CN113413900B - Copolymer based on carbon nitride and preparation method and application thereof - Google Patents
Copolymer based on carbon nitride and preparation method and application thereof Download PDFInfo
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- CN113413900B CN113413900B CN202110602456.5A CN202110602456A CN113413900B CN 113413900 B CN113413900 B CN 113413900B CN 202110602456 A CN202110602456 A CN 202110602456A CN 113413900 B CN113413900 B CN 113413900B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920001577 copolymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 90
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 150000004982 aromatic amines Chemical group 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 17
- 125000006413 ring segment Chemical group 0.000 description 13
- 239000012300 argon atmosphere Substances 0.000 description 11
- 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 10
- 150000004056 anthraquinones Chemical class 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical group C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical group C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- -1 monocyclic compound Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
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 invention relates to a copolymer based on carbon nitride, a preparation method and application thereof. The chain segments comprise (99% -99.7%) of a carbon nitride chain segment and (0.03% -0.1%) of a polyaramid chain segment based on the mass percentage of the copolymer. By introducing the polyaramine chain segment into the carbon nitride chain segment, the pi-pi conjugated system is prolonged and widened, and compared with pure carbon nitride, the copolymer provided by the invention has the advantages of wider light absorption range, narrower energy band structure, more excellent electronic characteristics, higher separation efficiency of photo-generated electrons and holes, and finally achieves the aim of improving the photocatalytic activity of the carbon nitride. Compared with pure carbon nitride, the copolymer of the invention is used as a catalyst for preparing hydrogen peroxide by photocatalysis, has better catalytic effect, can be recycled for multiple times, has good stability and is very green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of copolymers, in particular to a copolymer based on carbon nitride, a preparation method and application thereof.
Background
Hydrogen peroxide is an efficient and environmentally friendly oxidizing agent. In the reaction, it is converted only into water and oxygen, and no toxic by-products are produced in the reaction. Because of these advantages, hydrogen peroxide is widely used in the organic synthesis, wastewater treatment and disinfection, and pulp and paper industry. In addition, hydrogen peroxide is reported to be used as an oxidant and a reducing agent of a novel single-cabin fuel cell in the field of energy, and meanwhile, compared with hydrogen, the hydrogen peroxide is completely dissolved in water and is easy to transport, so that the hydrogen peroxide is an ideal energy for replacing the hydrogen.
Currently, the industrial production of hydrogen peroxide mainly uses the anthraquinone oxidation process (AQ) to produce hydrogen peroxide, and the yield of this process accounts for more than 95% of the total yield of hydrogen peroxide. The preparation of hydrogen peroxide by the anthraquinone oxidation method mainly comprises four steps: 1. in an organic solution, catalyzing and hydrogenating Anthraquinone (AQ) by utilizing a palladium or nickel catalyst to obtain HAQ;2. oxidizing HAQ in an oxygen-rich environment to obtain Anthraquinone (AQ) and hydrogen peroxide; 3. separating hydrogen peroxide and anthraquinone by organic extraction, and recycling anthraquinone; 4. purifying the hydrogen peroxide. These steps all require a large amount of energy and produce some waste water and solid waste, which can cause great environmental pollution. Thus, a very green process is required to produce hydrogen peroxide.
The semiconductor photocatalysis technology is a very promising solution, which uses a semiconductor as a photocatalyst, water and oxygen as raw materials, and solar energy as energy sources to synthesize hydrogen peroxide, and compared with the anthraquinone method, the solution is greener and energy-saving.
The carbon nitride (called carbon nitride) is a metal-free semiconductor photocatalyst, has the advantages of high thermal stability and chemical stability, convenient preparation, capability of absorbing visible light, no toxicity, rich sources and the like, and is therefore paid attention to a plurality of scientific researchers. The excellent performance of the catalyst is widely applied to the fields of pollutant degradation, hydrogen peroxide preparation by photolysis of water, oxygen preparation, organic synthesis and the like, but the catalyst has the defects of fast carrier recombination, insufficient light absorption range and the like, and the use of the catalyst is limited.
