CN108704656A - A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification and its application during producing hydrogen peroxide - Google Patents
A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification and its application during producing hydrogen peroxide Download PDFInfo
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- CN108704656A CN108704656A CN201810550193.6A CN201810550193A CN108704656A CN 108704656 A CN108704656 A CN 108704656A CN 201810550193 A CN201810550193 A CN 201810550193A CN 108704656 A CN108704656 A CN 108704656A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000012986 modification Methods 0.000 title claims abstract description 32
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 13
- 239000010439 graphite Substances 0.000 title claims abstract description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000005034 decoration Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 claims 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
-
- 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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The preparation method and its application during producing hydrogen peroxide that the present invention provides a kind of graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification, the preparation method have many advantages, such as raw material it is cheap and easy to get, it is simple for process, environmentally protective, be easy to industrialized production, the g-C of surface carbon vacancy modification obtained by the method for the invention3N4, compared to the g-C of pure phase3N4, because of the presence in carbon vacancy so that g-C3N4Band gap narrow, electron delocalization extension, and carbon vacancy will become charge-trapping center, and the presence in carbon vacancy make the g-C that surface carbon vacancy is modified3N4H is generated under the same conditions2O2Ability be common g-C3N414 times.
Description
Technical field
The invention belongs to catalysis materials to prepare and environmental contaminants processing technology field, and in particular to a kind of carbon vacancy repair
Graphite phase carbon nitride (the g-C of decorations3N4) preparation method and its production hydrogen peroxide (H2O2) during application.
Background technology
Hydrogen peroxide (H2O2) it is a kind of strong oxidizer of water white transparency.Since its reaction product only has water or oxygen, so
It is often used as environmentally friendly Green Oxidant.H2O2Be widely used in the various aspects of production and living, for example, paper pulp and
Textile bleaching, chemical synthesis, environmental protection, medical and food sterilizing etc..From the point of view of the production technology of hydrogen peroxide, mesh
There are mainly two types of preceding more mature production methods, is electrolysis respectively and anthraquinone.The wherein short production of electrolysis technological process
It is efficient, but its consumption electric power excessive cost is too high, gradually by market.
In recent years, it is concerned using solar energy as the Photocatalitic Technique of Semiconductor of driving force production hydrogen peroxide.The mistake
Journey does not need additional H2As reducing agent, therefore more safety and environmental protection.In in the past few decades, dioxygen is produced for photocatalysis
The photochemical catalyst of water is mainly TiO2Or modified TiO2；Maurino etc. proposes that surface fluorination can improve TiO2Photocatalysis is at production
H2O2Rate；Tsukamoto etc. has found that by depositing Au-Ag alloys on surface TiO can also be improved2Photocatalysis is at production H2O2's
Rate.However, due to TiO2With larger energy gap (3.0~3.2eV), therefore can only be issued in ultraviolet optical drive raw effective
Light-catalyzed reaction, and ultraviolet light only accounts for 4% or so of solar energy gross energy, this just limits TiO2To the extensive of solar energy
It utilizes.Even if in addition, TiO2Or modified TiO2It under ultraviolet light can be effectively by O2It is reduced to H2O2, the H of generation2O2It also can be
It decomposes under ultraviolet light.Therefore there is visible light catalysis activity to be avoided that H again simultaneously for exploitation2O2The photocatalysis of selfdecomposition
Agent is an important research direction.
