CN114669315B - Preparation method of all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis - Google Patents
Preparation method of all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- -1 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic Chemical compound 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-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
- 239000007789 gas Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 15
- 239000012298 atmosphere Substances 0.000 abstract description 8
- 239000011261 inert gas Substances 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- NAZODJSYHDYJGP-UHFFFAOYSA-N 7,18-bis[2,6-di(propan-2-yl)phenyl]-7,18-diazaheptacyclo[14.6.2.22,5.03,12.04,9.013,23.020,24]hexacosa-1(23),2,4,9,11,13,15,20(24),21,25-decaene-6,8,17,19-tetrone Chemical group CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=CC=1)C(=O)C2=CC=C3C(C=C1)=C2C4=CC=C3C(=O)N(C=4C(=CC=CC=4C(C)C)C(C)C)C(=O)C1=C23 NAZODJSYHDYJGP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000071 diazene Inorganic materials 0.000 abstract 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 32
- 239000000843 powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- 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
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- 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 discloses a preparation method of an all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis, which comprises the following steps: firstly, placing a nitrogen-containing precursor into a muffle furnace for calcination, and grinding to obtain g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Will g-C 3 N 4 Mixing with 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride, calcining under inert gas atmosphere, grinding, cleaning the obtained sample with methanol and deionized water until the supernatant is colorless, centrifuging, drying, and grinding. The invention prepares the full organic composite photocatalysis material, because of 1,6,7,12, -tetrachloro-3,5,9,10-perylene tetracarboxylic diimine and g-C 3 N 4 And a full organic heterojunction is formed between the two, chlorine atoms are substituted at the bay position of perylene tetracarboxylic diimide, so that electron migration inside carbon nitride is promoted, separation of carriers is facilitated, the recombination rate of electron-hole pairs is reduced, and the hydrogen peroxide production capability of photocatalysis is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of organic photocatalytic materials, and particularly relates to a preparation method of an all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis.
Background
Hydrogen peroxide, which is an environmentally friendly green chemical, has a rising market demand for years and is widely used in the industries of environmental protection, petrifaction, electronics, food and the like. At present, hydrogen peroxide is industrially produced by an anthraquinone method, but raw materials, products and production processes have high dangers, high energy consumption and serious pollution, and a novel energy-saving and environment-friendly hydrogen peroxide production process is imperative to be developed. Therefore, the photocatalyst is widely focused on the preparation of hydrogen peroxide by using water and oxygen under solar energy, and is considered to realize the advantages of cleanliness, sustainability and green and high efficiency.
With conventional photocatalysts such as metal oxides and metal sulfidesCompared with the metal-free organic photocatalyst, the metal-free organic photocatalyst has the advantages of no toxicity, biocompatibility, abundant surface properties, low cost, high photochemistry and thermal stability and the like, and is widely applied to the field of photocatalysis. However, some of the inherent disadvantages of single organic photocatalysts, such as low visible light absorption efficiency (below 460 nm), e - /h + The factors such as high recombination speed and low charge conductivity limit the process of generating hydrogen peroxide by photocatalysis, so that the problems can be effectively overcome, and the light absorption range is wide - /h + The preparation method has important significance for improving the photocatalytic hydrogen peroxide production of the organic photocatalyst.
Disclosure of Invention
The invention aims to provide a preparation method of an all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis, which has the advantages of high specific surface area, more reactive sites and high hydrogen peroxide producing capability by photocatalysis.
The technical scheme adopted by the invention is that the preparation method of the all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis is implemented according to the following steps:
step 1, placing a nitrogen-containing precursor into a crucible with a cover, sending the crucible into a muffle furnace for calcination, and grinding after natural cooling to obtain g-C 3 N 4 ；
Step 2, the g-C obtained in the step 1 is processed 3 N 4 Mixing with 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride uniformly, grinding, placing into a porcelain boat, feeding into a tube furnace, calcining under the protection of inert gas atmosphere, performing thermal polycondensation reaction, cooling to room temperature, and grinding;
and step 3, repeatedly cleaning the obtained sample with methanol and deionized water until the supernatant is colorless, centrifuging, drying in a vacuum drying oven, and grinding to obtain the full-organic composite photocatalytic material.