Disclosure of Invention
Based on the above, the invention provides a technical scheme capable of improving the conjugation degree of the carbon nitride and increasing the photocatalysis performance of the carbon nitride.
The technical proposal is as follows:
the segments of the copolymer based on the carbon nitride comprise (99% -99.7%) carbon nitride segments and (0.03% -0.1%) aromatic amine segments in percentage by mass of the copolymer.
In one embodiment, the monomer from which the polyaramid segment is prepared has a structure as shown in formula (1):
wherein:
Ar 1 and Ar is a group 2 Each independently is R 1 Aryl with 6 to 20 ring atoms which is substituted or unsubstituted;
l is selected from single bond, NR 1 Is at least one R 2 Substituted or unsubstituted aryl having 6 to 20 ring atoms, or substituted by R 1 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;
r is independently selected from the group consisting of-H, alkyl groups having 1 to 10 carbon atoms for each occurrence;
R 2 selected from-H, alkyl groups having 1 to 10 carbon atoms, and R 1 Aryl with 6 to 20 ring atoms which is substituted or unsubstituted;
R 1 is an amino group or an alkyl group having 1 to 10 carbon atoms.
In one embodiment, the Ar 1 And the Ar is as described 2 Each independently selected from phenyl, biphenyl, naphthyl, anthryl, or phenanthryl.
In one embodiment, each occurrence of R is independently selected from the group consisting of-H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and isobutyl.
In one embodiment, the R 1 Each occurrence is independently selected from-H, benzene substituted or unsubstituted with amino, naphthalene substituted or unsubstituted with amino, anthracene substituted or unsubstituted with amino.
In one embodiment, L is selected from any of the following groups:
* Represents a ligation site;
m is 0, 1 or 2.
In one embodiment, the monomer from which the polyaramid segment is made has a structure as shown in any one of the following:
in one embodiment, the monomer from which the carbon nitride segment is prepared is melamine, urea, or dicyandiamide.
The invention also provides a preparation method of the copolymer based on the carbon nitride, which comprises the following steps:
placing the monomer for preparing the carbon nitride chain segment in protective gas atmosphere, and reacting at 400-450 ℃ to prepare a precursor;
mixing the precursor and the monomer for preparing the polyaramid chain segment, placing the mixture in a protective gas atmosphere, and carrying out copolymerization reaction at the temperature of 500-600 ℃ to prepare the copolymer based on the carbon nitride.
In one embodiment, the mass ratio of the monomer for preparing the carbon nitride segment to the monomer for preparing the aromatic amine segment is (120-6000): 1.
In one embodiment, in the step of preparing the precursor, the reaction time is 2 to 6 hours; and/or
The reaction time of the copolymerization reaction is 2-8 hours; and/or
In the step of preparing the precursor and the copolymer, the precursor and the copolymer are annealed in a natural cooling mode after the reaction is finished.
In one embodiment, after mixing the precursor and the monomer for preparing the polyaramid segment, the obtained mixture is mixed with an alcohol solvent, ground and dried, and then subjected to copolymerization.
The invention also provides the use of the copolymer based on carbon nitride as described above as a catalyst for the photocatalytic preparation of hydrogen peroxide.
The invention has the following beneficial effects:
the photocatalytic activity of the carbon nitride is derived from the self conjugated structure, and the poly-aromatic amine chain segment is introduced into the carbon nitride chain segment, so that the pi-pi conjugated system is prolonged and widened.
Compared with pure carbon nitride, the copolymer of the invention is used as a catalyst for preparing hydrogen peroxide by photocatalysis, has better catalytic effect, and the catalytic effect can reach about 3 times of that of the pure carbon nitride by testing. Meanwhile, the copolymer can be recycled after the photocatalytic reaction is finished, and after the copolymer is used for multiple times, the catalyst still has higher photocatalytic activity, and is good in stability and environment-friendly. In addition, the preparation method of the copolymer is simple to operate, has easily available raw materials, and is suitable for large-scale preparation.
