CN113413921A - ZIF-8 type composite photocatalyst and preparation method thereof - Google Patents
ZIF-8 type composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 135
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002028 Biomass Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 91
- 239000010949 copper Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 20
- 150000001879 copper Chemical class 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 15
- 235000009496 Juglans regia Nutrition 0.000 claims description 14
- 235000020234 walnut Nutrition 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 235000017048 Garcinia mangostana Nutrition 0.000 claims description 13
- 240000006053 Garcinia mangostana Species 0.000 claims description 13
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- 241001070941 Castanea Species 0.000 claims description 8
- 235000014036 Castanea Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- -1 copper salt Chemical class 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- QEOWFDYSNYCPRK-UHFFFAOYSA-N OCC[Na] Chemical compound OCC[Na] QEOWFDYSNYCPRK-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 29
- 238000005303 weighing Methods 0.000 description 15
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 13
- 241000758789 Juglans Species 0.000 description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 13
- 239000002699 waste material Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 8
- 238000010009 beating Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229940112669 cuprous oxide Drugs 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000502 dialysis Methods 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 238000011403 purification operation Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000011206 ternary composite Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a ZIF-8 type composite photocatalyst and a preparation method thereof, belonging to the technical field of material science. The preparation method comprises the steps of using a biomass material as a raw material, firstly preparing biomass N-CQD by a hydrothermal method, then preparing the obtained biomass N-CQD and a metal organic framework material ZIF-8 into N-CQD/ZIF-8 by an in-situ synthesis method, and finally preparing Cu by a reduction precipitation method2O is introduced into N-CQD/ZIF-8 to prepare the ZIF-8 type composite photocatalyst. The ZIF-8 type composite photocatalyst prepared by the preparation method effectively improves the stability of the photocatalytic performance of the existing ZIF-8 type composite photocatalyst.
Description
Technical Field
The invention belongs to the technical field of material science, and relates to a ZIF-8 type composite photocatalyst and a preparation method thereof.
Background
Hexavalent chromium (Cr (VI)) generated in industrial wastewater of leather industry, textile production, printing and dyeing and the like is mainly chromate (-CrO)4) And dichromate (-Cr)2O7) In the form, it has a "triple effect", is carcinogenic when inhaled by the human body, is difficult to biodegrade and causes serious environmental pollution.
The technology for semiconductor photocatalytic reduction of Cr (VI) under the irradiation of visible light not only has the advantages of environmental protection, low energy consumption, high reaction efficiency, difficult generation of secondary pollution and the like, but also has obvious advantages in the degradation aspect of other organic pollutants. Therefore, the semiconductor photocatalytic reduction technology of Cr (VI) is widely considered as a promising treatment method of heavy metal chromium ions.
Among many catalysts, metal organic framework Materials (MOFs) are porous materials formed by self-assembly of metal ions and organic ligands, and are widely applied to the field of photocatalysis due to high specific surface area, tailorable structure, abundant catalytic active sites and the like, but most of MOFs still have the problems of poor stability, rapid recombination of photo-generated electron-hole pairs and the like.
Nitrogen-doped carbon quantum dots (N-CQD) serving as a novel fluorescent carbon nano material have the excellent performances of environmental protection, easiness in modification, low preparation cost and the like, and have the unique advantage of high photoproduction electron transfer rate, and the amino doping can greatly improve the utilization efficiency of visible light, so that the N-CQD is used for improving the photocatalytic performance of MOFs, but researches show that the stability of the N-CQD/ZIF-8 still needs to be improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the ZIF-8 type composite photocatalyst and the preparation method thereof, and the stability of the photocatalytic performance of the ZIF-8 type composite photocatalyst is improved.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a ZIF-8 type composite photocatalyst, which comprises the steps of utilizing a biomass material as a raw material, firstly preparing biomass N-CQD by adopting a hydrothermal method, then preparing N-CQD/ZIF-8 by adopting an in-situ synthesis method on the obtained biomass N-CQD and a metal organic framework material ZIF-8, and finally preparing Cu by adopting a reduction precipitation method2O is introduced into N-CQD/ZIF-8 to prepare the ZIF-8 type composite photocatalyst.
