CN113578394A - Inorganic/organic double-heterojunction visible light catalytic composite material and preparation method and application thereof - Google Patents
Inorganic/organic double-heterojunction visible light catalytic composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113578394A CN113578394A CN202111053030.5A CN202111053030A CN113578394A CN 113578394 A CN113578394 A CN 113578394A CN 202111053030 A CN202111053030 A CN 202111053030A CN 113578394 A CN113578394 A CN 113578394A
- Authority
- CN
- China
- Prior art keywords
- bob
- ped
- b4ob
- heterojunction
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 72
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000001338 self-assembly Methods 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 39
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 13
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000000593 degrading effect Effects 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 9
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 9
- 229930195725 Mannitol Natural products 0.000 claims description 9
- 235000004279 alanine Nutrition 0.000 claims description 9
- 239000000594 mannitol Substances 0.000 claims description 9
- 235000010355 mannitol Nutrition 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 16
- -1 perylene imide Chemical class 0.000 abstract description 11
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract description 2
- 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 55
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 51
- 239000000843 powder Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 238000010791 quenching Methods 0.000 description 6
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000032900 absorption of visible light Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
- TWDJZUXQDJFLNE-UHFFFAOYSA-N O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] Chemical compound O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] TWDJZUXQDJFLNE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002402 SrFe12O19 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses an inorganic/organic double-heterojunction visible-light-catalyzed composite material and a preparation method and application thereof, wherein the material takes BOB/B4OB (bismuth oxybromide heterojunction) as a main material and is loaded with a three-phase heterojunction structure of PED (perylene imide) on the BOB/B4OB through acidic self-assembly; the chemical formula of the visible light catalytic composite material is PED @ BOB/B4 OB. The BOB/B4OB inorganic two-type heterojunction material is formed by a one-pot hydrothermal method, has matched band gaps and a tight connection structure, and realizes the efficient separation of photon-generated carriers; and the double heterojunction is formed with PED, the charge separation efficiency is further improved, and the double heterojunction has the characteristic of light absorption response in a full spectrum range. The invention has the advantages of high catalytic activity, good stability and the like.
Description
Technical Field
The invention belongs to the field of environment functional materials, relates to a photocatalytic material, and particularly relates to an inorganic/organic double-heterojunction visible-light-catalyzed composite material as well as a preparation method and application thereof.
Background
The visible light catalytic oxidation technology has attracted extensive attention because of its low energy consumption and no secondary pollution. However, the current photocatalytic material has a problem of low photocatalytic efficiency under visible light, mainly because (1) the photo-generated carrier has a high recombination rate and a low utilization rate of photo-generated electrons; (2) the light absorption in the visible light range is small, and the excitation of a semiconductor cannot be realized by most of the energy of the visible light wavelength, so that the application in the field of photocatalysis is limited. In order to solve the above problems, the photocatalytic activity is generally improved by forming a semiconductor heterojunction or supporting the semiconductor heterojunction on the surface of the semiconductor. Applications for visible light catalytic materials have been published as follows:
the invention application with the application number of 202010085795.6 discloses an iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst and a preparation method thereof, and the method comprises the steps of firstly taking mesoporous silica as a carrier, and respectively loading iodine, bismuth oxybromide and titanium dioxide in a certain proportion on SBA-15 to prepare the iodine-doped titanium dioxide-bismuth oxybromide composite photocatalyst. The introduction of iodine can keep the composite material with higher adsorption capacity, ordered pore channel structure which is not easy to collapse, and can effectively prevent TiO2Agglomeration during heat treatment, but the efficiency of visible light utilization is low due to excitation of both host materials at near uv.