The present invention is also characterized in that,
in the step 1, the nitrogen-containing precursor is any one of urea, melamine, dicyandiamide, cyanamide and thiourea.
In the step 1, during calcination, the temperature is raised to 200-300 ℃ at a heating rate of 3-15 ℃/min, and then the temperature is kept for 1h, and the temperature is raised to 400-600 ℃ and kept for 3-5 h.
In step 2, 1,6,7,12, -tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride with g-C 3 N 4 The mass ratio of (2) is 0.1-1: 100.
in the step 2, during calcination, the temperature is raised to 300-500 ℃ at a heating rate of 3-10 ℃/min, and the temperature is kept for 1-3 h; the inert gas is argon or nitrogen, and the gas flow rate is 40-100 ml/min.
In the step 3, when methanol and deionized water are used for alternately cleaning, the rotating speed of a centrifugal machine is 7000-8000 r/min, and the centrifugal time is 2-6 min; the drying temperature is 60-100 ℃ and the drying time is 8-12 h.
The invention has the advantages that,
1. the preparation method is simple in process flow and simple and convenient to operate, and the full-organic copolymerized graphite phase carbon nitride photocatalytic material is prepared through high-temperature polycondensation reaction of the graphite phase carbon nitride and the organic dye, namely through calcination of the graphite phase carbon nitride and the organic dye in an inert atmosphere, so that the one-step calcination method not only saves cost, but also provides reference for researchers in the aspects of modification of similar nano materials and preparation of composite materials;
2. the invention relates to a preparation method of an all-organic composite photocatalytic material, which is 1,6,7,12, -tetrachloro-3,5,9,10-perylene tetracarboxylic diimide (PI) Cl ) And graphite phase carbon nitride (g-C) 3 N 4 ) And a full organic heterojunction is formed between the two layers, chlorine atoms (Cl) are substituted at the bay position of perylene tetracarboxylic diimide (PI), so that electron migration inside carbon nitride is promoted, a narrower band gap width can be obtained, and separation of carriers is facilitated, thereby reducing the recombination rate of electron-hole pairs and improving the hydrogen peroxide production capability of photocatalysis.
Drawings
FIG. 1 shows PI prepared in example 3 of the present invention Cl CN sampleThe ultraviolet visible diffuse reflection absorption spectrum of CN;
FIG. 2 is a transmission electron microscope image of a sample (CN);
FIG. 3 shows PI prepared in example 3 of the present invention Cl Transmission electron microscopy of CN samples;
FIG. 4 shows PI prepared in example 3 of the present invention Cl X-ray diffraction patterns of CN samples and CN;
FIG. 5 shows PI prepared in example 3 of the present invention Cl Fluorescence spectrograms of CN sample and CN;
FIG. 6 shows PI prepared in example 3 of the present invention Cl CN sample and photocatalytic hydrogen peroxide producing performance test chart.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a preparation method of an all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis, which comprises the steps of 1,6,7,12, -tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride and graphite-phase carbon nitride (g-C) 3 N 4 ) Is prepared by calcining raw materials in an inert atmosphere;
the method is implemented according to the following steps:
step 1, placing a nitrogen-containing precursor into a crucible with a cover, sending the crucible into a muffle furnace for calcination, and grinding after natural cooling to obtain g-C 3 N 4 ；
The nitrogen-containing precursor is any one of urea, melamine, dicyandiamide, cyanamide and thiourea;
during calcination, the temperature is raised to 200-300 ℃ at a heating rate of 3-15 ℃/min and is kept for 1h, and then the temperature is raised to 400-600 ℃ and is kept for 3-5 h;
step 2, the g-C obtained in the step 1 is processed 3 N 4 Mixing with 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride uniformly, grinding, placing into a porcelain boat, feeding into a tube furnace, calcining under the protection of inert gas atmosphere, performing thermal polycondensation reaction, cooling to room temperature, and grinding;
1,6,7,12, -tetrachloro-3,5,9,10-perylenetetracarboxylic dianhydride with g-C 3 N 4 The mass ratio of (2) is 0.1-1: 100;
the inert gas is argon or nitrogen, and the gas flow rate is 40-100 ml/min;
heating to 300-500 ℃ at a heating rate of 3-10 ℃/min during calcination, and preserving heat for 1-3 h;
step 3, repeatedly cleaning the obtained sample with methanol and deionized water until the supernatant is colorless, centrifuging, drying in a vacuum drying oven, grinding to obtain the sample which is the all-organic composite photocatalytic material, and named as PI Cl CN；
When methanol and deionized water are used for alternately cleaning, the rotating speed of a centrifugal machine is 7000-8000 r/min, and the centrifugal time is 2-6 min;
the drying temperature is 60-100 ℃ and the drying time is 8-12 h.