Drawings
FIG. 1 is an XRD pattern for PCN and PCN-TAPx;
FIG. 2 is a Fourier infrared (FTIR) spectrum of PCN and PCN-TAPx;
FIG. 3 is a UV-vis-DRS profile of PCN and PCN-TAPx;
FIG. 4 is a Photoluminescence (PL) spectrum of PCN and PCN-TAP1, PCN-TAP3 and PCN-TAP 5;
FIG. 5 shows the results of photocatalytic hydrogen peroxide production by PCN and PCN-TAPx as catalysts under irradiation with visible light (lambda >400 nm);
FIG. 6 is a graph showing the results of a cyclic test of the catalytic production of hydrogen peroxide by PCN-TAP3.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all 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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, unless a specifically defined term is used, such as "consisting of … … only," etc., another component may be added.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent. "substituted or unsubstituted" means that the groups defined may or may not be substituted.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, aryl refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic ring systems or heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatom is preferably selected from N, O, S. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings.
Specifically, examples of aryl groups are: benzene, biphenyl, naphthalene, anthracene, phenanthrene, and derivatives thereof. Examples of heteroaromatic groups are: furan, thiophene, pyrrole, pyrazole, carbazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, and derivatives thereof.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 10.
In the present invention, "×" means a linking or fusing site.
In the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site; such asMeaning that the substituent may be attached to any substitution site on the benzene ring.
The technical scheme of the invention is as follows:
the copolymer comprises a carbon nitride chain segment (99% -99.7%) and a polyaramid chain segment (0.03% -0.1%) in percentage by mass.
The photocatalytic activity of the carbon nitride is derived from the self conjugated structure, and the poly-aromatic amine chain segment is introduced into the carbon nitride chain segment, so that the pi-pi conjugated system is prolonged and widened.
In one embodiment, the monomer for preparing the polyaramid has a structure as shown in formula (1):
wherein:
Ar 1 and Ar is a group 2 Each independently is R 1 Aryl with 6 to 20 ring atoms which is substituted or unsubstituted;
l is selected from single bond, NR 1 Is at least one R 2 Substituted or unsubstituted aryl having 6 to 20 ring atoms, or substituted by R 1 A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;
r is independently selected from the group consisting of-H, alkyl groups having 1 to 10 carbon atoms for each occurrence;
R 2 selected from-H, alkyl groups having 1 to 10 carbon atoms, and R 1 Aryl with 6 to 20 ring atoms which is substituted or unsubstituted;
R 1 is an amino group or an alkyl group having 1 to 10 carbon atoms.
Preferably, the Ar 1 And the Ar is as described 2 Each independently selected from phenyl, biphenyl, naphthyl, anthryl, or phenanthryl. By adopting the structure, the pi-pi conjugated system is prolonged and widened, and meanwhile, the too large steric hindrance effect is not generated, so that the copolymerization reaction activity is too low and the reaction speed is too slow. More preferably, the Ar 1 Is phenyl or biphenyl. Further, the Ar 2 Is phenyl or biphenyl. Particularly preferably Ar 1 And Ar is a group 2 All are phenyl groups.
Preferably, each occurrence of R is independently selected from the group consisting of-H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and isobutyl. By adopting the structure, the reaction speed is improved. Particularly preferably, R is-H.
Preferably, said R 2 Each occurrence is independently selected from-H, benzene substituted or unsubstituted with amino, naphthalene substituted or unsubstituted with amino, anthracene substituted or unsubstituted with amino. By adopting the structure, the number of amino groups can be increased, which is more beneficial to prolonging and widening pi-pi conjugated system.
In one of the preferred embodiments, the L is selected from any of the following groups:
* Represents a ligation site; m is 0, 1 or 2.