Graphite phase carbon nitride (g-C3N4) it is a kind of novel with visible light-responded non-metal optical catalyst, due to its taboo
Bandwidth is moderate (2.7eV), g-C3N4Conduction band is located at -1.3V, compares O2/H2O2Reduction potential (+0.695V) it is low, so g-C3N4
Light induced electron in theory can be by O2It is reduced to H2O2.Shiraishi etc. has found in g-C3N4There is ethyl alcohol as sacrifice agent
In the case of can be effectively by O2It is reduced to H2O2.But H in the presence of no ethyl alcohol2O2Formation efficiency is very low.This hair
It is bright to propose the graphite phase carbon nitride (g-C for counting a kind of surface carbon vacancy modification3N4) preparation method and use it for production H2O2。
Invention content
In view of the problems of the existing technology, the present invention is the technical solution for solving problems of the prior art and using
It is as follows：
A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification, which is characterized in that including such as
Lower step：
A certain amount of melamine is placed in ceramic crucible with cover by step 1, and crucible is put into muffle furnace hearth later
The heart, with 20 DEG C of min-1Heating rate increase the temperature to 520 DEG C and keep the temperature 4h, take out sample after Muffle furnace cooled to room temperature
Product are simultaneously ground into uniform powder with agate mortar, and it is common g-C to obtain sample3N4；
Step 2, the common g-C that will be prepared3N4It is placed in ceramic crucible with cover, is put into tube furnace, be passed through high-purity argon gas
First drain the air in pipe, after in argon gas atmosphere with 20 DEG C of min-1Heating rate be warming up to 520 DEG C and calcine 2h, wait for pipe
Sample is taken out after formula stove cooled to room temperature and is ground into uniform powder, which is the g- of surface carbon vacancy modification
C3N4。
The concentration of high-purity argon gas is not less than 99.99% in the step 2.
A kind of graphite phase carbon nitride photocatalyst applications of surface carbon vacancy modification in production hydrogen peroxide the specific steps are：
The g-C for taking the surface carbon vacancy obtained in a certain amount of step 2 to modify3N4It is distributed in appropriate distilled water, and is added as catalyst
The fluorescence reaction liquid of certain volume, 2h is then stirred under dark condition makes oxygen in water reach absorption-in catalyst surface
Then desorption equilibrium is irradiated as visible light source using the xenon lamp added with 420nm optical filters, obtains H2O2Dispersion liquid.
The fluorescence reaction liquid group is divided into：Potassium Hydrogen Phthalate 8.2g/L, horseradish peroxidase 30mg/L, to hydroxyl
Phenylacetic acid 270mg/L.
The invention has the advantages that：
Graphite phase carbon nitride (the g-C of surface carbon vacancy modification provided by the invention3N4) photochemical catalyst preparation method,
In calcination process, high temperature makes argon molecules obtain huge energy and part argon molecules is enabled to become unstable irregular to make
Movement, the irregular movement molecule impact surface atom and may transfer energy to target atoms, if the energy transmitted
More than the combination energy of target atoms, then target atoms will sputter out from catalyst surface and be formed simultaneously vacancy.Due to carbon original
Son has the surface area of bigger and smaller relative atomic mass than nitrogen-atoms, and larger surface area enables carbon atom to receive
More energy, smaller molecular weight and larger energy make carbon atom more have an opportunity to splash out from surface, therefore, in High Temperature Argon
Atmosphere encloses interior calcination and catalyst is made to form carbon vacancy, the g-C of surface carbon vacancy modification3N4The preparation method of photochemical catalyst
Have many advantages, such as raw material it is cheap and easy to get, it is simple for process, environmentally protective, be easy to industrialized production.
Compared with prior art：The g-C of surface carbon vacancy modification prepared by the method for the present invention3N4, compared to the g- of pure phase
C3N4, because of the presence in carbon vacancy so that g-C3N4Band gap narrow, electron delocalization extension, and carbon vacancy will catch as charge
Center is obtained, this makes the g-C that surface carbon vacancy is modified3N4With stronger light abstraction width, stronger photogenerated charge separation effect
Rate possesses more light induced electrons for restoring oxygen molecule；The introducing in carbon vacancy makes g-C3N4O2Absorption is become by physical absorption
For chemisorption, it is more advantageous to light induced electron and is successfully transferred to O2；Carbon vacancy makes the also two step single electron side of reason of oxygen molecule
Formula becomes a step bielectron mode.The presence in carbon vacancy makes Cv-g-C3N4H is generated under the same conditions2O2Ability be g-
C3N414 times；Cv-g-C3N4H after being recycled at four times2O2Significant change does not occur for yield, has good stable circulation
Property.
The g-C of surface carbon vacancy modification of the present invention3N4With common g-C3N4Compared to there is no the conditions of sacrifice agent
Under, it can be with photo catalytic reduction O2Generate H2O2, H2O2Detection use fluorescence spectrophotometry, due to H2O2Fluorescence reaction liquid with
H2O2The substance generated after reaction has fluorescence signal, and the size and H of fluorescence intensity2O2Concentration has certain proportionate relationship,
So the fluorescence intensity that can detect sample by using sepectrophotofluorometer carrys out H in reflection system2O2Concentration variation.
