CN116496300A - Photocatalytic composite material and preparation method and application thereof - Google Patents
Photocatalytic composite material and preparation method and application thereof Download PDFInfo
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- CN116496300A CN116496300A CN202310368785.7A CN202310368785A CN116496300A CN 116496300 A CN116496300 A CN 116496300A CN 202310368785 A CN202310368785 A CN 202310368785A CN 116496300 A CN116496300 A CN 116496300A
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- China
- Prior art keywords
- composite material
- photocatalytic composite
- photocatalytic
- dcn
- aminobenzonitrile
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 claims description 84
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical group N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- -1 amino, hydroxy Chemical group 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 229910052736 halogen Chemical group 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 238000006303 photolysis reaction Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 8
- 238000001782 photodegradation Methods 0.000 abstract description 8
- 238000013508 migration Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000003306 harvesting Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 29
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000000227 grinding Methods 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- DKZXTOPFCDDGGX-UHFFFAOYSA-N tri-s-triazine Chemical compound C1=NC(N23)=NC=NC2=NC=NC3=N1 DKZXTOPFCDDGGX-UHFFFAOYSA-N 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005219 aminonitrile group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- 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
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalysis composite material and a preparation method and application thereof. Relates to the technical field of photocatalysis materials. The photocatalytic composite material has a compound with a structural formula shown in a formula I: i is a kind of. In the network structure of the photocatalytic composite material, the pi electron delocalization of the photocatalytic composite material can be enhanced by the-C (identical to that of N), the nitrogen defect and the aromatic ring, so that the rapid migration of light absorption and photo-generated electrons can be enhanced; furthermore, the photocatalytic composite material can harvest more photons under the irradiation of visible light and inhibit the recombination of photon-generated carriers, thereby obviously improving the photodegradation of PHE and BPA.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a photocatalytic composite material and a preparation method and application thereof.
Background
Fujishima and Honda in 1972 in TiO 2 The photo-decomposition reaction of water is found on the semiconductor single crystal electrode, the Honda-rattan island effect of the semiconductor material is found, the research of multiphase semiconductor photocatalysis is truly started, and the photo-catalytic water decomposition is started to solve the hot tide of energy crisis. Hydrogen plays an important role in the system as a renewable clean energy source, and can be used for fuel cells and chemical industry. The existing hydrogen production method mainly comprises the steps of photolysis of water to produce hydrogen, wherein the photolysis of water to produce hydrogen is an important mode for converting solar energy into available energy, and is also an effective mode for storing the solar energy. The photocatalytic water splitting performance is directly influenced by the photo-generated charge transfer, the band gap structure and the stability of the catalyst, so that the hydrogen production efficiency of the existing method is not high, and the design of a novel efficient environment-friendly photocatalyst is a key for improving the hydrogen production efficiency.
Graphite phase carbon nitride (Graphitic carbon nitride, g-C) 3 N 4 ) The conjugated polymer with a two-dimensional lamellar structure has stable property and is similar to a graphite structure. g-C 3 N 4 As a novel metal-free polymerization photocatalyst, the catalyst has the advantages of green, economy, good stability, good optical performance and electronic performance and the like, and is widely concerned in the field of photocatalysis; g-C 3 N 4 Can be applied to the field of photocatalytic degradation of pollutants, the field of hydrogen production by photocatalytic water splitting and CO reduction at present 2 Domain and selective organic synthesis reaction domain. g-C 3 N 4 As a typical representative of graphene-like materials, the band gap is 2.7eV, the graphene-like materials can absorb visible light, and have better chemical and thermodynamic stability due to the connection between layers by Van der Waals force, and the graphene-like materials have the following characteristics of g-C 3 N 4 It also has the advantages of no toxicity, abundant sources, low cost, simple preparation, etc. However, g-C 3 N 4 In practical applications, due to the pure phase g-C 3 N 4 There are a number of disadvantages in itself which affect the improvement of the photocatalytic properties thereof, such that g-C 3 N 4 Limited by fast charge carrier recombination, low surface area and limited absorption of visible light, especially g-C 3 N 4 Has higher electron-hole recombination rate, so that the photocatalytic efficiency is severely limited.
Therefore, there is a need to find a composite material to improve g-C 3 N 4 The photocatalytic performance widens the photoresponse range and improves the electron-hole separation rate of the photocatalyst.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a photocatalytic composite material is provided.
The second technical problem to be solved by the invention is as follows:
a method for preparing the photocatalytic composite material is provided.
The third technical problem to be solved by the invention is:
the application of the photocatalytic composite material.
In order to solve the first technical problem, the invention adopts the following technical scheme: a photocatalytic composite material having a structural formula as shown in formula I: formula I:wherein R is 1 And R is 2 Independently selected from structures of formula II or formula III: formula II: />
Formula III:
wherein R is 3 、R 4 And R is 5 Independent selectionAmino substituted from amino, alkyl substituted amino, hydroxy substituted amino or halogen substituted amino;
wherein R is 7 、R 8 And R is 10 Independently selected from imino, alkyl substituted imino, hydroxy substituted imino, or halo substituted imino;
wherein R is 6 、R 9 And R is 11 Independently selected from amino, alkyl substituted amino, hydroxy substituted amino or halogen substituted amino;
wherein R is 3 、R 6 、R 9 And R is 11 At least one of which is selected from-NH-C.ident.N or X;
wherein X comprises the following structure:
wherein M is a metal ion.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
in the network structure of the photocatalytic composite material, the pi electron delocalization of the photocatalytic composite material can be enhanced by the-C (identical to that of N), the nitrogen defect and the aromatic ring, so that the rapid migration of light absorption and photo-generated electrons can be enhanced; furthermore, the photocatalytic composite material can harvest more photons under the irradiation of visible light and inhibit the recombination of photon-generated carriers, thereby obviously improving the photodegradation of PHE (photocatalytic hydrogen evolution) and BPA (bisphenol A).