Particularly preferably, the monomer for preparing the polyaramid has a structure as shown in any one of the following:
the symmetrical structure or the para-substitution of amino is adopted, which is beneficial to accelerating the reaction speed and improving the conjugation degree.
The monomer for preparing the carbon nitride chain segment is melamine, urea or dicyandiamide.
The invention also provides a preparation method of the copolymer based on the carbon nitride, which comprises the following steps:
placing the monomer for preparing the carbon nitride chain segment in protective gas atmosphere, and reacting at 400-450 ℃ to prepare a precursor;
mixing the precursor and the monomer for preparing the polyaramid chain segment, placing the mixture in a protective gas atmosphere, and carrying out copolymerization reaction at the temperature of 500-600 ℃ to prepare the copolymer based on the carbon nitride.
The copolymer based on the carbon nitride is prepared by a heat treatment mode, and the preparation method is simple to operate and high in production efficiency.
In one embodiment, the mass ratio of the monomer for preparing the carbon nitride segment to the monomer for preparing the aromatic amine segment is (120-6000): 1.
In one embodiment, after mixing the precursor and the segment monomer for preparing the polyaramid, the obtained mixture is mixed with an alcohol solvent, ground and dried, and then subjected to copolymerization. By adding alcohol solvent for grinding, more uniform mixing of the precursor and the monomer for preparing the polyaramid chain segment is facilitated. Preferably, the alcohol solvent is ethanol, and the drying treatment is vacuum drying at 60 ℃ for 4-12 h.
In the present invention, the protective gas means argon or nitrogen. The temperature rising rate is 2 ℃/min-10 ℃/min.
In one embodiment, in the step of preparing the precursor, the reaction time (soak time) is 2 to 6 hours. Further, in the step of preparing the precursor, after the reaction is completed, annealing is performed in a natural cooling mode, and slow cooling is beneficial to crystal growth.
In one embodiment, the reaction time of the copolymerization reaction is 2 to 8 hours. Further, in the step of preparing the copolymer, after the copolymerization reaction is completed, the copolymer is annealed in a natural cooling mode, and slow cooling is beneficial to crystal growth.
In addition, the invention also provides application of the copolymer based on the carbon nitride as a catalyst for preparing hydrogen peroxide by photocatalysis.
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
Unless otherwise specified, all starting materials in the present invention are derived from commercially available products.
In the examples below, PCN represents a carbon nitride and the monomers used to prepare the polyaramid are(TAP), PCN-TAPx (x is a numerical number) represents the copolymer obtained in the examples.
Example 1
(1) 5g of melamine is placed in a covered crucible, then placed in a muffle furnace, heated to 420 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, kept at a constant temperature for 4 hours, and naturally cooled to room temperature to obtain melem which is white in shape.
(2) 3g of melem and 1mg of TAP are placed in a mortar, then 6mL of ethanol is added for soaking and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the dried sample in the step (2) in a covered crucible, placing in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, reacting for 6 hours, and naturally cooling to room temperature to obtain the light brown PCN-TAP1.
Example 2
(1) 5g of melamine is placed in a covered crucible, then placed in a muffle furnace, heated to 420 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, kept at a constant temperature for 4 hours, and naturally cooled to room temperature to obtain melem which is white in shape.
(2) 3g of melem and 10mg of TAP are placed in a mortar, then 6mL of ethanol is added for infiltration and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the dried sample in the step (2) in a covered crucible, placing in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, reacting for 6 hours, and naturally cooling to room temperature to obtain the PCN-TAP2 with light brown color.
Example 3
(1) 5g of melamine is placed in a covered crucible, then placed in a muffle furnace, heated to 420 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, kept at a constant temperature for 4 hours, and naturally cooled to room temperature to obtain melem which is white in shape.
(2) 3g of melem and 15mg of TAP are placed in a mortar, then 6mL of ethanol is added for infiltration and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the dried sample in the step (2) in a covered crucible, placing in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, reacting for 6 hours, and naturally cooling to room temperature to obtain the brown PCN-TAP3.