The invention application with the application number of 202011573177.2 discloses a binary composite nano catalyst and a preparation method and application thereof, the method comprises the steps of synthesizing BiOBr and CQDs by a hydrothermal method in advance, heating and stirring the two materials in absolute ethyl alcohol until the absolute ethyl alcohol is completely volatilized, then placing the materials in a muffle furnace for calcination, obtaining a material which tightly loads CQDs nanocrystals on the surface of BiOBr microspheres, and introducing oxygen vacancies in the BiOBr. However, the larger nanospheres result in the extension of the migration distance of the photon-generated carriers, the separation efficiency of the photon-generated carriers cannot be sufficiently improved, and the calcination mode may cause the polymerization of the material.
The invention application with the application number of 201910030245.1 discloses a preparation method of a bismuth sulfide-bismuth oxybromide magnetic ternary composite visible-light-driven photocatalyst, and the invention adopts a one-step hydrothermal method to prepareMagnetically complexed Bi2S3/BiOBr/SrFe12O19The visible light catalyst has the advantages that the disordered component can cause the disordered crystal structure of the whole material to form more photon-generated carrier recombination sites, and the invalid separation and recombination of photon-generated carriers can be caused because the migration direction of the photon-generated carriers is not clear.
Therefore, there is a need to develop a new visible light catalytic material for accelerating the electron-hole separation rate and improving the absorption and utilization performance of visible light.
Disclosure of Invention
Aiming at the defects of the photocatalytic material and the defects of the material in the prior art, BOB is used as a base material, the pH value in a reaction precursor solution is adjusted to generate B4OB with the conduction band valence band position higher than that of the BOB, the energy level matching between two traditional inorganic semiconductors is realized, the heterojunction material with the BOB/B4OB is spontaneously formed, the energy band is continuously bent by utilizing the tight chemical bond connection, and the separation of photon-generated carriers is promoted; and then self-assembled PED nano-fibers are formed on the surface of the BOB/B4OB through acid-base condition regulation, so that double heterojunctions are formed, the separation efficiency of photon-generated carriers is further improved, the visible light response range of the material is expanded due to the introduction of the PED, the degradation capability of the photocatalyst on organic pollutants is greatly improved, and a new idea is provided for designing and constructing visible light catalytic materials.
In order to achieve the above object, the present invention provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material having the following characteristics: BOB/B4OB is used as a main material, and a double heterojunction structure of PED is loaded on the BOB/B4OB through acidic self-assembly; the chemical formula of the visible light catalytic composite material is PED @ BOB/B4 OB. Wherein BOB means BiOBr, B4OB means Bi4O5Br2BOB/B4OB is a bismuth oxybromide heterojunction; PED refers to Perylene imide (Perylene diimide).
The invention also provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: the method comprises the following steps:
dissolving bismuth nitrate pentahydrate and sodium bromide with mannitol, uniformly stirring, adjusting the pH to 7-8 with sodium hydroxide, and curing to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating the reaction kettle for hydrothermal reaction, naturally cooling the reaction kettle after the hydrothermal reaction, taking out a sample for centrifugation, alternately cleaning the sample by deionized water and ethanol, and drying the sample to obtain a light yellow powder simultaneously with BiOBr and Bi4O5Br2Two phase BOB/B4OB material;
step three, introducing N into perylene-3, 4,9, 10-tetracarboxylic dianhydride, imidazole and alanine2Heating the three-necked flask for reaction, naturally cooling after the reaction, uniformly dispersing the mixture by using hydrochloric acid and ethanol, washing the mixture by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
dissolving the PED supermolecule precursor in water, adding triethylamine, and fully stirring to obtain a dark red, clear and transparent PED monomer solution;
and step five, adding the BOB/B4OB material into the PED monomer solution, uniformly stirring, heating in a water bath, adding acetic acid, continuously stirring to obtain flocculent precipitate, centrifuging, washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: wherein, in the first step, the molar ratio of the bismuth nitrate pentahydrate to the sodium bromide is 1: 1-2; the curing time is 0.5-4 h.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: wherein, in the second step, the reaction temperature of the closed hydrothermal reaction is 160-220 ℃, and the reaction time is 3-8 h.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: in the third step, the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the imidazole to the alanine is 1: 8-10: 70-80; the reaction temperature is 110-140 ℃, and the reaction time is 4-6 h.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: in the third step, 200-300 ml of 2M hydrochloric acid and 80-100 ml of absolute ethyl alcohol are used for every 1g of the product corresponding to the perylene-3, 4,9, 10-tetracarboxylic dianhydride.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: in the fourth step, the concentration of the PED supramolecular precursor in the PED supramolecular precursor aqueous solution is 200-400 mg/L; the molar ratio of triethylamine to PED supramolecular precursor is (6-10) to 1.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: in the fifth step, the mass ratio of the BOB/B4OB material to the PED supramolecular precursor in the PED monomer solution is 10: 1-2; the temperature of the water bath heating is 60 ℃, and the time is 1 h.