Compared with graphite phase carbon nitride, the photocatalytic composite material has greatly improved photocatalytic performance, and the prepared photocatalytic composite material also widens the photoresponse range of the material and improves the electron hole separation rate.
According to an embodiment of the invention, the alkyl group in the alkyl-substituted amino group comprises C 1-8 Alkyl and halogen substituted C 1-8 An alkyl group.
According to the inventionIn one embodiment, the alkyl-substituted imino group comprises C 1-8 Alkyl and halogen substituted C 1-8 An alkyl group.
According to an embodiment of the present invention, M includes at least one of potassium ion, calcium ion, zinc ion, magnesium ion, and sodium ion. For M in structure X, the metal ion M is doped into structure X by combining with the electronegativity of the N atom in the X structure. So as to enhance the light absorption and the rapid migration of photo-generated electrons of the photo-catalytic composite material and promote the photo-catalytic activity of the photo-catalytic composite material.
According to an embodiment of the present invention, the metal ion M is doped to R in addition to the structure X 10 Is a kind of medium.
According to an embodiment of the present invention, the metal ion M is doped on amino and imino groups in the photocatalytic material.
According to an embodiment of the invention, the R 1 The structural formula of (2) is shown as formula II; r is R 2 The structural formula of (2) is shown as a formula III; r is R 6 The structural formula of (C) is shown as X.
According to an embodiment of the present invention, the photocatalytic composite material has a structure as follows:
in the structure, nitrogen defects and-C.ident.N are introduced and potassium ions are doped, so that pi electrons of the composite material are enhanced in delocalization, and light absorption and rapid migration of photo-generated electrons are enhanced.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a method of preparing the photocatalytic composite material, comprising the steps of:
s1, mixing a compound containing a carbon nitride structure with aminobenzonitrile, and calcining to obtain an intermediate product;
s2, mixing the intermediate product with molten salt containing metal cations under protective atmosphere, and calcining to obtain the photocatalytic composite material.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
in the method for preparing the photocatalytic composite material, the photocatalytic composite material obtained by grafting the Aminonitrile (ABN) on the tri-S-triazine can be obtained by performing Schiff base reaction on the compound containing the carbon nitride structure and the Aminonitrile (ABN), and in the step S2, nitrogen defects and-C [ identical to ] N are introduced and metal cations are doped in the intermediate product under the fused salt calcination reaction of the intermediate product and the metal cations, so that the delocalization of the product is enhanced.
The method for preparing the photocatalytic composite material can graft the visible light responsive Aminobenzonitrile (ABN) on the CN network structure by using a high-temperature two-step thermal polymerization method so as to obtain the photocatalytic composite material.
In the method of the present invention, the carbon nitride (g-C) 3 N 4 ) An organic monomer Aminobenzonitrile (ABN) is introduced into the structure, so that the Aminobenzonitrile (ABN) is grafted on the carbon nitride network structure. In the network structure, the pi electron delocalization of the photocatalytic composite material can be enhanced by the-C.ident.N, nitrogen defects and aromatic rings in an aminobenzene nitrile (ABN) structure, and the photocatalytic composite material is favorable for enhancing light absorption and rapid migration of photo-generated electrons.
According to one embodiment of the invention, the mass ratio of the compound containing the carbon nitride structure to the aminobenzonitrile is 100-400:4-5. The difference of the mass ratio of the compound containing the carbon nitride structure to the aminobenzonitrile can influence the structure of the photocatalytic composite material, thereby influencing the photocatalytic efficiency, hydrogen production yield and catalytic stability of the photocatalytic composite material.
According to an embodiment of the present invention, the mass ratio of the carbon nitride structure-containing compound to the aminobenzonitrile includes any one of the following mass ratios: 100:4-5, 150:4-5, 200:4-5, 250:4-5, 300:4-5, 350:4-5, 400:4-5, 200:4. 200:4.5 and 200:5.
according to one embodiment of the invention, the mass ratio of the aminobenzonitrile to the molten salt containing metal cations is 4-5:4-12.
According to an embodiment of the present invention, the mass ratio of the carbon nitride structure-containing compound to the aminobenzonitrile includes any one of the following mass ratios: 4.5:4-12, 5:4-12, 4-5:4. 4-5:4.5, 4-5:5. 4-5:5.5, 4-5:6. 4-5:6.5, 4-5:7. 4-5:7.5, 4-5:8. 4-5:8.5, 4-5:9. 4-5:9.5, 4-5:10. 4-5:10.5, 4-5:11. 4-5:11.5, 4-5: 12. 4:6 and 5:6.
according to one embodiment of the invention, the carbon nitride structure-containing compound comprises dicyandiamide.