Preferably, the method specifically comprises the following steps:
crushing and drying a biomass material to obtain biomass powder, and carrying out hydrothermal reaction on the biomass powder and urea to obtain biomass N-CQD; respectively and uniformly dispersing the obtained biomass N-CQD in two solutions to respectively obtain a solution A and a solution B, and respectively dissolving a metal zinc-based precursor and an imidazole ligand in the solution A or the solution B to obtain a reaction solution A and a reaction solution B; reacting the obtained reaction liquid A and the reaction liquid B based on an in-situ synthesis method to obtain a solid precipitate, and purifying and drying the obtained solid precipitate to obtain N-CQD/ZIF-8; dissolving a metal copper salt and N-CQD/ZIF-8 in water to prepare a metal copper salt/N-CQD/ZIF-8 solution; dissolving another copper salt with equal mass in water to prepare a copper salt solution; and (2) dripping the obtained metal copper salt solution into the obtained metal copper salt/N-CQD/ZIF-8 solution, continuously adding a sulfonate dispersant, an alkaline substance and a reducing agent to perform a reduction precipitation reaction at normal temperature, centrifuging after the reaction is finished to obtain a solid product, washing and drying the obtained solid product to obtain the ZIF-8 type composite photocatalyst.
Further preferably, the mass ratio of the biomass powder to the urea is 1g (0.1-0.4 g);
when preparing solution A or solution B, the solution is CH3The dosage ratio of the OH solution to the biomass N-CQD to the solvent is 0.001-0.003 g: 200-300 mL.
Further preferably, the mass ratio of the biomass N-CQD, the metal zinc-based precursor and the imidazole ligand is 0.001-0.003 g, 2.5-5 g and 4.1 g.
Further preferably, the metallic copper salt is cupric chloride dihydrate or cuprous sulfate;
the sulfonate dispersant is sodium dodecyl benzene sulfonate, alpha-olefin sulfonate or 2-hydroxy ethyl sodium sulfonate.
Further preferably, the alkaline substance is NaOH or KOH;
the reducing agent is ascorbic acid or glucose.
Preferably, when the solution of the metal copper salt/N-CQD/ZIF-8 is prepared, the mass ratio of the metal copper salt to the N-CQD/ZIF-8 is 0.1-0.2 g: 0.5-1 g;
the feeding ratio of the metal copper salt to the sulfonate dispersant, the alkaline substance to the reducing agent is 0.1-0.2 g, 1g, 0.8g and 0.8 g.
Preferably, the reaction temperature of the hydrothermal reaction is 100-200 ℃, and the reaction time is 12-24 h;
the reaction temperature of the in-situ synthesis method is 10-35 ℃;
the reaction temperature of the reduction precipitation method is 10-35 ℃.
Preferably, the biomass material is walnut shells, chestnut shells or mangosteen shells.
The invention discloses a ZIF-8 type composite photocatalyst prepared by adopting the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a ZIF-8 type composite photocatalyst, which introduces N-CQD and Cu2The heterostructure constructed by O promotes the qualitative movement of a photon-generated carrier, inhibits the rapid recombination of photon-generated electron-hole pairs, effectively improves the visible light absorption capacity of the ZIF-8, and combines the advantages of designability and controllability of a metal organic framework material ZIF-8.
The invention also discloses a ZIF-8 type composite photocatalyst prepared by the preparation method, which is prepared by adding Cu2O is introduced into N-CQD/ZIF-8 to prepare three-dimensional Cu2O/N-CQD/ZIF-8 composite photocatalyst prepared by using Cu2O as a relatively stable P-type semiconductor, in combination with N-CQD and Cu2And O, the photoresponse range of the ZIF-8 is effectively widened, and the defects of unstable N-CQD/ZIF-8 photocatalytic performance and the like are effectively relieved. In the specific embodiment of the invention, related experiments show that hexavalent chromium (cr (vi)) is used as a degradation target product of the ZIF-8 composite photocatalyst, and the photocatalytic performance of the hexavalent chromium (cr (vi)) is significantly improved.
