFFFAOYSA-N 2-Amino-4,6-dihydroxypyrimidine Chemical class NC1=NC(O)=CC(=O)N1 AUFJTVGCSJNQIF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract description 2
- 239000002800 charge carrier Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 150000003230 pyrimidines Chemical class 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LNDZXOWGUAIUBG-UHFFFAOYSA-N 6-aminouracil Chemical class NC1=CC(=O)NC(=O)N1 LNDZXOWGUAIUBG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- -1 carbon nitrides Chemical class 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- MPNBXFXEMHPGTK-UHFFFAOYSA-N pyrimidine-4,5,6-triamine Chemical compound NC1=NC=NC(N)=C1N MPNBXFXEMHPGTK-UHFFFAOYSA-N 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Prepared the invention belongs to material and photocatalysis technology field, be related to a kind of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst and its preparation method and application.The visible light catalyst, with the organic molecule (amino and/or hydroxyl substituted pyrimidines) of different carbon-nitrogen ratios for auto-dope carbon source, is obtained after being sufficiently mixed with melamine as predecessor through vacuum heat and hot copolymerization.Preparation process is simple, environmental protection, low cost.Compared with common graphite phase carbon nitride, the visible light catalyst is improved in terms of the absorption region and absorption intensity of visible region, and can realize the regulation and control for visible light-responded scope by the change of incorporation.In addition, the visible light catalyst overcomes the shortcoming of conventional graphite phase carbon nitride, the recombination rate of photo-generated charge carriers is reduced, and improve the effect that visible light catalytic decomposes aquatic products hydrogen.
Description
Technical field
Prepared the invention belongs to material and photocatalysis technology field, be related to a kind of efficient carbon auto-dope graphite phase carbon nitride can
See photochemical catalyst, it is based on thermal copolymerization into the preparation method of method, and its application in visible light catalytic decomposes aquatic products hydrogen.
Background technology
Nowadays, the mankind exacerbate energy crisis and environmental pollution for depending on unduly for fossil energy, thus find and can follow
The clean energy resource of ring is extremely urgent.Photochemical catalyst based on semiconductor is considered as to solve global energy with environmental problem most
Has one of technology of potentiality.However, photochemical catalyst has that unstable, active low, high cost, solar energy utilization ratio are low,
Photochemical catalyst is limited in real-life application.Therefore, obtain a kind of efficient, stable, environment-friendly and cheap
Visible light catalyst has turned into the important topic in this field.
As a kind of stabilization, cheap, environmental protection visible light catalyst, graphite phase carbon nitride (g-C3N4) cause recently extensively
General concern.It has the energy gap of 2.7eV, can absorb the visible ray at 460nm.Although graphite phase carbon nitride is in photocatalysis
Field has been achieved with some progress, but its photocatalysis efficiency is still not fully up to expectations.
Nowadays existing many methods are used to solve the above problems, wherein element doping as a kind of effective modification mode
Through being widely used in graphite phase carbon nitride.The A of CN 103263942 disclose a kind of load mesoporous graphite phase carbon nitride visible ray of cobalt
Catalyst, it improves photocatalysis efficiency by mesoporous graphite phase carbon nitride using infusion process is metal cobalt loaded, and compares
Supported precious metal catalyst it is cheap, but the biocompatibility of metal ion is poor, with nonmetal doping person's phase
Than with certain inferior position.The A of CN 103769213 disclose a kind of phosphorus doping graphite phase carbon nitride visible light catalyst, and it leads to
Crossing makes phosphoric acid molecules adsorb in the prepared phosphorus doping graphite phase carbon nitride visible light catalyst of melamine microparticle surfaces；CN
103920518 A disclose a kind of sulphur modification carbon nitride photocatalyst with high visible-light activity, and it is by by melamine
With sublimed sulfur ground and mixed and sulphur modification carbon nitride photocatalyst is obtained；A kind of sulfur doping stone is disclosed in the A of CN 104056648
Black phase carbon nitride visible light catalyst, its by the way that sulphur powder is scattered in the cyanamide aqueous solution after carry out polycondensation reaction again and sulphur be obtained
Doped graphite phase carbon nitride visible light catalyst, but the above method all can introducing hetero-atoms, so as to form defect, carried as photoproduction
Flow the complex centre of son.Comparatively speaking, this modification mode of auto-dope then will not introducing hetero-atoms, such that it is able to avoid well
The generation in complex centre.In recent years, researcher successfully synthesizes carbon auto-dope graphite phase carbon nitride, although it can
The efficiency of visible light catalytic hydrogen manufacturing is improved, but lifting effect is still limited (referring to Guohui Dong, Kun Zhao, Lizhi
Zhang,Carbon self-doping induced high electronic conductivity and
photoreactivity of g-C3N4[J],Chem.Commun.,2012,48:6178-6180)。
The content of the invention
For the less efficient problem of the photocatalysis hydrogen production of existing carbon auto-dope graphite phase carbon nitride visible light catalyst, this
Invention aims to provide a kind of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst and its preparation method and application.