According to one embodiment of the invention, the Aminobenzonitrile (ABN) accounts for 2-2.5% of the raw materials of the photocatalytic composite material by mass. The difference of the mass ratio of the Aminobenzonitrile (ABN) in the photocatalytic composite material can influence the structure of the photocatalytic composite material, thereby influencing the photocatalytic efficiency, hydrogen production yield and catalytic stability of the photocatalytic composite material.
According to one embodiment of the present invention, in step S1, the compound having a carbon nitride structure may be prepared by a polymerization reaction. Further, the polymerization reaction is a thermal polycondensation method. The thermal polycondensation method is to prepare g-C by pyrolysis treatment of nitrogen-rich precursor 3 N 4 . The method has the characteristics of cheap raw materials, simple preparation process and good product crystal form.
According to one embodiment of the present invention, step S1 further comprises heating the nitrogen-containing organic matter to obtain a carbon nitride structure-containing compound having a structural unit of tris-S-triazine through polymerization.
According to one embodiment of the invention, the metal cation-containing molten salt comprises at least one of a melt of an alkali metal, a melt of an alkaline earth metal halide. The metal ions in the metal cation-containing molten salt act as charge compensators to balance NH in the molten salt thermal polymerization in the reaction of step S2 3 By balancing C-N - The charge of C introduces metal ions, i.e. the metal ions combine with the electronegativity of the N atoms, doping into the photocatalytic composite material.
According to one embodiment of the invention, the molten salt containing metal cations comprises NaCl-KCl molten salt, wherein the mass ratio of NaCl to KCl is 4.28-6.28:1.72-5.72. The molten salt mass ratio is such as to ensure the progress of the reaction. Different molten salts can affect the structure of the product. In addition, the change in the proportion of the molten salt and the kind of the molten salt also affects the reaction conditions.
According to one embodiment of the invention, in step S1, the calcination temperature is 400-500 ℃, and in step S2, the calcination temperature is 600-700 ℃.
According to one embodiment of the present invention, in step S1, the temperature of calcination is selected from the temperature interval consisting of either or both of the following temperatures: 400 ℃, 450 ℃, 500 ℃.
According to one embodiment of the present invention, in step S2, the temperature of calcination is selected from the temperature interval consisting of either or both of the following temperatures: 600 ℃, 650 ℃, 700 ℃.
According to one embodiment of the invention, in step S1, the calcination time is 2-4 hours, and in step S2, the calcination time is 2-4 hours.
According to one embodiment of the invention, in step S1, the time of calcination is selected from the time interval consisting of either or both of the following times: 2 hours, 2.5 hours, 3 hours, 3.5 hours and 4 hours.
According to one embodiment of the invention, in step S2, the time of calcination is selected from the time interval consisting of either or both of the following times: 2 hours, 2.5 hours, 3 hours, 3.5 hours and 4 hours.
According to one embodiment of the present invention, when the calcination temperature in step S1 is different from the calcination temperature in step S2, it is required that both require the same calcination time.
According to one embodiment of the present invention, in step S1, the intermediate product is cooled and then ground. The ground reactants are subjected to thermal polymerization in step S2, and the reaction is more sufficient.
According to one embodiment of the present invention, step S2 further includes a step of washing the calcined product with hot water and performing a drying process.
According to one embodiment of the invention, the step of drying treatment comprises the step of drying the product in a vacuum drying oven for 2-4 hours.
In another aspect, the invention also relates to the use of the photocatalytic composite material in a hydrogen production device. Comprising a photocatalytic composite material as described in the embodiment of aspect 1 above. The application adopts all the technical schemes of the photocatalytic composite material, so that the photocatalytic composite material has at least all the beneficial effects brought by the technical schemes of the embodiment.
In another aspect, the invention also relates to application of the photocatalytic composite material in bisphenol A degradation and hydrogen production reaction by photodecomposition of water under visible light. Comprising a photocatalytic composite material as described in the embodiment of aspect 1 above. The application adopts all the technical schemes of the photocatalytic composite material of the embodiment, so that the photocatalytic composite material has at least all the beneficial effects brought by the technical schemes of the embodiment.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of the method for preparing a photocatalytic composite material in example 1.
FIG. 2 is a graph showing the ultraviolet-visible diffuse reflectance spectrum of the photocatalytic composite materials obtained in examples 1 to 3 and comparative examples 1 to 3.
FIG. 3 is a graph showing the photocatalytic hydrogen production rate test of the photocatalytic composite materials obtained in examples 1-3 and comparative examples 1-3.
FIG. 4 is a graph showing photocatalytic degradation of the samples obtained in examples 1-3 and comparative examples 1-3.
FIG. 5 shows photoluminescence spectra of the samples obtained in examples 1 to 3 and comparative examples 1 to 3.
FIG. 6 is a graph showing the photocatalytic stability test of the sample obtained in example 2.
FIG. 7 is a nuclear magnetic resonance spectrum of the sample obtained in example 2.
Detailed Description
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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 fall within the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
In an embodiment, the term "alkyl" refers to a saturated hydrocarbon containing primary (positive) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, e.g., "C 1-8 Alkyl "refers to an alkyl group containing 1 to 8 carbon atoms. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH), 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3), 1-pentyl (n-pentyl, -CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 and octyl (- (CH) 2 ) 7 CH 3 )。
In the examples, "C 1～10 Alkyl "refers to an alkyl group having 1 to 10 carbon atoms and is meant to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, C 1 ～ 10 As in "C 1 ～ 10 Alkyl "is defined to include groups having 1, 2,3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a straight or branched chain structure. For example, "C 1 ～ 10 The alkyl group "specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
In the examples, "C 1～4 The alkyl group "means an alkyl group having 1 to 4 carbon atoms, and includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.