Further, the invention provides a preparation method of the inorganic/organic double-heterojunction visible light catalytic composite material, which has the following characteristics: in the fifth step, the molar ratio of acetic acid to triethylamine added into the PED monomer solution is (20-30) to 1; after adding acetic acid, stirring was continued for 1 h.
The invention also provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material used for degrading organic pollutants in a liquid environment. Wherein the organic pollutant is bisphenol A and the like.
The invention provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material and a preparation method and application thereof, aiming at the problems that a photogenerated carrier of the existing photocatalytic material is easy to compound and has low visible-light absorption utilization rate, B4OB under a bismuth-rich strategy is obtained by taking BOB as a main material through pH regulation, and the heterojunction material of BOB/B4OB is obtained through a hydrothermal method, wherein the valence band of a conduction band is higher than the energy band position of the BOB. Separation of photogenerated carriers is facilitated due to the continuous bending of the energy bands. And then, loading PED on BOB/B4OB through acidic self-assembly to obtain the photocatalytic material PED @ BOB/B4 OB. Under the irradiation of visible light, photogenerated carriers are efficiently separated through a BOB/B4OB heterojunction, and photogenerated electrons and photogenerated holes are transferred to the BOB and the B4OB respectively through energy band analysis. The light absorption of the material is greatly improved by forming a heterojunction by PED and BOB/B4 OB.
The invention has the beneficial effects that: the invention discloses an inorganic/organic double-heterojunction visible light catalytic material and a preparation method and application thereof.A BOB/B4OB inorganic type-II heterojunction material is formed by a one-pot hydrothermal method, has matched band gaps and a tight connection structure, and realizes the high-efficiency separation of photon-generated carriers; and the double heterojunction is formed with PED, the charge separation efficiency is further improved, and the double heterojunction has the characteristic of wide spectral response range. The method has the following beneficial effects:
firstly, the prepared photocatalytic material has good photocatalytic activity for degrading BPA.
And secondly, due to the construction of the inorganic/organic double heterojunction, the utilization efficiency of the photocatalytic material on visible light is obviously improved, and the separation efficiency of photon-generated carriers is improved.
Specifically, the main materials of the photocatalytic composite material are BiOBr (BOB) and Bi4O5Br2(B4OB), since B4OB under the bismuth-rich strategy has higher conduction and valence band positions than BOB, the directional transport of electrons from B4OB to BOB and holes from BOB to B4OB is promoted. The self-assembly of organic semiconductor material PED on BOB/B4OB heterojunction under acidic condition is realized by uniformly mixing the supramolecular precursor of organic material Perylene diimide (PED) and BOB/B4OB and regulating and controlling pH, and the self-assembly is loaded on the BOB/B4OB heterojunction in the form of nanofiber structure and forms an inorganic/organic double-heterojunction structure together with the combination of BOB/B4 OB. Due to the successful preparation of the double heterojunction and the excellent visible light absorption characteristic of the PED material, the material has extremely high photon-generated carrier separation efficiency and realizes visible light absorption in a wide spectral response range. The preparation method mainly comprises the steps of synthesizing the BOB/B4OB heterojunction material by a one-pot hydrothermal method, and realizing the purpose of havingSurface group modification of the organic supramolecular PED, and subsequent self-assembly of the PED on the surface of the BOB/B4OB through an acid-base regulation strategy. The invention has the advantages of high catalytic activity, good stability and the like.