Description of the drawings
Fig. 1 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4ESR signals；
Fig. 2 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4Density of photocurrent pair
Than figure；
Fig. 3 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4Fluorescence spectra；
Fig. 4 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4O2- TPD schemes；
Fig. 5 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4It produces under the same conditions
Raw H2O2Yield comparison figure；
Fig. 6 is the g-C of surface carbon vacancy modification prepared by present example 13N4Four cycle photocatalysis generate H2O2Concentration
Figure.
Specific implementation mode
Below with reference to the embodiments and with reference to the accompanying drawing the technical solutions of the present invention will be further described：
Embodiment 1
4g melamines are placed in 30ml ceramic crucibles with cover by step 1, and crucible is put into muffle furnace hearth later
The heart, with 20 DEG C of min-1Heating rate increase the temperature to 520 DEG C and keep the temperature 4h, take out sample after Muffle furnace cooled to room temperature
Product are simultaneously ground into uniform powder with agate mortar, which is common g-C3N4；
Step 2, the common g-C that will be prepared3N4It is placed in 30ml ceramic crucibles with cover, is put into tube furnace, be passed through high-purity
Argon gas (99.99%) first drains the air in pipe, after in argon gas atmosphere with 20 DEG C of min-1Heating rate be warming up to 520 DEG C
And 2h is calcined, sample is taken out after tube furnace cooled to room temperature and is ground into uniform powder.The sample is surface carbon
The g-C of vacancy modification3N4, it is named as Cv-g-C3N4；
Step 3, the Cv-g-C that will be obtained in step 2 respectively3N4With common g-C3N40.1g is respectively taken to be distributed to 100ml distillations
In water, and certain volume fluorescence reaction liquid (Potassium Hydrogen Phthalate 8.2g/L, horseradish peroxidase 30mg/L, to hydroxyl is added
Base phenylacetic acid 270mg/L), then under dark condition stir 2h so that oxygen in water catalyst surface reach absorption-take off
Attached balance is irradiated using the 300W xenon lamps added with 420nm optical filters as visible light source later；In During Illumination every
20min takes 4ml dispersion liquids from reactor, centrifuges and take supernatant liquor at once, is added 1mL 0.1mol/L's into supernatant
Sodium hydroxide solution shakes up, and stands 10min with determination sample fluorescence intensity (excitation wavelength 315nm, launch wavelength 409nm).
According to the g-C of surface carbon vacancy modification obtained in embodiment 13N4With common g-C3N4Several contrast tests are done to obtain
To Fig. 1-4, and respectively by the g-C of equivalent surface carbon vacancy modification3N4With common g-C3N4Hydrogen peroxide obtained does yield and follows
The test of ring concentration obtains Fig. 5-6, is analyzed as follows to each attached drawing：Attached drawing 1 is that surface carbon vacancy prepared by present example 1 is repaiied
The g-C of decorations3N4With common g-C3N4ESR signals；As can be seen from the figure since the C in triazine ring contains azygous single electricity
Son, therefore g-C3N4The one very strong single electron peak of appearance in test scope, and Cv-g-C prepared by the present invention3N4Peak here
Intensity is compared to g-C3N4It is substantially reduced, illustrates Cv-g-C3N4Middle carbon content reduces, that is, further demonstrates that Cv-g-C3N4Middle formation
Carbon vacancy；
Attached drawing 2 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4Density of photocurrent
Comparison diagram；The Cv-g-C prepared as we can see from the figure3N4Density of photocurrent value be about g-C3N4Twice, this illustrates Cv-
g-C3N4More light induced electrons can be generated for restoring O2；
Attached drawing 3 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4Fluorescence spectrum
Figure；As can be seen from the figure the Cv-g-C prepared3N4Fluorescence intensity be substantially reduced, illustrate that carbon vacancy makes the electronics-of catalyst
Hole separative efficiency significantly improves, this is because carbon vacancy will simultaneously be generated along with unsaturated nitrogen atom, and this unsaturation
Nitrogen-atoms can capture light induced electron and inhibit it compound with photohole, so that fluorescence intensity is reduced；
Attached drawing 4 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4O2- TPD schemes；From
It can be seen from the figure that O2In Cv-g-C3N4Surface there are two types of suction type, respectively chemisorption and physical absorption；And in g-
C3N4Surface only has physical absorption；
Attached drawing 5 is the g-C of surface carbon vacancy modification prepared by present example 13N4With common g-C3N4Under the same conditions
The H of generation2O2Yield comparison figure；As can be seen from the figure Cv-g-C3N4Photocatalysis generates H2O2Ability be far longer than g-C3N4,
Cv-g-C under the same terms3N4Photo catalytic reduction O2Generate H2O2Ability be g-C3N415 times；
Attached drawing 6 is the g-C of surface carbon vacancy modification prepared by present example 13N4Four cycle photocatalysis generate H2O2It is dense
Degree figure；As can be seen from the figure after catalyst is recycled at four times, H2O2Yield kept stable, this illustrates Cv-g-C3N4
H is generated in photo catalytic activation molecular oxygen2O2Aspect has superior stability.
Protection scope of the present invention is not limited to the above embodiments, it is clear that those skilled in the art can be to this hair
It is bright to carry out various changes and deformation without departing from scope and spirit of the present invention.If these changes and deformation belong to power of the present invention
In the range of profit requirement and its equivalent technologies, then including the intent of the present invention also includes these changes and deforms.
Claims (4)
1. a kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification, which is characterized in that including as follows
Step：
A certain amount of melamine is placed in ceramic crucible with cover by step 1, and crucible is put into muffle furnace hearth center later,
With 20 DEG C of min-1Heating rate increase the temperature to 520 DEG C and keep the temperature 4h, take out sample after Muffle furnace cooled to room temperature
It is used in combination agate mortar to be ground into uniform powder, it is common g-C to obtain sample3N4；
Step 2, the common g-C that will be prepared3N4It is placed in ceramic crucible with cover, is put into tube furnace, be passed through high-purity argon gas and first arrange
Although interior air, after in argon gas atmosphere with 20 DEG C of min-1Heating rate be warming up to 520 DEG C and calcine 2h, wait for tube furnace
Sample is taken out after cooled to room temperature and is ground into uniform powder, which is the g-C of surface carbon vacancy modification3N4。
2. a kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification as described in claim 1,
It is characterized in that：The concentration of high-purity argon gas is not less than 99.99% in the step 2.
3. the preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification a kind of is during producing hydrogen peroxide
Using, it is characterised in that：The g-C that surface carbon vacancy described in claim 1 is modified3N4The preparation method of photochemical catalyst is made
Surface carbon vacancy modification g-C3N4Photocatalyst applications are in production H2O2, the specific steps are：A certain amount of surface carbon vacancy is taken to repair
The g-C of decorations3N4It is distributed in appropriate distilled water as catalyst, and the fluorescence reaction liquid of certain volume is added, then in dark item
2h is stirred under part makes oxygen in water reach adsorption-desorption balance in catalyst surface, then with the xenon added with 420nm optical filters
Lamp is irradiated as visible light source, obtains H2O2Dispersion liquid.
4. a kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification as claimed in claim 3 is in life
Produce the application during hydrogen peroxide, it is characterised in that：The fluorescence reaction liquid group is divided into Potassium Hydrogen Phthalate 8.2g/L, horseradish
Peroxidase 30mg/L, p-hydroxyphenylaceticacid 270mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810550193.6A CN108704656A (en) | 2018-05-31 | 2018-05-31 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification and its application during producing hydrogen peroxide |
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| CN109433246B (en) * | 2018-12-26 | 2021-07-16 | 台州学院 | Carbon vacancy-containing nanosheet C3N4Photocatalyst and preparation method thereof |
| CN109433246A (en) * | 2018-12-26 | 2019-03-08 | 台州学院 | Nanometer sheet C containing carbon vacancy3N4Photochemical catalyst and preparation method |
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| CN115282996A (en) * | 2022-07-11 | 2022-11-04 | 华东理工大学 | Preparation method and application of P, S, B backfill nitrogen vacancy carbon nitride material for efficient photolysis of water to produce hydrogen |
| CN115845896A (en) * | 2022-11-17 | 2023-03-28 | 吉林大学 | Pyridine-doped modified graphite-phase carbon nitride photocatalyst, and preparation method and application thereof |
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