In the examples, "C 1 ～ 10 Alkoxy "means an alkyl group as defined above attached through an oxygen atom, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like. Similarly, "C 1 ～ 10 Haloalkyl "refers to halogen substituted alkyl as defined above.
In the examples, "alkenyl" is meant to include a radical having at least one unsaturated site, i.e., carbon-carbon sp 2 A hydrocarbon of a normal carbon atom, a secondary carbon atom, a tertiary carbon atom or a cyclic carbon atom of the double bond. Phrases containing this term, e.g., "C 2-8 Alkenyl "refers to alkenyl groups containing 2 to 8 carbon atoms. Suitable examples include, but are not limited to: vinyl (-ch=ch) 2 ) Propenyl (-CH) 2 CH＝CH 2 ) Cyclopentenyl (-C) 5 H 7 ) And 5-hexenyl (-CH) 2 CH 2 CH 2 CH 2 CH＝CH 2 )。
In embodiments, halogen "or" halo "refers to F, cl, br or I.
In embodiments, "halo substituted" means that an optional amount of H at any optional position on the corresponding group is substituted with halo, e.g., fluoromethyl, including monofluoromethyl, difluoromethyl, trifluoromethyl.
Example 1
A method for preparing a photocatalytic composite material, as shown in fig. 1, specifically comprises the following steps:
(1) Weighing 4g of dicyandiamide and 80mg of Aminobenzonitrile (ABN), uniformly mixing and grinding, then transferring the mixture into a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained and 6.0g of metal salt (4.28 g NaCl and 1.72g KCll) were milled for 20min, and then calcined in a nitrogen-fed tube furnace at 610℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic composite material is prepared through the steps, and a sample is named DCN-NaK-80ABN.
As shown in FIG. 1, wherein dicyandiamide is polymerized to give g-C 3 N 4 ，g-C 3 N 4 Having structural units of tris-s-triazine.
The method comprises the steps of preparing a three-s-triazine structural unit, wherein the structural unit is a photocatalytic composite material, and the photocatalytic composite material can further repeat the reaction to obtain a new structural unit of amino-benzonitrile (ABN) grafted on the three-s-triazine, wherein the structural unit is obtained by grafting amino-benzonitrile (ABN) on the three-s-triazine through Schiff base reaction; when other substances with a tri-s-triazine structure are further added, the photocatalytic composite material can further repeat the reaction to obtain a new structural unit of amino-benzonitrile (ABN) grafted on the tri-s-triazine, and thus the novel photocatalytic composite material is obtained. When the material is combined with 6.0g of gold in the second stepAfter grinding and calcining the metal salt (4.28 g NaCl and 1.72g KCl), K/Na ions are introduced into the material as charge compensation agent to balance NH in molten salt thermal polymerization 3 The eutectic NaCl-KCl salt would lead to nitrogen defects and-c≡n. Finally, the high-performance photocatalytic composite material with enhanced delocalization and containing-C.ident.N and nitrogen defects can be obtained.
The photocatalytic composite material prepared in example 1 has the structural formula:
example 2
A method of preparing a photocatalytic composite material comprising the steps of:
(1) Weighing 4g of dicyandiamide and 90mg of Aminobenzonitrile (ABN), uniformly mixing and grinding, then transferring the mixture into a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained and 6.0g of metal salt (4.28 g NaCl and 1.72g KCl) were milled for 20min, and then calcined in a nitrogen-fed tube furnace at 610℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic composite material is prepared through the steps, and a sample is named DCN-NaK-90ABN.
Compared with example 1, the sample prepared was designated DCN-NaK-90ABN, except that the amount of Aminobenzonitrile (ABN) added was 90 mg.
Example 3
A method of preparing a photocatalytic composite material comprising the steps of:
(1) Weighing 4g of dicyandiamide and 100mg of Aminobenzonitrile (ABN), uniformly mixing and grinding, then transferring the mixture into a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained and 6.0g of metal salt (4.28 g NaCl and 1.72g KCl) were milled for 20min, and then calcined in a nitrogen-fed tube furnace at 610℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic composite material is prepared through the steps, and a sample is named DCN-NaK-100ABN.
Compared with example 1, the sample prepared was designated DCN-NaK-100ABN, except that the amount of Aminobenzonitrile (ABN) added was 100 mg.
Examples 1-3 differ only in the amount of Aminobenzonitrile (ABN) added. The invention grafts the Aminobenzonitrile (ABN) to g-C 3 N 4 The photocatalytic composite material of the present invention can be obtained by a network structure and performing a second calcination treatment in a molten salt environment. The added amount of the Aminobenzonitrile (ABN) is different, so that the proportion of the Aminobenzonitrile (ABN) in the composite material of the CN network is different, and the chemical property and the catalytic efficiency of the composite material are also different to a certain extent. By adjusting the ratio of dicyandiamide to Aminobenzonitrile (ABN), the Aminobenzonitrile (ABN) in the final polymer is caused to be at g-C 3 N 4 The network structure is changed, and the photocatalytic composite material with different proportions is obtained.