Drawings
FIG. 1 is a transmission electron micrograph of PED @ BOB/B4OB from example 1;
FIG. 2 is an XRD spectrum of PED @ BOB/B4OB before and after the application of the experimental reaction in example 1;
FIG. 3 is an electron energy spectrum of PED @ BOB/B4OB in example 2;
FIG. 4 is a representation of the UV-Vis DRS of PED @ BOB/B4OB in example 3;
FIG. 5 is a PL profile of PED @ BOB/B4OB in example 4;
FIG. 6 is an electrochemical characterization of the PL profile of PED @ BOB/B4OB in example 5: I-T plot (A), EIS plot (B);
FIG. 7 is a graph showing the degradation effect of PED @ BOB/B4OB on bisphenol A at an initial concentration of 10ppm in examples 1-7;
FIG. 8 is a plot of the radical quenching experiment (A) and EPR spectrum (B) of PED @ BOB/B4OB in example 6;
FIG. 9 is a graph of batch experimental degradation effects of PED @ BOB/B4OB in example 7.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 2.5mmol of sodium bromide (the molar ratio is 1:1.25) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M sodium hydroxide, and curing for 1h to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at 160 ℃ for 3 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-neck flask to react at 110 ℃ for 4h, naturally cooling after the reaction, uniformly dispersing the mixture by using 200ml of 2M hydrochloric acid and 100ml of absolute ethyl alcohol, washing the mixture by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 20mg of dark red powder C in 50ml of water, adding 40 mu L of triethylamine, and fully stirring to obtain dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The above products were characterized by TEM images and XRD and the results are shown in fig. 1 and 2. As can be seen from FIG. 1, the prepared BOB/B4OB material is tightly combined into a two-dimensional lamellar structure, the migration distance of photogenerated carriers is reduced, and PED is loaded on the surface of BOB/B4OB in a strip-shaped nanofiber structure. Successful synthesis of the three materials is also demonstrated by analysis of the characteristic peaks in the XRD pattern of figure 2.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
XRD patterns of the materials before and after the reaction are characterized, and the result is shown in figure 2. As can be seen from FIG. 2, the crystal structure of the material before and after the reaction is not obviously changed, thus proving the good stability of the material.
Example 2
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 2mmol of sodium bromide (the molar ratio is 1:1) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M of sodium hydroxide, and curing for 1h to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at the reaction temperature of 180 ℃ for 4 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-necked flask for reaction at 120 ℃ for 5 hours, naturally cooling the reaction product after the reaction, uniformly dispersing the product by using 300ml of 2M hydrochloric acid and 100ml of absolute ethyl alcohol, washing the product by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 20mg of dark red powder C in 50ml of water, adding 40 mu L of triethylamine, and fully stirring to obtain dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The results of XPS characterization of the product from each step are shown in FIG. 3, and it can be seen from FIG. 3A that the characteristic peaks of BOB/B4OB for Bi, O and Br and the characteristic peaks of PED for C appear in XPS, indicating the successful synthesis of the material. As shown in FIG. 3B, Bi4f5/2The electron binding energies were 164.73 and 163.49ev, respectively, representing BOB and B4O, respectivelyB, and thus further demonstrates the presence of two electronic structures in the BOB/B4OB material.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
Example 3
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 2mmol of sodium bromide (the molar ratio is 1:1) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M of sodium hydroxide, and curing for 2 hours to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at 160 ℃ for 5 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-neck flask to react at 110 ℃ for 4h, naturally cooling after the reaction, uniformly dispersing the mixture by using 300ml of 2M hydrochloric acid and 80ml of absolute ethyl alcohol, washing the mixture by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 20mg of dark red powder C in 50ml of water, adding 40 mu L of triethylamine, and fully stirring to obtain dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The product prepared in each step above was characterized by UV-DIS, and the results are shown in FIG. 4. As can be seen from FIG. 4, BOB as a near ultraviolet absorption semiconductor only cuts off the absorption of visible light to 479nm, and after BOB/B4OB is successfully synthesized, the absorption of visible light by the material is improved to a certain extent due to the change of B4OB conductance and valence band position under the bismuth-rich strategy. The absorption of visible light is greatly enhanced after binding to PED, with the cut-off edge for light absorption extending to 721 nm. Visible light absorption over a wide spectral response range is achieved.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