Specifically, the present invention is adopted the following technical scheme that：
On the one hand, the invention provides a kind of preparation side of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst
Method, it comprises the following steps：
1) melamine and carbon nitrogen organic molecule are added in solvent, solvent evaporated after stirring, after grinding
To mixture；
2) by step 1) in the mixture that obtains be placed in 5~24h in 80~180 DEG C of vacuum environments, be then placed in Muffle furnace
In in 450~650 DEG C be heat-treated 2~8h, obtain efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
In above-mentioned preparation method, step 1) in carbon nitrogen organic molecule be selected from 2,4,6- Triaminopyrimidines, 2- amino -4,
Any one in 6- dihydroxy-pyrimidines, 4- amino -2,6- dihydroxy-pyrimidines.
In above-mentioned preparation method, step 1) in solvent be selected from ethanol, water, isopropanol any one.
In a preferred embodiment, 1 the step of above-mentioned preparation method) in melamine and carbon nitrogen organic molecule
Weight ratio be 1:0.005~0.2, preferably 1:0.01~0.15.
On the other hand, nitrogenized by efficient carbon auto-dope graphite-phase obtained in above-mentioned preparation method the invention provides one kind
Carbon visible light catalyst.
Last aspect, the invention provides above-mentioned efficient carbon auto-dope graphite phase carbon nitride visible light catalyst visible
Application in photocatalysis Decomposition aquatic products hydrogen, it can be catalytically decomposed water to prepare hydrogen under visible light.
Compared with prior art, using above-mentioned technical proposal the invention has the advantages that：
1) present invention, with melamine as predecessor, is auto-dope carbon source with the organic molecule of different carbon-nitrogen ratios, success
Efficient carbon auto-dope graphite phase carbon nitride visible light catalyst is obtained, preparation process is simple, energy consumption are low；
2) compared with common graphite phase carbon nitride visible light catalyst, efficient carbon auto-dope graphite phase carbon nitride of the invention
Visible light catalyst is improved in terms of the absorption region and absorption intensity of visible region, and can be by incorporation
Change and realize the regulation and control for visible light-responded scope, while inhibit photo-generate electron-hole to be combined, with stably, can
Reclaim, cheap, environmental protection the features such as；
3) photochemical catalyzing system is carried out using efficient carbon auto-dope graphite phase carbon nitride visible light catalyst of the invention
Hydrogen, it is found that it possesses photocatalysis Decomposition aquatic products hydrogen activity higher under visible light, and easily reclaims, and repeats and utilizes.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of carbon auto-dope graphite phase carbon nitride visible light catalyst in embodiment 1.
Fig. 2 is the Fourier transform infrared spectroscopy figure of carbon auto-dope graphite phase carbon nitride visible light catalyst in embodiment 1
(FT-IR)。
Fig. 3 is that the carbon auto-dope graphite phase carbon nitride of different 2,4,6- Triaminopyrimidines additions is mutually nitrogenized with conventional graphite
The outward appearance of carbon compares figure.
Fig. 4 is that the carbon auto-dope graphite phase carbon nitride of different 2,4,6- Triaminopyrimidines additions is mutually nitrogenized with conventional graphite
The UV-vis DRS spectrogram (UV-Vis DRS) of carbon.
Fig. 5 is that the carbon auto-dope graphite phase carbon nitride of different 2,4,6- Triaminopyrimidines additions is mutually nitrogenized with conventional graphite
Carbon carries out the Performance comparision figure of visible light catalytic hydrogen production by water decomposition.
Specific embodiment
Technical scheme is made further instructions below in conjunction with the drawings and specific embodiments.Except as otherwise rule
Fixed outer, instrument, reagent, material for being used in the following example etc. can be obtained by routine business means.