Example 4
A photocatalytic composite material, the material having a compound of the formula: formula I:wherein R is 1 Is of a structure shown in a formula II;
wherein R is 2 The structure shown in the formula III:
formula II:formula III:wherein R is 3 is-NHCl;
wherein R is 4 Is amino;
wherein R is 5 Is amino;
wherein, the liquid crystal display device comprises a liquid crystal display device,R 6 is-NH-C.ident.N;
wherein R is 7 Is imino;
wherein R is 8 Is imino;
wherein R is 9 Is imino;
wherein R is 10 Is imino;
wherein R is 11 Is X;
wherein X comprises the following structure:wherein M is potassium ion.
Example 5
A photocatalytic composite material, the material having a compound of the formula: formula I:wherein R is 1 And R is 2 The structure shown in the formula III:
formula III:wherein R is 6 is-NH-C.ident.N;
wherein R is 7 Is imino;
wherein R is 8 Is imino;
wherein R is 9 Is imino;
wherein R is 10 Is imino;
wherein R is 11 Is X;
wherein X comprises the following structure:wherein M is sodium ion.
Example 6
A photocatalytic composite material, the material having a compound of the formula: formula I:wherein R is 1 Is of a structure shown in a formula II;
wherein R is 2 The structure shown in the formula III:
formula II:formula III:wherein R is 3 Is amino;
wherein R is 4 Is amino;
wherein R is 5 Is amino;
wherein R is 6 Is X;
wherein R is 7 Is imino;
wherein R is 8 Is imino;
wherein R is 9 is-NH-C.ident.N;
wherein R is 10 Is imino;
wherein R is 11 Is X;
wherein X comprises the following structure:
wherein M is potassium ion.
Comparative example 1
Pure phase g-C 3 N 4 The preparation method of the photocatalyst comprises the following steps:
weighing 4g of dicyandiamide, uniformly grinding, placing the dicyandiamide in a 100ml aluminum oxide crucible with a cover, placing the crucible in a muffle furnace, gradually heating to 610 ℃ at a heating rate of 5 ℃/min, and then heating at the constant temperature of 610 ℃ for 2 hours; naturally cooling to room temperature, and grinding the obtained sample again sufficiently.
In comparison with example 2, except that Aminobenzonitrile (ABN) and 6.0g of metal salt (4.28 g of NaCl and 1.72g of KCl) were not added, the prepared sample was designated DCN.
Comparative example 2
A method of preparing a photocatalytic composite material comprising the steps of:
(1) Weighing 4g of dicyandiamide and 90mg of Aminobenzonitrile (ABN), uniformly mixing and grinding, then transferring the mixture into a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) Grinding the obtained solid powder for 20min, and calcining for 2h at 610 ℃ in a tube furnace filled with nitrogen;
(3) Naturally cooling to room temperature, grinding and collecting.
The photocatalytic composite material is prepared through the steps, and a sample is named DCN-90ABN.
In comparison with example 2, the sample prepared was designated DCN-90ABN, except that 6.0g of metal salt (4.28 g of NaCl and 1.72g of KCl) was not added and that the drying process was water-washed.
Comparative example 3
A method of preparing a photocatalytic composite material comprising the steps of:
(1) Weighing 4g of dicyandiamide, grinding uniformly, transferring to a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained and 6.0g of metal salt (4.28 g NaCl and 1.72g KCl) were milled for 20min, and then calcined in a nitrogen-fed tube furnace at 610℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic composite material is prepared through the steps, and a sample is named DCN-NaK.
In comparison with example 2, the only difference was that 90mg of Aminobenzonitrile (ABN) was not added, and the prepared sample was designated DCN-NaK.
Performance test:
test example 1:
ultraviolet visible diffuse reflection experiment:
the photocatalytic composite materials obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to ultraviolet-visible diffuse reflection spectra, and the test is shown in fig. 2.
Wherein the ultraviolet visible diffuse reflection lightThe instruments used for the spectrum test are: hitachi U-3010UV-vis spectrometer using BaSO 4 As a reference.
As can be seen from fig. 2, it is evident that the light absorption of DCN-NaK-xABN increases gradually between 460nm and 700nm with increasing ABN loading, which results from the improvement of grafted benzene rings and delocalization. The optical absorption of the sample is enhanced, indicating stable electrons and holes in the excited state, indicating that photochemistry may be utilized even at wavelengths greater than 500 nm. The color of the sample gradually deepens from pale yellow of DCN to bright yellow of DCN-NaK, to brown of DCN-NaK-90ABN. The visible light absorption range of the photocatalytic composite material prepared by the invention is gradually widened, which is greatly beneficial to the improvement of the photocatalytic hydrogen production performance of the material.
Test example 2:
photocatalytic hydrogen production rate experiments:
the specific experimental conditions and methods are as follows: labsora-6A photocatalytic on-line analysis System, available from Beijing Porphy technologies Co.