Example 4
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of bismuth nitrate pentahydrate and 4mmol of sodium bromide (the molar ratio is 1:2) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 7 by using 1M of sodium hydroxide, and curing for 2 hours to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at the reaction temperature of 200 ℃ for 4 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-necked flask for reaction at 140 ℃ for 4h, naturally cooling after the reaction, uniformly dispersing the mixture by using 200ml of 2M hydrochloric acid and 80ml of absolute ethyl alcohol, washing the mixture by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 10mg of dark red powder C in 50ml of water, adding 20 mu L of triethylamine, and fully stirring to obtain a dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
PL characterization was performed on the product prepared in each step above, and as a result, as shown in fig. 5, since the PL emission spectrum is due to recombination of photogenerated carriers, the PL spectrum can be used to evaluate the separation efficiency of the photogenerated carriers. As can be seen from FIG. 5, the successful preparation of PED @ BOB/B4OB greatly reduces the recombination efficiency of the photon-generated carriers, and proves the efficient separation efficiency of the photon-generated carriers in the PED @ BOB/B4OB inorganic/organic double heterojunction.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
Example 5
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 2mmol of sodium bromide (the molar ratio is 1:1) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M of sodium hydroxide, and curing for 1h to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at the reaction temperature of 220 ℃ for 8 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-necked flask for reaction at 120 ℃ for 4 hours, naturally cooling the reaction product after the reaction, uniformly dispersing the product by using 300ml of 2M hydrochloric acid and 100ml of absolute ethyl alcohol, washing the product by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 10mg of dark red powder C in 50ml of water, adding 20 mu L of triethylamine, and fully stirring to obtain a dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The electrochemical characterization of the product prepared in each step is performed, and the transient photocurrent response measurement and the electrochemical impedance spectrum test are respectively performed, and the result is shown in fig. 6. As can be seen from fig. 6A, the successful synthesis of the PED @ BOB/B4OB double heterojunction improves the photocurrent density, and promotes the separation efficiency of the photo-generated carriers of the catalytic material; as can be seen from FIG. 6B, the double heterojunction PED @ BOB/B4OB has the lowest charge transfer resistance, and further proves the efficient separation efficiency of the electron-hole pairs.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
Example 6
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 2mmol of sodium bromide (the molar ratio is 1:1) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M of sodium hydroxide, and curing for 1h to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at 160 ℃ for 3 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating the three-neck flask to react at 130 ℃ for 4h, naturally cooling after the reaction, uniformly dispersing the mixture by using 200ml of 2M hydrochloric acid and 100ml of absolute ethyl alcohol, washing the mixture by using ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 20mg of dark red powder C in 50ml of water, adding 40 mu L of triethylamine, and fully stirring to obtain dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
The reaction process was subjected to a radical quenching experiment using t-butanol to quench hydroxyl radicals, L-histidine to quench singlet oxygen, sodium oxalate to quench the void, and p-benzoquinone to quench the superoxide radical. And EPR characterization was performed by capturing free radicals with DMPO, demonstrating the presence of free radicals, the results are shown in FIG. 8. As can be seen from fig. 8, the superoxide radical, singlet oxygen and photo-generated hole play a major role in the degradation of bisphenol a, the hydroxyl radical is mainly generated by the reaction of the superoxide radical and hydroxyl radical in water, and has only a weak role in the degradation of bisphenol a, and the types of the main active radicals in the PED @ BOB/B4OB inorganic/organic double heterojunction are verified.