Example 1
Weighing 25g of melamine, placing in a crucible with a cover, placing in a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, keeping the temperature for 3 hours, naturally cooling, taking out, and grinding to obtain light yellow powder g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Weighing 5g of light yellow powder and 0.01g of 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride, grinding the two, uniformly mixing, putting into a porcelain boat, placing into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, reacting for 2 hours, and taking out after natural cooling; repeatedly cleaning with methanol and deionized water, vacuum drying, and grinding to obtain brown powder PI Cl CN。
Example 2:
weighing 25g of melamine, placing in a crucible with a cover, placing in a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, keeping the temperature for 3 hours, naturally cooling, taking out, and grinding to obtain light yellow powder g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Weighing 5g of light yellow powder and 0.01g of 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride, grinding the two, uniformly mixing, putting into a porcelain boat, placing into a tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon for reaction for 2 hours, and taking out after natural cooling; repeatedly cleaning with methanol and deionized water, vacuum drying, and grinding to obtain brown powder PI Cl CN。
Example 3
Weighing 25g of melamine, placing in a crucible with a cover, placing in a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, keeping the temperature for 3 hours, naturally cooling, taking out, and grinding to obtain light yellow powder g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the 5g of pale yellow powder and 0.01g of 1,6,7,12, -tetrachloro-3,5,9,10-perylenetetracarboxylic dianhydride (PA) were weighed out Cl ) Grinding the two materials, uniformly mixing, putting into a porcelain boat, placing into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, reacting for 2 hours, and taking out after natural cooling; repeated washing with methanol and deionized water, vacuum drying, and grinding to obtain PA Cl Grafted at g-C 3 N 4 Composite photocatalyst PI Cl CN, the substitution of chlorine atom in PA bay site of the catalyst inhibits pi-pi aggregation among perylene diimide molecules, thereby influencing interface electron transmission and improving photocatalytic performance.
As a comparative example, the pale yellow powder g-C in this example was prepared 3 N 4 (1g) Placing the sample in a tube furnace with a porcelain boat, heating to 400 ℃ in an argon atmosphere, preserving heat for 2 hours, grinding in an agate mortar, and collecting the sample to obtain the sample CN.
FIG. 1 shows an all-organic composite photocatalytic material (PI) for producing hydrogen peroxide by photocatalysis prepared in example 3 of the present invention Cl CN) and comparative sample (CN), from which it can be seen that CN shows an absorption band at 475nm, the absorption band at 475nm being assigned to a pi-pi transition in the conjugated heptazine ring; PI (proportional integral) Cl CN shows strong absorption in the visible region, and the absorption edge is about 620nm; the absorption performance in the visible light region is obviously enhanced compared with CN, so that more photo-generated charges can be generated under the light excitation, and the photo-catalytic reaction is more facilitated. Proved by the invention, the fully organic copolymerization carbon nitride photocatalysis composite material PI prepared by the thermal polymerization method Cl The CN spectral response range is significantly extended.