Embodiment 1：The preparation of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
Melamine (2g) and 2,4,6- Triaminopyrimidines (0.03g) are added in ethanol (6mL), are steamed after stirring
Dry ethanol, is fully ground uniformly, obtains mixture.Said mixture is placed into 12h under 100 DEG C of vacuum conditions, is then placed in
4h is heat-treated in 550 DEG C in Muffle furnace, efficient carbon auto-dope graphite phase carbon nitride visible light catalyst (0.90g) is obtained, its X is penetrated
Ray diffraction diagram is as shown in figure 1, its Fourier transform infrared spectroscopy figure is as shown in Figure 2.
As shown in Figure 1, two obvious diffraction maximums are respectively belonging to (100) of graphite phase carbon nitride at 13.0 ° and 27.4 °
(002) crystal face.As shown in Figure 2, in 810cm-1With 1200~1600cm-1The peak at place is respectively belonging to the breathing vibration of piperazine ring
With the stretching vibration of CN heterocycles, in 3200cm-1The more NH not being bonded that the broad peak Master Home at place exists in nitridation carbon surface2
With the stretching vibration caused by NH.
Embodiment 2：The preparation of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
Melamine (2g) and 2- amino -4,6- dihydroxy-pyrimidines (0.02g) are added in ethanol (10mL), stirring is equal
Ethanol is evaporated after even, is fully ground uniformly, obtain mixture.Said mixture is placed into 10h under 80 DEG C of vacuum conditions, then
It is put into Muffle furnace and is heat-treated 5h in 530 DEG C, obtains efficient carbon auto-dope graphite phase carbon nitride visible light catalyst (0.88g).
Embodiment 3：The preparation of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
Melamine (2g) and 2- amino -4,6- dihydroxy-pyrimidines (0.04g) are added in water (30mL), stirred
After be evaporated water, be fully ground uniform, obtain mixture.Said mixture is placed into 24h, Ran Houfang under 120 DEG C of vacuum conditions
Enter in Muffle furnace and be heat-treated 6h in 520 DEG C, obtain efficient carbon auto-dope graphite phase carbon nitride visible light catalyst (0.87g).
Embodiment 4：The preparation of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
Melamine (2g) and 4- amino -2,6- dihydroxy-pyrimidines (0.06g) are added in isopropanol (20mL), are stirred
Isopropanol is evaporated after uniform, is fully ground uniformly, obtain mixture.Said mixture is placed into 5h under 180 DEG C of vacuum conditions,
It is then placed in being heat-treated 2h in 600 DEG C in Muffle furnace, obtains efficient carbon auto-dope graphite phase carbon nitride visible light catalyst
(0.80g)。
Embodiment 5：Influence of the carbon nitrogen organic molecule addition to visible light catalyst is investigated.
4 kinds of carbon auto-dopes of difference 2,4,6- Triaminopyrimidine additions are prepared using the preparation method in embodiment 1
Graphite phase carbon nitride visible light catalyst, wherein the consumption of 2,4,6- Triaminopyrimidines be respectively 0.01g, 0.03g, 0.06g and
0.09g, the product for obtaining is respectively designated as CN-1, CN-2, CN-3 and CN-4.
As shown in figure 3, compared with conventional graphite phase carbon nitride (CN-0), 4 kinds of carbon auto-dope graphite phase carbon nitride visible rays
The apparent colour of catalyst is deeper, and with 2, the increase of 4,6- Triaminopyrimidine additions shows apparent colour and adds step by step
Deep trend.
UV-vis DRS spectrum is carried out to above-mentioned 4 kinds of carbon auto-dope graphite phase carbon nitrides and conventional graphite phase carbon nitride
Test, its result is as shown in Figure 4.As shown in Figure 4, compared to the graphite phase carbon nitride (CN-0) of undoped p, carbon auto-dope graphite
The visible absorption scope of phase carbon nitride all there occurs red shift, and with the increase of doping, the amplitude of red shift also increases therewith
Plus, absorbing wavelength can be more than 700nm, therefore greatly expand the photoresponse scope of photochemical catalyst；In addition, carbon auto-dope graphite
Absorption intensity of the phase carbon nitride in visible region is also enhanced.As can be seen here, carbon auto-dope graphite phase carbon nitride energy
Enough greatly improve utilization ratio of the photochemical catalyst to light.