Wherein, specific reaction solution: 50mg of the photocatalytic composite material was added to 100mL of an aqueous solution containing 10mL of the sacrificial agent triethanolamine, and 3wt% of Pt was used as a cocatalyst, light source PLS-SXE 300/300UV, light intensity: 100mW/cm 2 ，λ>420nm。
The photocatalytic hydrogen production rates of the photocatalytic composite materials obtained in examples 1 to 3 and comparative examples 1 to 3 were measured by the above experimental conditions and methods, and the results are shown in fig. 3, wherein (a) in fig. 3 is a hydrogen production rate test chart at a wavelength of about 420nm, and (b) in fig. 3 is a hydrogen production rate test chart at wavelengths of 500nm, 550nm, and 600 nm.
As can be seen from FIG. 3, almost all of the g-C grafted with Aminobenzonitrile (ABN) under NaCl-KCl molten salt compared with the original sample DCN (material prepared in comparative example) 3 N 4 Composite material: DCN-NaK-xABN has obvious improvement of photocatalytic hydrogen production performance.
Specifically, the sample DCN prepared in comparative example 1 had a hydrogen production rate of 30. Mu. Mol h -1 g -1 Is significantly lower than that of sample example 2210 mu mol h of DCN-NaK-90ABN obtained -1 g -1 ；
The hydrogen production rate of DCN-NaK-80ABN prepared in example 1 was 177. Mu. Mol h -1 g -1 Lower than the DCN-NaK-90ABN prepared in example 2;
the hydrogen production rate of DCN-NaK-100ABN prepared in example 3 was 154. Mu. Mol h -1 g -1 Lower than the DCN-NaK-90ABN prepared in example 2;
more importantly, DCN-NaK-xABN still has good performance of hydrogen evolution in long wavelength of 500nm and 550 nm. In particular, the sample DCN prepared by the comparative example has hydrogen production rate of only 4 mu mol h at 500nm -1 g -1 Significantly lower than the hydrogen production rate of DCN-NaK-90ABN prepared in sample example 2 at 500nm, 44 mu mol h -1 g -1 The method comprises the steps of carrying out a first treatment on the surface of the And the hydrogen production rate of DCN-NaK-90ABN at 550nm still has 25 mu mol h -1 g -1 At this time, DCN produced no hydrogen at 550 nm.
The hydrogen production rate of DCN-90ABN prepared in comparative example 2 at 500nm is 5. Mu. Mol h -1 g -1 Far lower than the DCN-NaK-90ABN of example 2, the hydrogen production rate of DCN-NaK prepared in comparative example 5 at 500nm is 10. Mu. Mol h -1 g -1 Lower than the DCN-NaK-90ABN of example 2. The DCN of the sample prepared in comparative example 1, the DCN-90ABN prepared in comparative example 2 and the DCN-NaK prepared in comparative example 3 are all higher than the DCN prepared in comparative example.
In summary, the sample DCN-NaK-90ABN obtained by grafting a proper amount of Aminobenzonitrile (ABN) with a CN network structure under the assistance of NaCl-KCl molten salt has the highest photocatalytic hydrogen production performance, namely the photocatalytic hydrogen production rate of the photocatalytic composite material prepared in the embodiment 2 is optimal. With further increase of the amount of Aminobenzonitrile (ABN), the hydrogen production performance of the prepared photocatalytic composite material sample gradually decreases, which may be caused by excessive doping, and damage some characteristics of the semiconductor to affect the photocatalytic performance of the material.
Test example 3:
photocatalytic degradation of BPA experiments:
the specific experimental conditions and methods are as follows: the filtrate was analyzed by High Performance Liquid Chromatography (HPLC) and fluorescence detector (Waters e2695 Alliance, USA) at 245 nm.
Wherein, specific reaction solution: 50mg of the photocatalytic composite material was dispersed in 100mL of an aqueous solution of BPA (bisphenol A) (20 mg L -1 ) And continuously stirring for 60min to perform a dark pre-adsorption experiment. The system was then exposed to irradiation with a 300W xenon lamp (PLS-SXE 300D, beijing Perfectlight technologies ltd) equipped with a 420nm cut-off filter. 3mL of the reaction solution (filtrate) was periodically extracted with a 0.45 μm membrane.
The photocatalytic degradation curves of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 were tested by the above experimental conditions and methods, and the results are shown in fig. 4, wherein (a) in fig. 4 is a graph of degradation efficiency of the material for bisphenol a under irradiation of visible light, including adsorption process and degradation of the material after addition of visible light, (b) in fig. 4 is a graph of relationship between irradiation time and concentration at t/initial concentration after addition of different capturing agents to example 2, which part of degradation in the material is mainly responsible by addition of different capturing agents to example 2, for example, N2 was added for removal of superoxide radicals in the material, and (c) in fig. 4 is a graph of kinetic data-dependent reaction rate constant (k) of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 for photodegradation according to pseudo first-order correlation fit, and (d) in fig. 4 is a graph of relationship between irradiation time and initial concentration at 500 nm/concentration of the samples obtained in examples 1 to 3. D-f in FIG. 4 is a graph showing the relationship between the irradiation time at 550nm and the t-time concentration/initial concentration of the samples obtained in examples 1-3 and comparative examples 1-3, and the kinetic-related reaction constant K after the addition of the capturing agent, and d-f in FIG. 4 is a graph showing the relationship between the kinetic-related reaction constant K after the addition of the capturing agent of the samples obtained in examples 1-3 and comparative examples 1-3.