FIG. 2 is a TEM image of a comparative sample (CN), and FIG. 3 is an all-organic composite light for photocatalytic hydrogen peroxide production prepared in example 3 of the present inventionCatalytic material (PI) Cl CN), from the TEM image, it can be seen that comparative CN and all-organic copolymerized carbon nitride photocatalytic composite material (PI Cl CN) maintains the lamellar structure of the graphite phase desalinated carbon, but PI prepared in example 3 Cl CN, PI can be seen at the edge of CN sheet Cl The nano-fiber structure of (2) proves that the PI can be prepared by the thermal polymerization method Cl Successfully compound with the carbon nitride nano-sheet.
FIG. 4 is a schematic diagram showing an all-organic composite photocatalytic material (PI) for producing hydrogen peroxide by photocatalysis prepared in example 3 of the present invention Cl CN) and comparative sample (CN) XRD comparison patterns, from which it can be seen that two characteristic peaks (100) and (002) appear at 13.2 and 27.4 °, respectively, correspond to in-plane repeated interplanar stacking of heptazine units and conjugated C-N heterocycles, PI compared to CN Cl The peak of CN at 27.6 ° moves to a high angle, indicating that the heterojunction material has a smaller interlayer spacing, which means that the electron cloud overlap density is greater, facilitating separation and migration of photogenerated carriers. The invention proves that the carboxyl-containing perylene imide and the carbon nitride nanosheets can be successfully compounded by a thermal polymerization method.
FIG. 5 is a schematic diagram of an all-organic composite photocatalytic material (PI) for photocatalytic hydrogen peroxide production prepared in example 3 of the present invention Cl CN) and comparative sample (CN), it can be seen from the PL comparison graph that CN shows a strong fluorescence emission peak at 371nm excitation wavelength, the emission peak is located at 469nm, PI Cl The emission peak intensity of CN is weaker than that of CN, and fluorescence quenching phenomenon appears, which shows that the recombination probability of photo-generated electron-hole pairs is obviously reduced. Meanwhile, PI Cl The emission peak of CN at 469nm is blue shifted, indicating PI Cl With CN, i.e. CN and self-assembled PI Cl A built-in electric field is formed between the two layers, so that photo-generated charges can be effectively transferred. The invention proves that the thermal polymerization method can reduce the photon-generated electron-hole recombination probability and improve the photon-generated charge migration capability.
For the sample obtained in example 3, the hydrogen peroxide production performance of the product was tested, and the specific test method and the result analysis were as follows:
50mg of g-C obtained in this example 3 was weighed out 3 N 4 And PI (proportional integral) Cl CN samples are respectively dispersed in 50mL deionized water and respectively placed in a 100mL beaker for photocatalytic hydrogen production test, in order to keep the photocatalytic hydrogen production in a constant temperature state, an ice bath method is adopted, the reaction temperature is kept at 0 ℃, a magnetic stirrer below the reactor is turned on to drive a bar-shaped magnet in the reactor to rotate in the reaction process, the solution is kept to be continuously stirred, a xenon lamp power supply is turned on, the photocatalytic hydrogen production reaction is carried out under visible light, 3mL of detection and sampling are carried out every 10min, a water filter head with the thickness of 0.22 mu m is used for filtering, the catalyst in the solution is removed, then 100 mu L of fluorescent reagent is added, after the reaction is carried out for 10min, 1mL of 0.1mol/L NaOH solution is added, the measurement is carried out under the conditions that the excitation wavelength is 315nm and the emission wavelength is 409nm, and the fluorescence intensity is used for representing the hydrogen peroxide yield.
FIG. 6 shows the prepared all-organic composite photocatalytic material (PI) Cl CN) and comparative sample (CN) of hydrogen peroxide production, the catalyst PI synthesized by the invention Cl The CN is used for synthesizing hydrogen peroxide by taking oxygen in water and air as raw materials under the condition of not needing any sacrificial agent, and the quantity of the hydrogen peroxide produced by visible light catalysis is far higher than that of a comparative sample (CN). Proved by the invention, the full-organic type photocatalysis composite material PI prepared by the thermal polymerization method Cl CN has good hydrogen peroxide producing performance.