Example 4
(1) 5g of melamine is placed in a covered crucible, then placed in a muffle furnace, heated to 420 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, kept at a constant temperature for 4 hours, and naturally cooled to room temperature to obtain melem which is white in shape.
(2) 3g of melem and 20mg of TAP are placed in a mortar, then 6mL of ethanol is added for infiltration and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the dried sample in the step (2) in a covered crucible, placing in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, reacting for 6 hours, and naturally cooling to room temperature to obtain the brown PCN-TAP4.
Example 5
(1) 5g of melamine is placed in a covered crucible, then placed in a muffle furnace, heated to 420 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, kept at a constant temperature for 4 hours, and naturally cooled to room temperature to obtain melem which is white in shape.
(2) 3g of melem and 30mg of TAP are placed in a mortar, then 6mL of ethanol is added for infiltration and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the dried sample in the step (2) in a covered crucible, then placing the crucible in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere, reacting for 6 hours, and naturally cooling to room temperature to obtain the PCN-TAP5 with dark brown color, wherein the PCN-TAP1, the PCN-TAP2, the PCN-TAP3 and the PCN-TAP4 are observed to be from PCN-TAP5 to PCN-TAP5, and the proportion of the formed polyaramid chain segments in the copolymer is increased along with the increase of the addition amount of the TAP, and the color of the copolymer is brown and is deepened sequentially.
Comparative example 1
3g of melamine is placed in a covered crucible, then placed in a muffle furnace, and is heated to 550 ℃ at a heating rate of 2 ℃/min under the condition of argon atmosphere to be baked, the temperature is kept for 4 hours, then the melamine is naturally cooled to room temperature, solid is obtained, and the solid is ground to obtain pale yellow PCN powder.
Test part
1. PCN and PCN-TAPx structural analysis:
(1)XRD：
fig. 1 shows XRD patterns of PCN and PCN-TAPx, and as can be seen from fig. 1, two characteristic diffraction peaks can be displayed at 2θ=13.2° and 27.4 °, which are consistent with standard card (JCPDS-87-1526), corresponding to (100) and (002) crystal planes, respectively. In addition, as can be seen from FIG. 1, as the amount of TAP added gradually increases, the intensity of the diffraction peak at 27.4℃is gradually decreased and then is weaker to a certain extent and then increased, compared to that of pure PCN, which may be attributed to the fact that the introduction of TAP changes the polymerization degree of PCN itself, resulting in the crystallinity of the catalyst becoming lower and then higher.
(2) And (3) infrared:
FIG. 2 shows Fourier infrared (FTIR) spectra of PCN and PCN-TAPx, as can be seen from FIG. 2, PCN is 812cm in length -1 There is an absorption peak, which is a stretching vibration peak caused by the s-triazine structure. Comparing the infrared spectra of PCN-TAPx and PCN, five of them were found to be 812cm -1 The peak position coincidence of (c) is very high and there is no shift, which indicates that copolymerization with TAP does not cause damage to the structure of carbon nitride. At the same time at 1243cm -1 、1315cm -1 、1400cm -1 、1460cm -1 、1637cm -1 The infrared absorption peak appearing at this point is a peak of a C-N (-C) -C or C-NH-C unit. Finally, PCN and PCN-TAPx were at 3194cm -1 There is a very broad peak, caused by N-H stretching vibration, which indicates that part of-NH or-NH is also present in the PCN skeleton itself 2 Functional groups (ref. Rational Ionothermal Copolymerization of TCNQ with PCN Semiconductor for Enhanced Photocatalytic Full Water Splitting).
(3) Ultraviolet:
FIG. 3 shows UV-vis-DRS spectra of PCN and PCN-TAPx, and it is apparent from FIG. 3 that the PCN-TAPx has a wider light absorption range and red shift in absorption wavelength compared with PCN. Meanwhile, as the proportion of the polyaramid chain segments in the copolymer is increased, the red shift effect is more obvious, and the light is absorbed to a certain extent even in the near infrared region.