As can be seen from fig. 4, all samples had weak adsorption (< 4.5%) of BPA, indicating that adsorption did not play a critical role in photocatalysis. However, under the irradiation of visible light, compared with DCN, the removal efficiency of DCN-NaK-xABN on BPA is obviously improved. The photodegradation efficiencies of DCN-NaK-80ABN, DCN-NaK-90ABN and DCN-NaK-100ABN are 88.3%, 100% and 88.7%, respectively, which are far higher than those of DCN (only 5.6%), DCN-NaK (43.8%) and DCN-90ABN (5.1%), indicating that the formation of defects and enhanced delocalization contained in DCN-NaK-xABN can effectively improve the photocatalytic activity thereof. The significant increase in photodegradation efficiency stems from the inclusion of formation defects in the DCN-NaK-xABN and the enhanced delocalization and adsorption capacity increase. And a sample DCN-NaK-90ABN obtained by grafting a proper amount of Aminobenzonitrile (ABN) with a CN network structure has the highest photocatalytic degradation efficiency. In addition, the addition of Aminobenzonitrile (ABN) enhances the delocalization and significantly improves the optical absorption in the long wavelength range, allowing for effective photodegradation of BPA at 500nm and 550 nm. It is evident that the kinetics-dependent reaction rate constant (k) for photodegradation of DCN-NaK-90ABN at 500nm is 95, much higher than DCN (k=3), DCN-NaK (k=10), DCN-90ABN (k=2); the kinetics-dependent reaction rate constant (k) for photodegradation of DCN-NaK-90ABN at 550nm is 62, still much higher than DCN (k=2), DCN-NaK (k=9), DCN-90ABN (k=0.4).
In summary, with the assistance of NaCl-KCl molten salt, a proper amount of Aminobenzonitrile (ABN) is grafted with a CN network structure to obtain a sample DCN-NaK-90ABN, which has the highest photocatalytic degradation BPA performance, namely the photocatalytic degradation BPA performance of the photocatalytic composite material prepared in the embodiment 2 is optimal. With further increase of the dosage of the Aminobenzonitrile (ABN), the degradation BPA performance of the prepared photocatalytic composite material sample gradually decreases, which further indicates that the effective doping of the Aminobenzonitrile (ABN) monomer can lead the sample DCN-NaK-90ABN obtained by the CN network structure to have the highest photocatalytic degradation efficiency.
Test example 4:
photoluminescence spectrum test:
wherein, the specific experimental conditions are as follows: FLS-980 fluorescence spectrometer was used at room temperature.
Photoluminescence spectra of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 are shown in fig. 5.
As can be seen from FIG. 5, the PL intensity is significantly reduced relative to DCN when NaCl-KCl molten salt or ABN is used, due to the inclusion of production defects (e.g. -C.ident.N and nitrogen defects) in DCN-NaK and the enhanced delocalization in DCN-90ABN. A significant decay in peak intensity indicates a reduction in carrier recombination. In addition, the red shifts of DCN-NaK and DCN-NaK-90ABN are respectively from 462nm to 498nm and 533nm, which highlights the improvement of the stability of photo-generated electrons and holes. With the addition of the Aminobenzonitrile (ABN), the composite material obtained after grafting the Aminobenzonitrile (ABN) on the CN network structure can effectively promote the separation of the photogenerated electrons and the photogenerated holes of the sample. This is due to the rapid migration of photogenerated electrons with enhanced pi-electron delocalization as the organic monomer Aminobenzonitrile (ABN) grafts to the CN network structure. Thereby inhibiting the rapid recombination of photo-generated holes and photo-generated electrons and promoting the photocatalytic degradation and hydrogen production activity of the catalyst.
Test example 5:
photocatalytic stability experiments:
the photocatalytic stability test of the sample DCN-NaK-90ABN obtained in example 2 is shown in FIG. 6.
As can be seen from fig. 6, after testing for 5 cycles (evacuating and discharging generated hydrogen every 4 hours, calculating one cycle) with continuous illumination for 20 hours, the hydrogen generating activity of the sample DCN-NaK-90ABN is basically not attenuated, which proves that the catalyst has good stability and good application prospect in practical application.
Test example 6:
nuclear magnetic resonance spectroscopy experiments:
nuclear magnetic resonance spectra 7 of the samples DCN-NaK and DCN-NaK-90ABN obtained in example 2 are shown.
As can be seen from FIG. 7, two typical characteristic peaks can be detected at 162.8 and 156.2ppm for DCN-NaK, corresponding to the carbon atoms of melem (CN 3, 1) and CN2 (NHx) (2) in the heptazine units, respectively. The chemical shift of DCN-NaK-90ABN is slightly shifted to the high field (fig. 7, inset), which means improved electron delocalization. The peaks of DCN-NaK and DCN-NaK-xABN were at 168.0 and 111.0ppm, respectively, which can be attributed to the-C.ident.N structure formed and the adjacent carbon atoms. Based on these characterization results, the aromatic ring structure can be grafted into the CN framework by adding ABN. The use of eutectic NaCl-KCl salts leads to nitrogen defects and-C.ident.N. In addition, aromatic rings in C.ident.N and Aminobenzonitrile (ABN) can enhance pi electron delocalization, thereby being beneficial to enhancing light absorption and fast migration of photo-generated electrons and promoting the photocatalytic hydrogen production activity of the catalyst.
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in the relevant art are intended to be included in the scope of the present invention.