The above description is only of the preferred embodiments of the invention, but the protection scope of the invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the invention pertains should make equivalent substitutions or modifications according to the technical solution of the invention and its inventive concept within the scope of the invention.
Claims (2)
1. The preparation method of the all-organic composite photocatalytic material for producing hydrogen peroxide by photocatalysis is characterized by comprising the following steps of:
step 1, placing a nitrogen-containing precursor into a crucible with a cover, and feeding into a muffle furnaceCalcining, naturally cooling, grinding to obtain g-C 3 N 4 ；
During calcination, the temperature is raised to 200-300 ℃ at a heating rate of 3-15 ℃/min, the temperature is kept for 1h, and then the temperature is raised to 400-600 ℃ and the temperature is kept for 3-5 h;
step 2, the g-C obtained in the step 1 is processed 3 N 4 Mixing with 1,6,7, 12-tetrachloro-3,5,9,10-perylene tetracarboxylic dianhydride uniformly, grinding, placing into a porcelain boat, feeding into a tube furnace, calcining under the protection of argon or nitrogen atmosphere, performing thermal polycondensation reaction, cooling to room temperature, and grinding;
1,6,7,12, -tetrachloro-3,5,9,10-perylenetetracarboxylic dianhydride with g-C 3 N 4 The mass ratio of (2) is 0.1-1: 100;
heating to 300-500 ℃ at a heating rate of 3-10 ℃/min during calcination, and preserving heat for 1-3 h; the gas flow rate is 40-100 mL/min;
and step 3, repeatedly cleaning the obtained sample with methanol and deionized water until the supernatant is colorless, centrifuging, drying in a vacuum drying oven, and grinding to obtain the full-organic composite photocatalytic material.
2. The method for preparing an all-organic composite photocatalytic material for photocatalytic hydrogen peroxide production according to claim 1, wherein in the step 1, the nitrogen-containing precursor is any one of urea, melamine, dicyandiamide, cyanamide and thiourea.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190127225A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Carbon nitride modified with perylenetetracarboxylic dianhydride / graphene oxide aerogel composite material, preparation method and application thereof |
| CN111393663A (en) * | 2020-04-07 | 2020-07-10 | 曲靖师范学院 | Perylene bisimide base coordination polymer, preparation method and application thereof |
| CN112574237A (en) * | 2020-12-16 | 2021-03-30 | 河南盛鼎建设集团有限公司 | g-C3N4PTCDI-Br composite material and preparation method and application thereof |
| CN112871196A (en) * | 2021-01-17 | 2021-06-01 | 北京工业大学 | Preparation method of aminated fluorine-doped carbon nitride photocatalyst |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190127225A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Carbon nitride modified with perylenetetracarboxylic dianhydride / graphene oxide aerogel composite material, preparation method and application thereof |
| CN111393663A (en) * | 2020-04-07 | 2020-07-10 | 曲靖师范学院 | Perylene bisimide base coordination polymer, preparation method and application thereof |
| CN112574237A (en) * | 2020-12-16 | 2021-03-30 | 河南盛鼎建设集团有限公司 | g-C3N4PTCDI-Br composite material and preparation method and application thereof |
| CN112871196A (en) * | 2021-01-17 | 2021-06-01 | 北京工业大学 | Preparation method of aminated fluorine-doped carbon nitride photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| Tetrachloro-substituted Perylene Bisimide Dyes as Promising n-Type Organic Semiconductors: Studies on Structural, Electrochemical and Charge Transport Properties;Zhijian Chen et al;ChemPhysChem;第137页、第139页 * |
| Two-channel photocatalytic production of H2O2 over g-C3N4 nanosheets modified with perylene imides;Liping Yang et al.;Journal of Catalysis;abstract 2. Experimental * |
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