(4) Fluorescence:
FIG. 4 shows Photoluminescence (PL) spectra of PCN and PCN-TAP1, PCN-TAP3 and PCN-TAP5, and it is apparent from FIG. 4 that PCN has very high fluorescence intensity, and it is shown that photogenerated electrons and holes of PCN are easily recombined, and that the separation rate of carriers is low. After copolymerization modification, the fluorescence intensity of the obtained PCN-TAP1, PCN-TAP3 and PCN-TAP5 is obviously reduced, which proves that after the TAP copolymerization is introduced, the recombination of electrons and holes of the carbon nitride is more difficult, and the separation efficiency is greatly improved.
2. Application of
(1) Catalytic production of hydrogen peroxide using PCN and PCN-TAPx as photocatalysts
10mg of the catalyst was placed in a custom 50mL quartz bottle, 5mL of isopropanol and 45mL of deionized water were added to the inside, and oxygen was introduced to the inside for 30 minutes. Then sealing the solution by using a rubber plug, respectively placing the solution in a dark place for ultrasonic treatment for 30 minutes, stirring for 30 minutes to ensure that oxygen reaches adsorption-desorption balance, then reacting in a multi-channel, taking out a sample every 30 minutes, taking out about 4mL of the solution from a quartz bottle by using a syringe during sampling, and then placing a disposable filter membrane on the syringe, wherein the purpose of the filter membrane is to separate a solid catalyst from the solution so as to prevent the influence on the test effect when the hydrogen peroxide is measured by using an iodometry. Finally, 3mL of the solution was taken out in a glass vial by a pipette, and 1mL of a 0.1M potassium hydrogen phthalate solution and a 0.4M potassium iodide solution were added to the solution, respectively, to obtain a mixed solution. And (3) oscillating the mixed solution for 1-2 minutes, placing the mixed solution in the dark for 1 hour, measuring the absorbance at 350nm, and finally calculating the hydrogen peroxide production of the catalyst in different time periods.
FIG. 5 shows the results of photocatalytic hydrogen peroxide production by each of the PCN and PCN-TAPx catalysts under irradiation with visible light (lambda >400 nm). As can be seen from FIG. 5, the performance of PCN-TAPx in photocatalytic hydrogen peroxide production is improved to a different extent compared with PCN, and the hydrogen peroxide production capacity of the corresponding catalyst is gradually improved to a highest value and then reduced with the increase of the TAP addition amount. After 3 hours, about 6. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN, about 10.2. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN-TAP1, about 11.9. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN-TAP2, about 18.5. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN-TAP3, about 13.3. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN-TAP4, and about 7.2. Mu. Mol of hydrogen peroxide was produced by catalysis with PCN-TAP5, which showed the most remarkable effect of promoting the PCN-TAP3 catalyst, which produced about 18. Mu.5 mol of hydrogen peroxide, exhibiting three times the catalytic performance of PCN.
2. Recycling performance of PCN-TAPx as photocatalyst for catalyzing hydrogen peroxide
(1) First experiment: 10mg of the catalyst was placed in a custom 50mL quartz bottle, 5mL of isopropanol and 45mL of deionized water were added to the inside, and oxygen was introduced to the inside for 30 minutes. Then sealing the solution by using a rubber plug, respectively placing the solution in a dark place for ultrasonic treatment for 30 minutes, stirring for 30 minutes to ensure that oxygen reaches adsorption-desorption balance, then reacting in a multi-channel, taking out a sample every 30 minutes, taking out about 4mL of the solution from a quartz bottle by using a syringe during sampling, and then placing a disposable filter membrane on the syringe, wherein the purpose of the filter membrane is to separate a solid catalyst from the solution so as to prevent the influence on the test effect when the hydrogen peroxide is measured by using an iodometry. Finally, 3mL of the solution was taken out in a glass vial by a pipette, and 1mL of a 0.1M potassium hydrogen phthalate solution and a 0.4M potassium iodide solution were added to the solution, respectively, to obtain a mixed solution. And (3) oscillating the mixed solution for 1-2 minutes, placing the mixed solution in the dark for 1 hour, measuring the absorbance at 350nm, finally calculating the hydrogen peroxide production amount of the catalyst in different time periods, and reserving the residual solid-liquid mixture in the centrifuge tube for standby.