Example 7
The embodiment provides an inorganic/organic double-heterojunction visible-light-catalyzed composite material, which is a double-heterojunction structure that takes BOB/B4OB as a main material and supports PED on BOB/B4OB through acidic self-assembly; the chemical formula is PED @ BOB/B4 OB.
The preparation method of the visible light catalytic composite material comprises the following steps:
step one, dissolving 2mmol of pentahydrate bismuth nitrate and 3mmol of sodium bromide (the molar ratio is 1:1.5) in 60mL of 0.1M mannitol solution, uniformly stirring, adjusting the pH value to 8 by using 1M sodium hydroxide, and curing for 1h to obtain a BOB/B4OB precursor solution;
step two, pouring the BOB/B4OB precursor solution into a reaction kettle with a polytetrafluoroethylene inner container, sealing and heating for hydrothermal reaction at the reaction temperature of 220 ℃ for 4 hours, naturally cooling after the reaction, taking out a sample for centrifugation, alternately cleaning with deionized water and ethanol, and drying to obtain a light yellow powder BOB/B4OB material;
step three, 1.376g of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 18g of imidazole and 2.5g of alanine are added with N2Heating in a three-neck flask at 120 deg.C for 4 hr, naturally cooling, and reacting with 2Dispersing 200ml of M hydrochloric acid and 100ml of absolute ethyl alcohol uniformly, washing with ultrapure water, and performing suction filtration to obtain a dark red powder PED supramolecular precursor;
step four, dissolving 20mg of dark red powder C in 50ml of water, adding 40 mu L of triethylamine, and fully stirring to obtain dark red clear and transparent PED monomer solution;
step five, adding 100mg of BOB/B4OB material into PED monomer solution, uniformly stirring, heating in water bath at 60 ℃, and continuously stirring for 1 h; adding 5ml of 4M acetic acid stock solution, continuously stirring for 1h to obtain flocculent precipitate, and centrifugally washing and drying to obtain dark red solid powder PED @ BOB/B4 OB.
The visible light catalytic composite material PED @ BOB/B4OB is used for degrading bisphenol A in a liquid environment.
50mL of 10mg/L bisphenol A solution is prepared and placed in a light reaction device, 25mg of PED @ BOB/B4OB is added, pre-adsorption is carried out for 30min under a dark condition, a 350W xenon lamp is used for simulating sunlight, sampling is carried out every 15min to determine the bisphenol A concentration, and the degradation effect is shown in figure 7.
The recycling effect of visible light catalytic degradation of bisphenol A is shown in FIG. 9, and after three times of recycling, the removal rate of bisphenol A is maintained above 80%, which proves that the stability of the photocatalytic material is good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. An inorganic/organic double-heterojunction visible light catalytic composite material is characterized in that:
BOB/B4OB is used as a main material, and a double heterojunction structure of PED is loaded on the BOB/B4OB through acidic self-assembly; the chemical formula of the visible light catalytic composite material is PED @ BOB/B4 OB.
2. The method for preparing the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 1, wherein:
the method comprises the following steps:
dissolving bismuth nitrate pentahydrate and sodium bromide with mannitol, uniformly stirring, adjusting the pH value to 7-8, and curing to obtain a BOB/B4OB precursor solution;
step two, heating the BOB/B4OB precursor liquid in a sealed manner to carry out hydrothermal reaction, naturally cooling after the reaction, and centrifugally washing and drying to obtain a BOB/B4OB material;
step three, introducing N into perylene-3, 4,9, 10-tetracarboxylic dianhydride, imidazole and alanine2Heating and reacting in a container, naturally cooling after reaction, uniformly dispersing by using hydrochloric acid and ethanol, washing by using ultrapure water, and performing suction filtration to obtain a PED supramolecular precursor;
dissolving the PED supermolecule precursor in water, adding triethylamine, and fully stirring to obtain a PED monomer solution;
and step five, adding the BOB/B4OB material into the PED monomer solution, uniformly stirring, heating in a water bath, adding acetic acid, continuously stirring to obtain flocculent precipitate, centrifuging, washing and drying to obtain the PED @ BOB/B4 OB.
3. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
wherein, in the first step, the molar ratio of the bismuth nitrate pentahydrate to the sodium bromide is 1: 1-2;
the curing time is 0.5-4 h.
4. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
wherein, in the second step, the reaction temperature of the closed hydrothermal reaction is 160-220 ℃, and the reaction time is 3-8 h.
5. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
in the third step, the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the imidazole to the alanine is 1: 8-10: 70-80;
the reaction temperature is 110-140 ℃, and the reaction time is 4-6 h.
6. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
in the third step, 200-300 ml of 2M hydrochloric acid and 80-100 ml of absolute ethyl alcohol are used for every 1.376g of the product corresponding to the perylene-3, 4,9, 10-tetracarboxylic dianhydride.
7. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
in the fourth step, the concentration of the PED supramolecular precursor in the PED supramolecular precursor aqueous solution is 200-400 mg/L;
the molar ratio of triethylamine to PED supramolecular precursor is (6-10) to 1.
8. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
in the fifth step, the mass ratio of the BOB/B4OB material to the PED supramolecular precursor in the PED monomer solution is 10: 1-2;
the temperature of the water bath heating is 60 ℃, and the time is 1 h.
9. The preparation method of the inorganic/organic double-heterojunction visible-light-catalyzed composite material as claimed in claim 2, wherein:
in the fifth step, the molar ratio of acetic acid to triethylamine added into the PED monomer solution is (20-30) to 1;
after adding acetic acid, stirring was continued for 1 h.
10. Use of the inorganic/organic double heterojunction visible light-catalyzed composite material according to any one of claims 1 to 9 for degrading organic pollutants in a liquid environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111053030.5A CN113578394A (en) | 2021-09-09 | 2021-09-09 | Inorganic/organic double-heterojunction visible light catalytic composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111053030.5A CN113578394A (en) | 2021-09-09 | 2021-09-09 | Inorganic/organic double-heterojunction visible light catalytic composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113578394A true CN113578394A (en) | 2021-11-02 |
Family
ID=78241723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111053030.5A Pending CN113578394A (en) | 2021-09-09 | 2021-09-09 | Inorganic/organic double-heterojunction visible light catalytic composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113578394A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190445A (en) * | 2014-08-19 | 2014-12-10 | 河北科技大学 | Visible-light catalytic activity BiOBr-based heterojunction and preparation method thereof |
| CN108262050A (en) * | 2018-01-03 | 2018-07-10 | 东南大学 | A kind of two dimension composite visible light catalyst and preparation method and application |
| CN110538664A (en) * | 2019-09-23 | 2019-12-06 | 重庆科技学院 | preparation method of Bi4O5Br2/BiOBr composite photocatalyst for oilfield wastewater treatment |
| CN110841711A (en) * | 2019-11-19 | 2020-02-28 | 南京师范大学 | Supermolecular heterojunction organic photocatalyst and preparation method and application method thereof |
-
2021
- 2021-09-09 CN CN202111053030.5A patent/CN113578394A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190445A (en) * | 2014-08-19 | 2014-12-10 | 河北科技大学 | Visible-light catalytic activity BiOBr-based heterojunction and preparation method thereof |
| CN108262050A (en) * | 2018-01-03 | 2018-07-10 | 东南大学 | A kind of two dimension composite visible light catalyst and preparation method and application |
| CN110538664A (en) * | 2019-09-23 | 2019-12-06 | 重庆科技学院 | preparation method of Bi4O5Br2/BiOBr composite photocatalyst for oilfield wastewater treatment |