Drawings
FIG. 1 is an infrared spectrum of a ZIF-8 type composite photocatalyst in example 1;
FIG. 2 is a chart showing an ultraviolet-visible diffuse reflectance spectrum of the ZIF-8 type composite photocatalyst of example 1;
FIG. 3 is a fluorescence spectrum of a ZIF-8 type composite photocatalyst in example 1;
FIG. 4 is a graph showing the comparison of the performances of the ZIF-8 type composite photocatalyst, the N-CQD/ZIF-8 composite material and ZIF-8 photocatalytic reduction of Cr (VI) in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a preparation method of a ZIF-8 type composite photocatalyst, which is prepared from N-CQD, a metal organic framework material ZIF-8 and a P type semiconductor Cu2And (C) O. By introducing N-CQD and Cu2And O, the photoresponse range of the ZIF-8 is effectively widened, and the photocatalytic performance of the ZIF-8 is further remarkably improved.
The method specifically comprises the following steps:
the method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
And (3) placing the waste biomass material in an oven for drying, beating the waste biomass material into small blocks, crushing the small blocks by using a crusher, placing the small blocks in a sample bag for drying for later use, and obtaining biomass powder. The method comprises the steps of taking biomass powder and urea as raw materials, carrying out hydrothermal reaction for 12-24 hours at the reaction temperature of 100-200 ℃, and then preparing nitrogen-doped carbon quantum dots (N-CQD), namely the biomass N-CQD. Wherein the mass ratio of the biomass powder to the urea is 1g (0.1-0.4 g); the biomass material is walnut shell, chestnut shell or mangosteen shell.
Preferably, the reaction conditions of the biomass nitrogen-doped carbon quantum dots (N-CQD) are as follows: m (walnut shells): and m (urea) is 1g to 0.2g, the temperature is 180 ℃, and the reaction time is 18 h.
Preferably, the reaction conditions of the biomass nitrogen-doped carbon quantum dots (N-CQD) are as follows: m (chestnut shell): and m (urea) is 1g to 0.1g, the temperature is 150 ℃, and the reaction time is 16 h.
Preferably, the reaction conditions of the biomass nitrogen-doped carbon quantum dots (N-CQD) are as follows: m (mangosteen shell) ═ m: and m (urea) is 1g to 0.4g, the temperature is 130 ℃, and the reaction time is 24 h.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively dissolving 0.001-0.003 g of biomass N-CQD in 200-300 mL of methanol (CH)3OH) solution, marking as solution A and solution B, after completely dissolving by ultrasonic, respectively dissolving 2.5-5 g of metal zinc-based precursor and 4.1g of imidazole ligand in the solution A and the solution B to obtain reaction liquid A and reaction liquid B, and continuously reacting the obtained reaction liquid A and reaction liquid B for 30min at room temperature (10-35 ℃) by adopting an in-situ synthesis method to obtain solid precipitate; purifying and drying the obtained solid precipitate to obtain N-CQD/ZIF-8. Wherein the zinc-based precursor is zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O), and the imidazole ligand is 2-methylimidazole. The operation of purifying the solid precipitate comprises: subjecting the obtained solid precipitate to CH treatment at 20-35 deg.C3And soaking in the OH solution for 12-24 hours.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Taking a metal copper salt and N-CQD/ZIF-8 as raw materials, wherein 0.1-0.2 g of the metal copper salt and 0.5-1 g of the N-CQD/ZIF-8 are dissolved in 100mL of water to prepare a metal copper salt/N-CQD/ZIF-8 solution, stirring the solution at normal temperature for 30min, dissolving the metal copper salt with the same mass (0.1-0.2 g) in 100mL of water to prepare a metal copper salt solution, fully stirring the solution, dropwise adding 1-5 mL of the metal copper salt solution, sequentially adding a sulfonate dispersant and an alkaline substance, stirring the solution at 10-35 ℃ for 30min, adding a reducing agent, continuously stirring the solution at 10-35 ℃ for 1h to perform a reduction precipitation reaction, centrifugally washing the solution, and drying the solution in a vacuum drying oven to obtain Cu2The novel O/N-CQD/ZIF-8 composite photocatalyst is the ZIF-8 composite photocatalyst. The copper salt in the third step is copper chloride dihydrate (CuCl)2·2H2O) or cuprous sulphate (Cu)2SO4) One of (1); the sulfonate dispersant is one of Sodium Dodecyl Benzene Sulfonate (SDBS), alpha-olefin sulfonate (AOS) or 2-hydroxyethyl sodium sulfonate (SHES); the alkaline substance is one of NaOH or KOH; the reducing agent is one of ascorbic acid or glucose. Wherein, the first and second connecting parts are connected with each other; the drying temperature is 60-80 ℃; the drying time is 10-20 h.
The invention will be further illustrated with reference to specific examples:
example 1
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
The method comprises the steps of placing the walnut shells made of the waste biomass materials into an oven, drying, beating into small blocks, crushing by using a crusher, placing in a sample bag, and drying for later use. Weighing 1.0g of walnut shell and 0.2g of urea, and fully dissolving the walnut shell and the urea in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 180 ℃ for 18h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified biomass N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.0015g of biomass N-CQD with equal mass, and respectively dissolving in 300mL of CH3OH and 250mL CH3In OH solution, marking as solution A and solution B, after ultrasonic treatment for 30min, nitrate hexahydrate is addedZinc salt ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 3.7g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 25 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 20 DEG)3OH solution is soaked for 24 hours) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.17g of CuCl was weighed2·2H2Dissolving O and 0.5g N-CQD/ZIF-8 catalyst in 100mL water, stirring at room temperature for 30min, and dropwise adding CuCl2·2H2O solution (0.17g CuCl)2·2H2Dissolving O in 100mL of water), sequentially adding 1g of SDBS and 0.8g of NaOH, stirring at normal temperature for 30min, then adding 0.8g of ascorbic acid, stirring at 35 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 2
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
The method comprises the steps of placing the walnut shells made of the waste biomass materials into an oven, drying, beating into small blocks, crushing by using a crusher, placing in a sample bag, and drying for later use. Weighing 1.0g of walnut shell and 0.2g of urea, and fully dissolving the walnut shell and the urea in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 180 ℃ for 18h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.0015g of biomass N-CQD with equal mass to be dissolved in 300mL of CH3OH and 250mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 2.5g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 10 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 35 DEG)3OH solution soaking for 12h) dryingDrying to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.17g of CuCl was weighed2·2H2Dissolving O and 0.5g N-CQD/ZIF-8 catalyst in 100mL water, stirring at room temperature for 30min, and dropwise adding CuCl2·2H2O solution (0.17g CuCl)2·2H2Dissolving O in 100mL of water), sequentially adding 1g of SDBS and 0.8g of NaOH, stirring at normal temperature for 30min, then adding 0.8g of ascorbic acid, stirring at 10 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 3
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
The method comprises the steps of placing the walnut shells made of the waste biomass materials into an oven, drying, beating into small blocks, crushing by using a crusher, placing in a sample bag, and drying for later use. Weighing 1.0g of walnut shell and 0.2g of urea, and fully dissolving the walnut shell and the urea in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 180 ℃ for 18h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.0015g of biomass N-CQD with equal mass, and respectively dissolving in 300mL of CH3OH and 250mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2Dissolving O) and 2-methylimidazole in solution A and B at a mass ratio of 5g:4.1g, continuously performing in-situ synthesis reaction at 35 deg.C for 30min, and purifying (subjecting the obtained solid precipitate to CH reaction at 25 deg.C)3OH solution is soaked for 18h) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.17g of CuCl was weighed2·2H2O and0.5g of N-CQD/ZIF-8 catalyst is dissolved in 100mL of water, stirred at normal temperature for 30min, and dropwise added with CuCl2·2H2O solution (0.17g CuCl)2·2H2Dissolving O in 100mL of water), sequentially adding 1g of SDBS and 0.8g of NaOH, stirring at normal temperature for 30min, then adding 0.8g of ascorbic acid, stirring at 15 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 4
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
And (3) placing the waste biomass material plate chestnut shells in an oven for drying, then beating the chestnut shells into small blocks, crushing the small blocks by using a crusher, and placing the small blocks in a sample bag for drying for later use. Weighing 1.0g of chestnut shell and 0.1g of urea, and fully dissolving the chestnut shell and the urea in 50mL of deionized water and uniformly stirring. And (3) continuously carrying out hydrothermal reaction for 16h at 150 ℃, and carrying out purification operations such as centrifugation, dialysis and the like, and freeze-drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.0015g of biomass N-CQD with equal mass, and respectively dissolving in 300mL of CH3OH and 250mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 3.7g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 20 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 30 DEG)3OH solution is soaked for 14h) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.17g of CuCl was weighed2·2H2Dissolving O and 0.5g N-CQD/ZIF-8 catalyst in 100mL water, stirring at room temperature for 30min, and dropwise adding CuCl2·2H2O solution (0.17g CuCl)2·2H2Dissolving O in 100mL of water), adding 1g of SDBS and 0.8g of NaOH in sequence, stirring at normal temperature for 30min, and adding0.8g ascorbic acid, stirring at 20 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 5
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
And (3) placing the waste biomass material mangosteen shells in an oven for drying, then beating the waste biomass material mangosteen shells into small blocks, crushing the small blocks by using a crusher, and placing the small blocks in a sample bag for drying for later use. Weighing 1.0g of mangosteen shell and 0.4g of urea, and fully dissolving the two in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 130 ℃ for 24h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.0015g of biomass N-CQD with equal mass, and respectively dissolving in 300mL of CH3OH and 250mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 3.7g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 20 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 30 DEG)3OH solution is soaked for 20h) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.2g of CuCl is weighed out2·2H2Dissolving O and 0.5g N-CQD/ZIF-8 catalyst in 100mL water, stirring at room temperature for 30min, and dropwise adding CuCl2·2H2O solution (0.2g CuCl)2·2H2Dissolving O in 100mL of water), sequentially adding 1g of SDBS and 0.8g of NaOH, stirring at normal temperature for 30min, then adding 0.8g of ascorbic acid, stirring at 25 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 6
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
And (3) placing the waste biomass material mangosteen shells in an oven for drying, then beating the waste biomass material mangosteen shells into small blocks, crushing the small blocks by using a crusher, and placing the small blocks in a sample bag for drying for later use. Weighing 1.0g of mangosteen shell and 0.3g of urea, and fully dissolving the two in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 130 ℃ for 24h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.001g of biomass N-CQD with equal mass, and respectively dissolving in 200mL of CH3OH and 300mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 4.1g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 18 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 20 DEG)3OH solution is soaked for 24 hours) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
0.1g of CuCl is weighed out2·2H2Dissolving O and 1gN-CQD/ZIF-8 catalyst in 100mL water, stirring at normal temperature for 30min, and dropwise adding CuCl2·2H2O solution (0.1g CuCl)2·2H2Dissolving O in 100mL of water), sequentially adding 1g of alpha-olefin sulfonate (AOS) and 0.8g of KOH, stirring at normal temperature for 30min, then adding 0.8g of glucose, stirring at 35 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 70 ℃ for 20h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
Example 7
The method comprises the following steps: preparation of biomass nitrogen-doped carbon quantum dots (N-CQD)
And (3) placing the waste biomass material mangosteen shells in an oven for drying, then beating the waste biomass material mangosteen shells into small blocks, crushing the small blocks by using a crusher, and placing the small blocks in a sample bag for drying for later use. Weighing 1.0g of mangosteen shell and 0.1g of urea, and fully dissolving the two in 50mL of deionized water and uniformly stirring. And continuously carrying out hydrothermal reaction at 130 ℃ for 24h, carrying out purification operations such as centrifugation and dialysis, and carrying out freeze drying to obtain the purified N-CQD.
Step two: preparation of nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Respectively weighing 0.003g of biomass N-CQD with equal mass, and respectively dissolving the biomass N-CQD in 250mL of CH3OH and 200mL CH3In the OH solution, marked as solution A and solution B, after being subjected to ultrasonic treatment for 30min, zinc nitrate hexahydrate ((Zn (NO)3)2·6H2O) and 2-methylimidazole are respectively dissolved in the solution A and the solution B according to the mass ratio of 4.6g to 4.1g, the in-situ synthesis reaction is continuously carried out for 30min at the temperature of 30 ℃, and the obtained solid precipitate is purified (the obtained solid precipitate is treated by CH at the temperature of 35 DEG)3OH solution is soaked for 12h) and dried to obtain N-CQD/ZIF-8.
Step three: cuprous oxide (Cu)2Preparation of O)/nitrogen-doped carbon quantum dot (N-CQD)/metal organic framework material ZIF-8
Weighing 0.12g of cuprous sulfate and 0.8g of N-CQD/ZIF-8 catalyst, dissolving in 100mL of water, stirring at normal temperature for 30min, dropwise adding a cuprous sulfate solution (0.12g of cuprous sulfate is dissolved in 100mL of water), sequentially adding 1g of sodium 2-hydroxyethyl sulfonate (SHES) and 0.8g of KOH, stirring at normal temperature for 30min, then adding 0.8g of glucose, stirring at 10 ℃ for 1h, centrifuging, washing, and drying in a vacuum drying oven at 80 ℃ for 10h to obtain Cu2An O/N-CQD/ZIF-8 ternary composite photocatalyst, namely a ZIF-8 type composite photocatalyst.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, it can be seen that the characteristic absorption peaks shown in the figure are all matched with the characteristic absorption peaks of the functional groups (e.g., N-H, C-C, C-H, O-H) which are generated in the reaction. Proves that N-CQD and metal organic framework material ZIF-8 are firmly combined together through functional group reaction, and Cu2O is successfully loaded on the N-CQD/ZIF-8 composite material.
Referring to FIG. 2, it can be seen that ZIF-8 exhibits selective absorption at a wavelength of 200-400 nm, and Cu is introduced2After O, the absorption peak shifts to the long-wave directionThe red shift occurs and the absorption strength is enhanced accordingly.
Referring to FIG. 3, it can be seen that Cu2The fluorescence intensity of the O/N-CQD/ZIF-8 composite photocatalyst (namely the ZIF-8 composite photocatalyst) is far lower than that of ZIF-8 and N-CQD/ZIF-8 composite materials, and the result shows that Cu2The introduction of O inhibits the rapid recombination of photogenerated electron-hole pairs generated by the material, thereby improving the Cu content2The performance of the O/N-CQD/ZIF-8 composite material in photocatalytic reduction of Cr (VI).
Referring to FIG. 4, the loads N-CQD and Cu are known2After O, the photocatalytic performance of the metal organic framework material ZIF-8 is remarkably improved to about six times of the original photocatalytic performance.
In conclusion, the invention discloses a ZIF-8 type composite photocatalyst and a preparation method thereof, and aims to provide a novel composite photocatalyst prepared by improving the ZIF-8 photocatalytic performance. The method utilizes walnut shells made of biomass materials as raw materials, prepares N-CQD by a hydrothermal method, and effectively combines the biomass N-CQD and a metal organic framework material ZIF-8 by an in-situ synthesis method to prepare the N-CQD/ZIF-8. Then Cu is reduced and precipitated2O is introduced into N-CQD/ZIF-8 to prepare three-dimensional Cu2The novel O/N-CQD/ZIF-8 composite photocatalyst is a ZIF-8 composite photocatalyst, effectively improves the photocatalytic performance of ZIF-8, has short process flow, low energy consumption and cheap and easily-obtained raw materials, and is an ideal ZIF-8 composite photocatalyst Cu2A preparation method of O/N-CQD/ZIF-8.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a ZIF-8 type composite photocatalyst is characterized in that a biomass material is used as a raw material, firstly a hydrothermal method is adopted to prepare biomass N-CQD, then the obtained biomass N-CQD and a metal organic framework material ZIF-8 are prepared into N-CQD/ZIF-8 by an in-situ synthesis method, and finally a reduction precipitation method is adopted to prepare Cu by Cu2O is introduced into N-CQD/ZIF-8,and preparing the ZIF-8 type composite photocatalyst.
2. The preparation method of the ZIF-8 type composite photocatalyst as claimed in claim 1, which is characterized by comprising the following steps:
crushing and drying a biomass material to obtain biomass powder, and carrying out hydrothermal reaction on the biomass powder and urea to obtain biomass N-CQD;
respectively and uniformly dispersing the obtained biomass N-CQD in two solutions to respectively obtain a solution A and a solution B, and respectively dissolving a metal zinc-based precursor and an imidazole ligand in the solution A or the solution B to obtain a reaction solution A and a reaction solution B; reacting the obtained reaction liquid A and the reaction liquid B based on an in-situ synthesis method to obtain a solid precipitate, and purifying and drying the obtained solid precipitate to obtain N-CQD/ZIF-8;
dissolving a metal copper salt and N-CQD/ZIF-8 in water to prepare a metal copper salt/N-CQD/ZIF-8 solution; dissolving another copper salt with equal mass in water to prepare a copper salt solution; and (2) dripping the obtained metal copper salt solution into the obtained metal copper salt/N-CQD/ZIF-8 solution, continuously adding a sulfonate dispersant, an alkaline substance and a reducing agent to perform a reduction precipitation reaction at normal temperature, centrifuging after the reaction is finished to obtain a solid product, washing and drying the obtained solid product to obtain the ZIF-8 type composite photocatalyst.
3. The preparation method of the ZIF-8 composite photocatalyst as claimed in claim 2, wherein the mass ratio of the biomass powder to the urea is 1g (0.1-0.4) g;
when preparing solution A or solution B, the solution is CH3The dosage ratio of the OH solution to the biomass N-CQD to the solvent is 0.001-0.003 g: 200-300 mL.
4. The preparation method of the ZIF-8 type composite photocatalyst, as claimed in claim 2, wherein the mass ratio of the biomass N-CQD, the metal zinc-based precursor and the imidazole ligand is 0.001-0.003 g: 2.5-5 g:4.1 g.
5. The method for preparing the ZIF-8 type composite photocatalyst as defined in claim 2, wherein the metallic copper salt is cupric chloride dihydrate or cuprous sulfate;
the sulfonate dispersant is sodium dodecyl benzene sulfonate, alpha-olefin sulfonate or 2-hydroxy ethyl sodium sulfonate.
6. The method for preparing a ZIF-8 type composite photocatalyst as defined in claim 2, wherein the basic substance is NaOH or KOH;
the reducing agent is ascorbic acid or glucose.
7. The method for preparing the ZIF-8 type composite photocatalyst as claimed in claim 2, wherein the mass ratio of the metal copper salt to the N-CQD/ZIF-8 is 0.1-0.2 g: 0.5-1 g when preparing the metal copper salt/N-CQD/ZIF-8 solution;
the feeding ratio of the metal copper salt to the sulfonate dispersant, the alkaline substance to the reducing agent is 0.1-0.2 g, 1g, 0.8g and 0.8 g.
8. The preparation method of the ZIF-8 type composite photocatalyst as claimed in claim 1, wherein the reaction temperature of the hydrothermal reaction is 100-200 ℃ and the reaction time is 12-24 hours;
the reaction temperature of the in-situ synthesis method is 10-35 ℃;
the reaction temperature of the reduction precipitation method is 10-35 ℃.
9. The method for preparing a ZIF-8 type composite photocatalyst as defined in claim 1, wherein the biomass material is walnut shells, chestnut shells or mangosteen shells.
10. A ZIF-8 type composite photocatalyst prepared by the preparation method of any one of claims 1 to 9.
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Cited By (2)
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| CN114471734A (en) * | 2022-01-19 | 2022-05-13 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of visible light response cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN115532236A (en) * | 2022-10-25 | 2022-12-30 | 陕西科技大学 | Cu 2 Preparation method and application of O composite amidoxime group adsorbing material |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150069295A1 (en) * | 2013-09-09 | 2015-03-12 | National University Of Singapore | Hydrogel nanocomposite |
| CN106111137A (en) * | 2016-06-21 | 2016-11-16 | 上海交通大学 | A kind of preparation method and applications of carbon quantum dot Red copper oxide composite |
| CN106252676A (en) * | 2016-07-28 | 2016-12-21 | 青岛大学 | A kind of quantum dot modified metal organic backbone embeds the preparation of carbon nano-tube material |
| CN107754861A (en) * | 2017-11-01 | 2018-03-06 | 中国科学院福建物质结构研究所 | A kind of preparation method and application of carbon quantum dot/metal organic framework catalyst |
| CN108187722A (en) * | 2018-01-13 | 2018-06-22 | 常州大学 | A kind of preparation method of nitrogen-doped carbon quantum dot/cuprous oxide composite photo-catalyst |
| CN108479855A (en) * | 2018-03-28 | 2018-09-04 | 北京工业大学 | A kind of nucleocapsid metal organic framework base composite photocatalyst and preparation method thereof |
| CN108686705A (en) * | 2018-05-04 | 2018-10-23 | 大连理工大学 | A kind of carbon quantum dot-ZIF-67 absorption-photochemical catalyst and preparation method thereof |
| CN109847799A (en) * | 2019-03-07 | 2019-06-07 | 常州大学 | With highlight catalytic active C-dots/UiO-66-NH2The preparation method and applications of composite material |