(2) Second experiment: and (3) carrying out suction filtration on the solid-liquid mixture in the quartz bottle and the solid-liquid mixture in the centrifuge tube for the first time, separating the solid from the liquid, drying filter paper (the catalyst is on the filter paper), repeating the first time experiment on the obtained catalyst, testing the performance of hydrogen peroxide production, and reserving the residual solid-liquid mixture in the centrifuge tube for standby.
(3) Third experiment: and (3) carrying out suction filtration on the solid-liquid mixture in the quartz bottle and the solid-liquid mixture in the centrifuge tube for the second experiment, then drying filter paper (the catalyst is on the filter paper), repeating the first experiment on the obtained catalyst, testing the hydrogen peroxide production performance, and reserving the residual solid-liquid mixture in the centrifuge tube for later use.
FIG. 6 shows the results of a cyclic test of the catalytic production of hydrogen peroxide by PCN-TAP3. As can be seen from FIG. 6, the catalyst still has higher photocatalytic activity after 3 uses, and the stability of PCN-TAP3 is good.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described 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.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logic analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (5)
1. The application of a copolymer based on carbon nitride in preparing hydrogen peroxide by photocatalysis is characterized in that the chain segments comprise (99% -99.7%) carbon nitride chain segments and (0.03% -0.1%) aromatic amine chain segments in percentage by mass of the copolymer;
the monomer for preparing the polyaramid chain segment has the following structure:
；
the preparation method of the copolymer based on the carbon nitride comprises the following steps:
placing the monomer for preparing the carbon nitride chain segment in protective gas atmosphere, and reacting at 400-450 ℃ to prepare a precursor;
and mixing the precursor and the monomer for preparing the polyaramid chain segment, placing the mixture in a protective gas atmosphere, and carrying out copolymerization reaction at the temperature of 500-600 ℃ to prepare the copolymer based on the carbon nitride.
2. Use of a carbon nitride based copolymer according to claim 1 for the photocatalytic production of hydrogen peroxide, characterized in that the monomer for the production of the carbon nitride segment is melamine, urea or dicyandiamide.
3. Use of a copolymer based on carbon nitride according to claim 1 for the photocatalytic production of hydrogen peroxide, characterized in that the mass ratio of the monomer for producing carbon nitride and the monomer for producing the polyaramid is (120-6000): 1.
4. The use of a carbon nitride based copolymer according to claim 1 for the photocatalytic production of hydrogen peroxide, characterized in that in the step of preparing the precursor, the reaction time is between 2 and h h; and/or
The reaction time of the copolymerization reaction is 2 h-8 hours; and/or
In the step of preparing the precursor and the copolymer, annealing is performed in a natural cooling mode after the reaction is finished; and/or
After mixing the precursor and the monomer for preparing the polyaramid, firstly mixing the obtained mixture with an alcohol solvent, grinding and drying, and then carrying out copolymerization reaction.
5. The use of the copolymer based on carbon nitride according to claim 4 for preparing hydrogen peroxide by photocatalysis, wherein the alcohol solvent is ethanol, and the drying treatment is vacuum drying at 60 ℃ for 4-12 h.
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Inventor after: Zhang Qitao Inventor after: Wang Jie Inventor after: Yu Lei Inventor after: Yin Suna Inventor after: Li Ying Inventor after: Su Chenliang Inventor before: Wang Jie Inventor before: Zhang Qitao Inventor before: Yu Lei Inventor before: Yin Suna Inventor before: Li Ying Inventor before: Su Chenliang |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |