CN115646521B - Method for preparing hydrogen peroxide by graphite phase nitrogen carbide photocatalyst and application thereof - Google Patents
Method for preparing hydrogen peroxide by graphite phase nitrogen carbide photocatalyst and application thereof Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title abstract description 72
- 229910052757 nitrogen Inorganic materials 0.000 title abstract description 36
- 229910002804 graphite Inorganic materials 0.000 title description 7
- 239000010439 graphite Substances 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000000243 solution Substances 0.000 claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 14
- 238000005286 illumination Methods 0.000 claims abstract description 12
- 239000002262 Schiff base Substances 0.000 claims abstract description 11
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- -1 heterocyclic modified graphite Chemical class 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- CHNYVNOFAWYUEG-UHFFFAOYSA-N 1h-pyrrole-3-carbaldehyde Chemical compound O=CC=1C=CNC=1 CHNYVNOFAWYUEG-UHFFFAOYSA-N 0.000 claims description 4
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- AZVSIHIBYRHSLB-UHFFFAOYSA-N 3-furaldehyde Chemical compound O=CC=1C=COC=1 AZVSIHIBYRHSLB-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing hydrogen peroxide by using a graphite-phase nitrogen carbide photocatalyst and application thereof, wherein the method comprises the steps of carrying out thermal polymerization reaction on urea, grinding to obtain graphite-phase nitrogen carbide powder, mixing the graphite-phase nitrogen carbide powder with a penta-heterocycle ligand, adding the penta-heterocycle ligand into a1, 4-dioxane solution, carrying out ultrasonic dispersion, heating and stirring in an oil bath after uniformity, carrying out Schiff base reaction, carrying out centrifugal washing reaction on the penta-heterocycle modified graphite-phase nitrogen carbide with an N, N-dimethylformamide solution and anhydrous methanol to obtain penta-heterocycle modified graphite-phase nitrogen carbide, forming a mixed solution in a photocatalytic reaction bottle, continuously exposing oxygen, sealing the reaction bottle, carrying out illumination reaction, and filtering to obtain hydrogen peroxide. The invention can effectively utilize the amino functional group hung at the edge of the g-C 3N4, and graft other functional groups or organic molecules through chemical reaction, so that the electronic structure and active site of the material are regulated and controlled while the original g-C 3N4 structure is maintained, thereby improving the efficiency of producing H 2O2 by photocatalysis.
Description
Technical Field
The invention relates to a method for preparing hydrogen peroxide and application thereof, in particular to a method for preparing hydrogen peroxide by using a graphite phase nitrogen carbide photocatalyst and application thereof.
Background
Hydrogen peroxide (H 2O2) is an environmentally friendly multifunctional oxidizer that has found applications in the chemical industry, medical, energy and environmental fields. The current industrial production method H 2O2 is usually an anthraquinone method, and has the defects of high energy consumption, environment friendliness, explosion hazard and the like. The photocatalytic preparation of H 2O2 is to convert water and oxygen into hydrogen peroxide by utilizing solar energy, is considered as a sustainable, safe and green process, and is expected to realize the low-cost and high-efficiency on-site preparation of H 2O2. Meanwhile, graphite-phase carbon nitride (g-C 3N4) has been attracting attention from researchers in the field of photocatalysis due to its visible light activity, low cost synthesis process, chemical stability and unique layered structure. However, the pure g-C 3N4 photocatalyst has the defects of low separation efficiency of photo-generated carriers, few active sites, poor selective production of H 2O2, and the like, so that the efficiency of the photocatalytic production of H 2O2 is not ideal, and the requirements of people cannot be met.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen peroxide by utilizing a modified graphite phase nitrogen carbide photocatalyst and application thereof
The invention provides the following scheme:
a preparation method of a five-membered heterocyclic modified graphite-phase nitrogen carbide photocatalyst comprises the following steps:
placing urea into a heating device for thermal polymerization reaction, and grinding the obtained solid after the reaction is finished to obtain graphite-phase nitrogen carbide powder;
Weighing a certain amount of graphite phase nitrogen carbide powder, mixing with five-membered heterocyclic ligand, adding into 1, 4-dioxane solution, performing ultrasonic dispersion, heating in an oil bath, stirring, and performing Schiff base reaction;
The g-C 3N4 rich in amino functional groups is prepared through heating thermal polymerization reaction, and then Schiff base reaction grafting five-membered heterocyclic molecules are carried out on the edge of the g-C 3N4 through a solvothermal method;
After the Schiff base reaction is finished, performing centrifugal washing reaction by using an N, N-dimethylformamide solution and absolute methanol, and then performing vacuum drying on the obtained material to finally obtain the five-membered heterocyclic modified graphite phase nitrogen carbide.
Further, the heating device is a muffle furnace, and the thermal polymerization reaction is carried out for 2-6 hours at the temperature of 500-600 ℃.
Further, the five-membered heterocyclic ligand includes: thiophene-3-carbaldehyde, pyridine-3-carbaldehyde, pyrrole-3-carbaldehyde.
Further, ultrasonic dispersion is carried out, oil bath is carried out at the temperature of 80-120 ℃ after uniform dispersion, heating and stirring are carried out for 6-24h, and Schiff base reaction is carried out.
Further, the mass of the urea is 30g, the thermal polymerization time is 3 hours, and the temperature rise and fall rate of the muffle furnace is 3 ℃/min.
A method for preparing hydrogen peroxide by utilizing modified graphite phase nitrogen carbide photocatalyst comprises the steps of adding modified graphite phase nitrogen carbide into a photocatalysis reaction bottle containing water and isopropanol, and using five-membered heterocycle modified g-C 3N4 with high catalytic activity as a semiconductor catalyst to prepare H 2O2 under the condition of visible light;
Uniformly dispersing the mixed solution by ultrasonic waves, continuously exposing oxygen into the mixed solution, and sealing the reaction bottle;
The reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction;
filtering the mixed reaction solution after the light reaction is finished to obtain hydrogen peroxide in the solution.
Further, the modified graphite phase nitrogen carbide comprises: the mass of the modified graphite phase nitrogen carbide is 20mg, g-C 3N4-TP、g-C3N4-FF、g-C3N4 -PD or g-C 3N4 -DP.
Further, the reaction flask was placed in the multi-channel photocatalytic reactor for a 2-hour period of time for the photoreaction.
Further, the reaction bottle contains 36mL of water and 4mL of isopropanol.
Application of five-membered heterocycle modified graphite phase nitrogen carbide photocatalyst in preparing hydrogen peroxide.
Compared with the prior art, the invention has the following advantages:
according to the preparation method, the amino functional groups hung at the edge of the g-C 3N4 can be effectively utilized through chemical grafting, and other functional groups or organic molecules are grafted through chemical reaction, so that the electronic structure and active sites of the material are regulated and controlled while the original g-C 3N4 structure is maintained, and the efficiency of photocatalytic H 2O2 production is improved.
According to the invention, urea is used as a raw material, the g-C 3N4 rich in amino functional groups is prepared through a heating thermal polymerization reaction, schiff base reaction grafting five-membered heterocyclic molecules is performed on the edge of the g-C 3N4 through a solvothermal method, the preparation method is simple to operate, and the prepared five-membered heterocyclic modified graphite phase nitrogen carbide has the high-efficiency photocatalytic H 2O2 production performance and has a great application prospect in the photochemical field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a five membered heterocyclic modified graphite phase nitrogen carbide photocatalyst.
FIG. 2 is a flow chart of a method for producing hydrogen peroxide using a modified graphite phase nitrogen carbide photocatalyst.
FIG. 3 is an X-ray diffraction pattern of grafts g-C 3N4 of different thiophene contents.
FIG. 4 is a Fourier infrared spectrum of g-C 3N4 grafted with different thiophene contents.
FIG. 5 is an X-ray diffraction pattern of furan, pyrrole, pyridine grafts g-C 3N4.
FIG. 6 is a Fourier infrared spectrum of furan, pyrrole, pyridine grafts g-C 3N4.
FIG. 7 is a graph showing the efficacy of five membered heterocycle grafted g-C 3N4 in photocatalytic H 2O2 production.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The central idea of the invention is to provide a preparation method of five-membered heterocyclic ring modified g-C 3N4 and application of the five-membered heterocyclic ring modified g-C 3N4 in photocatalytic H 2O2 production, wherein the preparation method of the five-membered heterocyclic ring modified g-C 3N4 comprises preparation of g-C 3N4 and five-membered heterocyclic ring modified g-C 3N4, and in the process of preparing g-C 3N4 from urea by thermal polymerization, the quantity of urea, the thermal polymerization reaction time and the rate of temperature rise and fall of a muffle furnace are all selectable, wherein the optimal urea quantity is given to 30g, the optimal thermal polymerization time is three hours, and the optimal muffle furnace temperature rise and fall rate is 3 ℃/min. Meanwhile, the amount of the five-membered heterocyclic ligand, the amount of the 1,4 dioxane, the reaction temperature and the reaction time are also selectable in the preparation process of the five-membered heterocyclic modified g-C 3N4, and the optimal reaction conditions are as follows: 100mg of g-C 3N4 are weighed into 20mL of 1,4 dioxane solution, followed by 2mM of five-membered heterocyclic ligand.
It is obvious that the main idea of the present invention includes optional parts and preferred parts, and a person skilled in the art can freely select the optional parts and the preferred parts according to the general technical knowledge in the art, or adopt ways of superposition combination, optimization selection, etc. to form infinite embodiments, so long as the technical problem of the present invention can be solved and corresponding technical effects can be achieved without departing from the central idea of the present invention, the embodiments shall fall within the scope of protection defined by the appended claims, and the present invention is limited to the preparation method of graphite phase nitrogen carbide and hydrogen peroxide and a plurality of specific embodiments and application embodiments by way of examples only, and the embodiments are used for explaining and explaining the claims so that the person skilled in the art can better understand the core content of the present invention, and not limit the scope of protection of the claims.
The preparation method of the five-membered heterocyclic modified graphite-phase nitrogen carbide photocatalyst shown in fig. 1 specifically comprises the following steps:
Step S01, urea is placed in a heating device for thermal polymerization reaction, and after the reaction is finished, the obtained solid is ground to obtain graphite-phase nitrogen carbide powder;
specifically, the heating device is a muffle furnace, and the thermal polymerization reaction is carried out for 2-6 hours at the temperature of 500-600 ℃;
The mass of urea was 30g, the thermal polymerization time was 3 hours, and the ramp rate of the muffle furnace was 3 ℃/min.
Step S02, weighing a certain amount of graphite phase nitrogen carbide powder, mixing the graphite phase nitrogen carbide powder with a five-membered heterocyclic ligand, adding the mixture into a1, 4-dioxane solution, performing ultrasonic dispersion, heating and stirring in an oil bath after uniform dispersion, and performing Schiff base reaction;
Specifically, the five-membered heterocyclic ligands include: thiophene-3-carbaldehyde, pyridine-3-carbaldehyde, pyrrole-3-carbaldehyde;
specifically, ultrasonic dispersion is carried out, oil bath is carried out at the temperature of 80-120 ℃ after uniform dispersion, heating and stirring are carried out for 6-24 hours, and Schiff base reaction is carried out;
and S03, after the Schiff base reaction is finished, performing centrifugal washing reaction by using an N, N-dimethylformamide solution and absolute methanol, and then performing vacuum drying on the obtained material to finally obtain the five-membered heterocyclic modified graphite phase nitrogen carbide.
The method for preparing hydrogen peroxide by using the modified graphite phase nitrogen carbide photocatalyst as shown in fig. 2 specifically comprises the following steps:
step S11, adding modified graphite phase nitrogen carbide into a photocatalysis reaction bottle containing water and isopropanol;
Specifically, the modified graphite phase nitrogen carbide includes: the mass of the modified graphite phase nitrogen carbide is 20mg, g-C 3N4-TP、g-C3N4-FF、g-C3N4 -PD or g-C 3N4 -DP.
Illustratively, the reaction flask was placed in the multi-channel photocatalytic reactor for 2 hours with 36mL of water and 4mL of isopropyl alcohol.
Step S12, uniformly dispersing the mixed solution by ultrasonic waves, continuously exposing oxygen into the mixed solution, and sealing the reaction bottle;
Step S13, placing the reaction bottle into a multi-channel photocatalytic reactor for illumination reaction;
And step S14, filtering the mixed reaction solution after the light reaction is finished to obtain hydrogen peroxide in the solution.
The invention also discloses application of the five-membered heterocyclic modified graphite phase nitrogen carbide photocatalyst in preparation of hydrogen peroxide.
For the purposes of simplicity of explanation, the method steps disclosed in the above embodiments are depicted as a series of acts in a combination, but it should be understood by those skilled in the art that the embodiments of the present invention are not limited by the order of acts described, as some steps may occur in other order or concurrently in accordance with the embodiments of the present invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred embodiments, and that the acts are not necessarily required by the embodiments of the invention.
As can be seen from the X-ray diffraction patterns, fourier infrared spectra, five-membered heterocyclic grafting g-C 3N4 photo-catalysis H 2O2 production efficacy patterns and the like shown in the figures 3 to 7, the invention not only provides a preparation method of five-membered heterocyclic modification g-C 3N4, but also uses five-membered heterocyclic modification g-C 3N4 with high catalytic activity as a semiconductor catalyst for preparing H 2O2 under the condition of visible light. Compared with the original g-C 3N4, the five-membered heterocyclic modified g-C 3N4 prepared by adopting a simple solvothermal method shows more excellent photocatalytic H 2O2 production activity, and the material disclosed by the invention is simple in preparation process, high in cost efficiency and convenient for large-scale preparation of the high-efficiency modified g-C 3N4 catalyst.
Example 1:
a preparation method of five-membered heterocycle (thiophene) modified graphite-phase nitrogen carbide comprises the following steps:
(1) Weighing 30g of urea, putting into a crucible with a cover, then putting into a muffle furnace, heating to 550 ℃ at a speed of 3 ℃/min in air, keeping the temperature of 550 ℃ for reaction for 3 hours, naturally cooling to room temperature, and grinding the obtained solid into fine powder to obtain original g-C 3N4;
(2) 100mg of original g-C 3N4 is weighed and added into a 100mL high-temperature and high-pressure resistant glass bottle, and then 20mL of 1,4 dioxane solution is added, and the mixed solution is subjected to ultrasonic treatment for 20 minutes until the powder is uniformly dispersed. Thiophene-3-carbaldehyde (1, 2 and 4mmol, respectively) was then added to the above mixture, and after sealing the glass bottle, it was placed in an oil bath to react with stirring for 12 hours.
(3) After the oil bath heating reaction is finished, centrifuging the obtained mixed solution to obtain a corresponding solid, centrifugally washing the corresponding solid by using a large amount of N, N-dimethylformamide solution and absolute methanol, and finally, placing the centrifuged solid in a vacuum drying oven and drying at 60 ℃ for 12 hours to obtain thiophene grafted g-C 3N4(g-C3N4 -TP.
Example 2:
A preparation method of five-membered heterocycle (furan) modified graphite-phase nitrogen carbide comprises the following steps:
(1) Weighing 30g of urea, putting into a crucible with a cover, then putting into a muffle furnace, heating to 550 ℃ at a speed of 3 ℃/min in air, keeping the temperature of 550 ℃ for reaction for 3 hours, naturally cooling to room temperature, and grinding the obtained solid into fine powder to obtain original g-C 3N4;
(2) 100mg of original g-C 3N4 is weighed and added into a 100mL high-temperature and high-pressure resistant glass bottle, and then 20mL of 1,4 dioxane solution is added, and the mixed solution is subjected to ultrasonic treatment for 20 minutes until the powder is uniformly dispersed. 3-furaldehyde (1, 2 and 4mmol, respectively) was then added to the above mixture, and after sealing the glass bottle, it was placed in an oil bath to be heated and stirred for reaction for 12 hours.
(3) After the oil bath heating reaction is finished, centrifuging the obtained mixed solution to obtain a corresponding solid, centrifugally washing the corresponding solid by using a large amount of N, N-dimethylformamide solution and absolute methanol, and finally, placing the centrifuged solid in a vacuum drying oven and drying at 60 ℃ for 12 hours to obtain thiophene grafted g-C 3N4(g-C3N4 -FF.
Example 3:
a preparation method of five-membered heterocyclic (pyridine) modified graphite-phase nitrogen carbide comprises the following steps:
(1) Weighing 30g of urea, putting into a crucible with a cover, then putting into a muffle furnace, heating to 550 ℃ at a speed of 3 ℃/min in air, keeping the temperature of 550 ℃ for reaction for 3 hours, naturally cooling to room temperature, and grinding the obtained solid into fine powder to obtain original g-C 3N4;
(2) 100mg of original g-C 3N4 is weighed and added into a 100mL high-temperature and high-pressure resistant glass bottle, and then 20mL of 1,4 dioxane solution is added, and the mixed solution is subjected to ultrasonic treatment for 20 minutes until the powder is uniformly dispersed. Pyridine-3-carbaldehyde (1, 2 and 4mmol, respectively) was then added to the above mixture, and after sealing the glass bottle, it was placed in an oil bath to react with stirring for 12 hours.
(3) After the oil bath heating reaction is finished, centrifuging the obtained mixed solution to obtain a corresponding solid, centrifugally washing the corresponding solid by using a large amount of N, N-dimethylformamide solution and absolute methanol, and finally, placing the centrifuged solid in a vacuum drying oven and drying at 60 ℃ for 12 hours to obtain thiophene grafted g-C 3N4(g-C3N4 -PD.
Embodiment 4:
A preparation method of five-membered heterocycle (pyrrole) modified graphite phase nitrogen carbide comprises the following steps:
(1) Weighing 30g of urea, putting into a crucible with a cover, then putting into a muffle furnace, heating to 550 ℃ at a speed of 3 ℃/min in air, keeping the temperature of 550 ℃ for reaction for 3 hours, naturally cooling to room temperature, and grinding the obtained solid into fine powder to obtain original g-C 3N4;
(2) 100mg of original g-C 3N4 is weighed and added into a 100mL high-temperature and high-pressure resistant glass bottle, and then 20mL of 1,4 dioxane solution is added, and the mixed solution is subjected to ultrasonic treatment for 20 minutes until the powder is uniformly dispersed. Pyrrole-3-carbaldehyde (1, 2 and 4mmol, respectively) was then added to the above mixture, and after sealing the glass bottle, it was placed in an oil bath to react with stirring for 12 hours.
(3) After the oil bath heating reaction is finished, centrifuging the obtained mixed solution to obtain a corresponding solid, centrifugally washing the corresponding solid by using a large amount of N, N-dimethylformamide solution and absolute methanol, and finally, placing the centrifuged solid in a vacuum drying oven and drying at 60 ℃ for 12 hours to obtain thiophene grafted g-C 3N4(g-C3N4 -DP.
Application example 1:
20mg of g-C 3N4(g-C3N4 -TP prepared in example 1 was added to a photocatalytic reaction flask containing 36mL of water and 4mL of isopropyl alcohol, sonicated for 10 minutes until the mixture was uniformly dispersed, and then the mixture was continuously exposed to oxygen for 20 minutes, and the reaction flask was closed. Finally, the reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction. After two hours of illumination, the mixed reaction solution was filtered, and the H 2O2 content in the filtered solution was 552.1. Mu.M.
Application example 2:
20mg of g-C 3N4(g-C3N4 -FF prepared in example 2 was added to a photocatalytic reaction flask containing 36mL of water and 4mL of isopropyl alcohol, and the mixture was sonicated for 10 minutes until the mixture was uniformly dispersed, and then the reaction flask was closed after continuously exposing the mixture to oxygen for 20 minutes. Finally, the reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction. After two hours of illumination, the mixed reaction solution was filtered, and the content of H 2O2 in the filtered solution was 356.6. Mu.M.