| CN110229662A (en) * | 2019-07-09 | 2019-09-13 | 长春工业大学 | A kind of preparation method of carbon quantum dot and metal organic framework composite material |
| CN111013664A (en) * | 2019-11-26 | 2020-04-17 | 燕山大学 | Composite photocatalyst and preparation method thereof |
| US20200129971A1 (en) * | 2016-02-19 | 2020-04-30 | Chinese Research Academy Of Enviromental Sciences | Cu CATALYST BASED ON METAL ORGANIC FRAMEWORK, PREPARATION METHOD AND USE THEREOF |
| CN111617805A (en) * | 2020-06-04 | 2020-09-04 | 吉林大学 | Light Fenton catalyst, preparation method, application and water treatment agent thereof |
| CN112808313A (en) * | 2020-12-30 | 2021-05-18 | 陕西科技大学 | Nitrogen-doped carbon quantum dot/metal organic framework material MOF-5 photocatalyst and preparation method and application thereof |
-
2021
- 2021-07-30 CN CN202110870968.XA patent/CN113413921B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150069295A1 (en) * | 2013-09-09 | 2015-03-12 | National University Of Singapore | Hydrogel nanocomposite |
| US20200129971A1 (en) * | 2016-02-19 | 2020-04-30 | Chinese Research Academy Of Enviromental Sciences | Cu CATALYST BASED ON METAL ORGANIC FRAMEWORK, PREPARATION METHOD AND USE THEREOF |
| CN106111137A (en) * | 2016-06-21 | 2016-11-16 | 上海交通大学 | A kind of preparation method and applications of carbon quantum dot Red copper oxide composite |
| CN106252676A (en) * | 2016-07-28 | 2016-12-21 | 青岛大学 | A kind of quantum dot modified metal organic backbone embeds the preparation of carbon nano-tube material |
| CN107754861A (en) * | 2017-11-01 | 2018-03-06 | 中国科学院福建物质结构研究所 | A kind of preparation method and application of carbon quantum dot/metal organic framework catalyst |
| CN108187722A (en) * | 2018-01-13 | 2018-06-22 | 常州大学 | A kind of preparation method of nitrogen-doped carbon quantum dot/cuprous oxide composite photo-catalyst |
| CN108479855A (en) * | 2018-03-28 | 2018-09-04 | 北京工业大学 | A kind of nucleocapsid metal organic framework base composite photocatalyst and preparation method thereof |
| CN108686705A (en) * | 2018-05-04 | 2018-10-23 | 大连理工大学 | A kind of carbon quantum dot-ZIF-67 absorption-photochemical catalyst and preparation method thereof |
| CN109847799A (en) * | 2019-03-07 | 2019-06-07 | 常州大学 | With highlight catalytic active C-dots/UiO-66-NH2The preparation method and applications of composite material |
| CN110229662A (en) * | 2019-07-09 | 2019-09-13 | 长春工业大学 | A kind of preparation method of carbon quantum dot and metal organic framework composite material |
| CN111013664A (en) * | 2019-11-26 | 2020-04-17 | 燕山大学 | Composite photocatalyst and preparation method thereof |
| CN111617805A (en) * | 2020-06-04 | 2020-09-04 | 吉林大学 | Light Fenton catalyst, preparation method, application and water treatment agent thereof |
| CN112808313A (en) * | 2020-12-30 | 2021-05-18 | 陕西科技大学 | Nitrogen-doped carbon quantum dot/metal organic framework material MOF-5 photocatalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 潘柯等: ""Zif-8吸附剂对水中重金属离子的吸附性能研究"", 《广州化工》, vol. 46, no. 9, 31 May 2018 (2018-05-31), pages 46 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471734A (en) * | 2022-01-19 | 2022-05-13 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of visible light response cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN114471734B (en) * | 2022-01-19 | 2023-12-08 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of visible light response cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN115532236A (en) * | 2022-10-25 | 2022-12-30 | 陕西科技大学 | Cu 2 Preparation method and application of O composite amidoxime group adsorbing material |
| JP7486222B2 (en) | 2022-10-25 | 2024-05-17 | 陝西科技大学 | Method for producing Cu2O composite amidoxime group adsorbent and its application |
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