Visible light catalytic decomposition water system is carried out to above-mentioned 4 kinds of carbon auto-dope graphite phase carbon nitrides and conventional graphite phase carbon nitride
The experiment of standby hydrogen, its result is as shown in Figure 5.As shown in Figure 5, compared to the graphite phase carbon nitride (CN-0) of undoped p, own
The visible light catalytic decomposition water hydrogen-producing speed of carbon auto-dope graphite phase carbon nitride all gets a promotion, and wherein the hydrogen-producing speed of CN-2 is most
Height (52.0 μm of olh-1), about CN-0 (4.8 μm of olh-1) 11 times.
Claims (7)
1. a kind of preparation method of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst, it comprises the following steps：
1) melamine and carbon nitrogen organic molecule are added in solvent, solvent evaporated after stirring is mixed after grinding
Compound；
2) by step 1) in the mixture that obtains be placed in 5~24h in 80~180 DEG C of vacuum environments, be then placed in Muffle furnace in
450~650 DEG C of 2~8h of heat treatment, obtain efficient carbon auto-dope graphite phase carbon nitride visible light catalyst.
2. preparation method according to claim 1, it is characterised in that：
Step 1) described in carbon nitrogen organic molecule be selected from 2,4,6- Triaminopyrimidines, 2- amino -4,6- dihydroxy-pyrimidines, 4- ammonia
Any one in base -2,6- dihydroxy-pyrimidines.
3. preparation method according to claim 1, it is characterised in that：
Step 1) described in solvent be selected from ethanol, water, isopropanol in any one.
4. preparation method according to claim 1, it is characterised in that：
Step 1) described in the weight ratio of melamine and the carbon nitrogen organic molecule be 1:0.005~0.2.
5. preparation method according to claim 1, it is characterised in that：
Step 1) described in the weight ratio of melamine and the carbon nitrogen organic molecule be 1:0.01~0.15.
6. a kind of efficient carbon auto-dope graphite phase carbon nitride visible light catalyst, it is by according to any one of claim 1 to 5
Described preparation method is obtained.
7. efficient carbon auto-dope graphite phase carbon nitride visible light catalyst according to claim 6 is decomposed in visible light catalytic
Application in aquatic products hydrogen.
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Cited By (9)
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| CN108355692A (en) * | 2018-01-22 | 2018-08-03 | 华中科技大学 | Graphite phase carbon nitride/titanic oxide nano compound material of carbon auto-dope and preparation method thereof, application |
| CN109012726A (en) * | 2018-07-25 | 2018-12-18 | 江苏理工学院 | A kind of molten salt method production of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst and application |
| CN111318297A (en) * | 2020-02-24 | 2020-06-23 | 江苏大学 | High-hydrophilicity g-C3N4And preparation method and application thereof |
| CN112536056A (en) * | 2019-09-20 | 2021-03-23 | 湖北大学 | Tungsten disulfide quantum dot/C-doped graphite-like phase carbon nitride nanosheet heterostructure photocatalyst and preparation method thereof |
| CN112744797A (en) * | 2020-12-18 | 2021-05-04 | 中国计量大学上虞高等研究院有限公司 | Nitrogen-boron doped graphite phase carbon nitride quantum dot and preparation method and application thereof |
| CN113600239A (en) * | 2021-08-09 | 2021-11-05 | 华侨大学 | Triptycene modified graphite-phase carbon nitride and preparation method and application thereof |
| CN114100665A (en) * | 2021-12-06 | 2022-03-01 | 合肥工业大学 | Preparation method and application of carbonyl functionalized graphite phase carbon nitride |
| CN115108861A (en) * | 2022-05-06 | 2022-09-27 | 广州大丘有机农产有限公司 | Fermentation treatment process of traditional Chinese medicine residues |
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| CN114100665B (en) * | 2021-12-06 | 2024-03-29 | 合肥工业大学 | Preparation method and application of carbonyl functionalized graphite phase carbon nitride |
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| CN115108861B (en) * | 2022-05-06 | 2023-04-07 | 广州大丘有机农产有限公司 | Fermentation treatment process of traditional Chinese medicine residues |
| CN117586523A (en) * | 2023-11-29 | 2024-02-23 | 山东大学 | Self-assembled supermolecular material containing six-membered carbon-nitrogen heterocycle, and preparation method and application thereof |
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