Application example 3:
20mg of g-C 3N4(g-C3N4 -PD prepared in example 3 was added to a photocatalytic reaction flask containing 36mL of water and 4mL of isopropyl alcohol, and the mixture was sonicated for 10 minutes until the mixture was uniformly dispersed, and then the reaction flask was closed after continuously exposing the mixture to oxygen for 20 minutes. Finally, the reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction. After two hours of illumination, the mixed reaction solution was filtered, and the H 2O2 content in the filtered solution was 284.2. Mu.M.
Application example 4:
20mg of g-C 3N4(g-C3N4 -DP prepared in example 4 was added to a photocatalytic reaction flask containing 36mL of water and 4mL of isopropyl alcohol, and the mixture was sonicated for 10 minutes until the mixture was uniformly dispersed, and then the reaction flask was closed after continuously exposing the mixture to oxygen for 20 minutes. Finally, the reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction. After two hours of illumination, the mixed reaction solution was filtered, and the H 2O2 content in the filtered solution was 251.1. Mu.M.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or steps not listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. The preparation method of the five-membered heterocyclic modified graphite-phase carbon nitride photocatalyst for producing H 2O2 is characterized by comprising the following steps:
placing urea into a heating device, performing thermal polymerization reaction at 500-600 ℃, and grinding the obtained solid after the reaction is finished to obtain graphite-phase carbon nitride powder, wherein the mass of the urea is 30g, the thermal polymerization time is 2-6 hours, and the temperature rise and fall rate of a muffle furnace is 3 ℃/min;
Weighing a certain amount of graphite-phase carbon nitride powder, mixing with 1 or 2 or 4mmol of five-membered heterocyclic ligand, adding into 1, 4-dioxane solution, performing ultrasonic dispersion uniformly, performing oil bath at 80-120 ℃, heating and stirring for 6-24h, and performing Schiff base reaction, wherein the five-membered heterocyclic ligand comprises: thiophene-3-carbaldehyde, pyridine-3-carbaldehyde and/or pyrrole-3-carbaldehyde;
After the Schiff base reaction is finished, performing centrifugal washing reaction by using an N, N-dimethylformamide solution and absolute methanol, and then drying the obtained material in vacuum at 60 ℃ for 12 hours to finally obtain the five-membered heterocyclic modified graphite-phase carbon nitride.
2. A five membered heterocyclic modified graphite phase carbon nitride photocatalyst for producing H 2O2, characterized by being obtained according to the preparation method of claim 1.
3. A method for preparing hydrogen peroxide by using a modified graphite phase carbon nitride photocatalyst, which is characterized in that the modified graphite phase carbon nitride photocatalyst of claim 2 is added into a photocatalytic reaction bottle containing water and isopropanol, and a penta-heterocycle modified g-C 3N4 with high catalytic activity is used as a semiconductor catalyst for preparing H 2O2 under the condition of visible light, wherein the modified graphite phase carbon nitride photocatalyst comprises: the mass of the modified graphite phase carbon nitride photocatalyst is 20mg, and the g-C 3N4-TP、g-C3N4-FF、g-C3N4 -PD or g-C 3N4 -DP;
Uniformly dispersing the mixed solution by ultrasonic waves, continuously exposing oxygen into the mixed solution, and sealing the reaction bottle;
The reaction bottle is put into a multi-channel photocatalytic reactor for illumination reaction;
filtering the mixed reaction solution after the light reaction is finished to obtain hydrogen peroxide in the solution.
4. The method for preparing hydrogen peroxide by using the modified graphite phase carbon nitride photocatalyst as claimed in claim 3, wherein the time for the reaction flask to be put into the multi-channel photocatalytic reactor for the photoreaction is 2 hours.
5. The method for preparing hydrogen peroxide using a modified graphite phase carbon nitride photocatalyst as recited in claim 3, wherein the reactor flask contains 36mL of water and 4mL of isopropyl alcohol.
6. Use of the five-membered heterocyclic modified graphite-phase carbon nitride photocatalyst as described in claim 2 in the preparation of hydrogen peroxide.
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| CN114471711A (en) * | 2022-01-24 | 2022-05-13 | 华南理工大学 | Polythiophene-carbon nitride composite photocatalyst and preparation method and application thereof |
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