Claims (10)
1. A photocatalytic composite material, characterized by: the structural formula of the photocatalytic composite material is shown as formula I:
wherein R is 1 And R is 2 Independently selected from structures of formula II or formula III:
wherein R is 3 、R 4 And R is 5 Independently selected from amino, alkyl substituted amino, hydroxy substituted amino or halogen substituted amino;
wherein R is 7 、R 8 And R is 10 Independently selected from imino, alkyl substituted imino, hydroxy substituted imino, or halo substituted imino; r is R 6 、R 9 And R is 11 Independently selected from amino, alkyl substituted amino, hydroxy substituted amino or halogen substituted amino;
and R is 3 、R 6 、R 9 And R is 11 At least one of which is selected from-NH-C.ident.N or X;
wherein X comprises the following structure:
wherein M is a metal ion.
2. The photocatalytic composite material according to claim 1, characterized in that: the R is 1 The structural formula of (2) is shown as formula II; r is R 2 The structural formula of (2) is shown as a formula III; r is R 6 The structural formula of (C) is shown as X.
3. A method of preparing the photocatalytic composite material according to claim 1 or 2, characterized in that: the method comprises the following steps:
s1, mixing a compound containing a carbon nitride structure with aminobenzonitrile, and calcining to obtain an intermediate product;
s2, mixing the intermediate product with molten salt containing metal cations under protective atmosphere, and calcining to obtain the photocatalytic composite material.
4. A method according to claim 3, characterized in that: the mass ratio of the compound containing the carbon nitride structure to the aminobenzonitrile is 100-400:4-5.
5. A method according to claim 3, characterized in that: the mass ratio of the aminobenzonitrile to the molten salt containing metal cations is 4-5:4-12.
6. A method according to claim 3, characterized in that: the carbon nitride structure-containing compound includes at least one of dicyandiamide, melamine, and urea.
7. A method according to claim 3, characterized in that: the metal cation-containing molten salt includes at least one of a melt of an alkali metal and a melt of an alkaline earth metal halide.
8. The method according to claim 7, wherein: the molten salt containing metal cations comprises NaCl-KCl molten salt, wherein the mass ratio of NaCl to KCl is 4.28-6.28:1.72-5.72.
9. A method according to claim 3, characterized in that: in the step S1, the calcining temperature is 400-500 ℃, and in the step S2, the calcining temperature is 600-700 ℃.
10. Use of the photocatalytic composite material according to claim 1 or 2 in a reaction for producing hydrogen by photodecomposition of water under bisphenol a degradation or visible light.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227529A (en) * | 2019-05-08 | 2019-09-13 | 五邑大学 | One carbon-based photochemical catalyst of type graphitic nitralloy and its preparation method and application |
| CN111298824A (en) * | 2020-03-20 | 2020-06-19 | 五邑大学 | Graphite-like carbon nitride-based photocatalytic composite material and 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 |
| CN115155657A (en) * | 2022-07-28 | 2022-10-11 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN115155643A (en) * | 2022-07-28 | 2022-10-11 | 五邑大学 | Photocatalytic composite material and preparation method and application thereof |
| CN117065797A (en) * | 2023-08-21 | 2023-11-17 | 兰州交通大学 | Preparation method and application of benzene ring grafted phosphorus doped carbon nitride hollow nanotube photocatalyst |
| CN117225453A (en) * | 2023-08-28 | 2023-12-15 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN117225444A (en) * | 2023-08-28 | 2023-12-15 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN117380265A (en) * | 2023-09-22 | 2024-01-12 | 五邑大学 | Photocatalytic material based on nitrogen carbide network structure and preparation method and application thereof |
-
2023
- 2023-04-07 CN CN202310368785.7A patent/CN116496300A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227529A (en) * | 2019-05-08 | 2019-09-13 | 五邑大学 | One carbon-based photochemical catalyst of type graphitic nitralloy and its preparation method and application |
| CN111298824A (en) * | 2020-03-20 | 2020-06-19 | 五邑大学 | Graphite-like carbon nitride-based photocatalytic composite material and 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 |
| CN115155657A (en) * | 2022-07-28 | 2022-10-11 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN115155643A (en) * | 2022-07-28 | 2022-10-11 | 五邑大学 | Photocatalytic composite material and preparation method and application thereof |
| CN117065797A (en) * | 2023-08-21 | 2023-11-17 | 兰州交通大学 | Preparation method and application of benzene ring grafted phosphorus doped carbon nitride hollow nanotube photocatalyst |
| CN117225453A (en) * | 2023-08-28 | 2023-12-15 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN117225444A (en) * | 2023-08-28 | 2023-12-15 | 五邑大学 | Photocatalytic material and preparation method and application thereof |
| CN117380265A (en) * | 2023-09-22 | 2024-01-12 | 五邑大学 | Photocatalytic material based on nitrogen carbide network structure and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ARNE THOMAS ET AL.: "Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts", 《JOURNAL OF MATERIALS CHEMISTRY》, 10 July 2008 (2008-07-10), pages 4893 - 4908 * |
| CHENGQUN XU ET AL.: "Molten-salt assisted synthesis of polymeric carbon nitride-based photocatalyst for enhanced photocatalytic activity under green light irradiation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, 2 May 2023 (2023-05-02), pages 1 - 11 * |
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