| CN110841711A (en) * | 2019-11-19 | 2020-02-28 | 南京师范大学 | Supermolecular heterojunction organic photocatalyst and preparation method and application method thereof |
Non-Patent Citations (2)
| Title |
|---|
| AUTTAPHON CHACHVALVUTIKUL ET AL.: "Double Z-scheme FeVO4/Bi4O5Br2/BiOBr ternary heterojunction photocatalyst for simultaneous photocatalytic removal of hexavalent chromium and rhodamine B", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| QIUYI JI ET AL.: "Enhancing the performance of pollution degradation through secondary self-assembled composite supramolecular heterojunction photocatalyst BiOCl/PDI under visible light irradiation", 《CHEMOSPHERE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111001439B (en) | Perylene bisimide and composite photocatalytic material thereof, preparation method and application thereof in removing organic pollutants in water body | |
| CN106732708A (en) | Graphite phase carbon nitride nanometer sheet load individual layer Bismuth tungstate nano-sheet heterojunction material and its preparation method and application | |
| CN107876079B (en) | Preparation method and application of sulfur-doped zinc oxide quantum dot modified porous graphite phase nitrogen carbide composite material | |
| CN108855131B (en) | Preparation and application of silver-nickel bimetal doped titanium dioxide nano composite material | |
| CN111036272B (en) | C3N4/LaVO4Composite photocatalyst and preparation method thereof | |
| CN104689834A (en) | CdS-loaded Bi2WO6/CdS nano composite material as well as preparation method and application thereof | |
| CN111450871A (en) | Mn-doped g-C3N4Loaded porous ZnCo2O4The photocatalytic material and the preparation method thereof | |
| CN112007679B (en) | Co/V bimetal doped g-C3N4Photocatalyst and preparation method and application thereof | |
| CN111151285A (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| CN113457663A (en) | 3D nano flower-shaped Zn3(VO4)2Preparation method and application thereof | |
| CN112774718A (en) | Cuprous oxide/tubular graphite-like phase carbon nitride composite catalyst and preparation method and application thereof | |
| CN111054442B (en) | Preparation method of titanium dioxide-based nano composite photocatalyst for rapidly removing phenolic organic pollutants in water | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| Jing et al. | Enhanced photocatalytic hydrogen production under visible light of an organic-inorganic hybrid material based on enzo [1, 2-b: 4, 5-b'] dithiophene polymer and TiO2 | |
| CN110152701B (en) | Bi2O2CO3/Bi2WO6:Yb3+、Er3+Photocatalyst and preparation method and application thereof | |
| Zhang et al. | Solvent-exfoliated DA π-polymer@ ZnS heterojunction for efficient photocatalytic hydrogen evolution | |
| CN114733543A (en) | Boron-modified carbon nitride material and preparation method and application thereof | |
| CN113101980A (en) | TiO with visible light catalytic activity2Preparation method and application of/UiO-66 composite material | |
| CN112642456B (en) | Preparation method of composite photocatalyst | |
| CN107899594B (en) | Carbon-point-modified copper hydroxyphosphate photocatalytic material and preparation method thereof | |
| CN113578306A (en) | Preparation method of 2D/1D heterojunction photocatalyst and application thereof in hydrogen production | |
| CN106000370A (en) | Preparation method of photoinduced Ti<3+> self-doped TiO2 photocatalyst | |
| CN113477278A (en) | Pyridine quaternary ammonium salt and inorganic semiconductor hybrid system photocatalytic reduction CO2Applications of | |
| CN110227544B (en) | Honeycomb structured porphyrin COP and g-C3N4Synthesis of composite material and application of composite material in aspect of photocatalytic degradation of dye | |
| CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211102 |