CN111266114A - Metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst and preparation method and application thereof - Google Patents
Metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst and preparation method and application thereof Download PDFInfo
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- CN111266114A CN111266114A CN202010188854.2A CN202010188854A CN111266114A CN 111266114 A CN111266114 A CN 111266114A CN 202010188854 A CN202010188854 A CN 202010188854A CN 111266114 A CN111266114 A CN 111266114A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 155
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 47
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229960001860 salicylate Drugs 0.000 claims description 19
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 19
- VGMSDKOZHVRRAW-UHFFFAOYSA-J zinc;iron(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Zn+2] VGMSDKOZHVRRAW-UHFFFAOYSA-J 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000003751 zinc Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical group [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000009830 intercalation Methods 0.000 claims description 8
- 230000002687 intercalation Effects 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 229960004025 sodium salicylate Drugs 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 claims description 2
- 229960003629 potassium salicylate Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
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- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J35/33—
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- B01J35/39—
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- B01J35/393—
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- B01J35/399—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/16—Reducing
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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
-
- 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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to a metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst, a preparation method and application thereof, belonging to the technical field of semiconductor photocatalysts. The invention aims to solve the problems of narrow photoresponse range, low photocatalytic activity, difficult recovery and the like of the semiconductor zinc oxide. The invention takes the layered double hydroxide as a single precursor, prepares the ternary nano composite visible light catalyst by adopting a simple one-step solid pyrolysis reaction, and does not need to add any reducing agent, template agent and additional carbon source in the whole preparation process. The prepared photocatalyst has the advantages that iron and zinc oxide nanoparticles are uniformly dispersed in graphitized carbon, and the photocatalyst has excellent photocatalytic performance in visible light catalytic degradation of organic pollutants. The preparation method is simple, economic, green and controllable, and the prepared photocatalyst has excellent performances of high crystallinity, high activity, high stability, magnetic recovery and the like, and is expected to be widely applied in the field of photocatalysis.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalysts, and particularly relates to a metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst as well as a preparation method and application thereof.
Background
The nano zinc oxide (ZnO) is an important direct band gap wide bandgap semiconductor, has a bandgap width of 3.37eV at room temperature, and has the advantages of greenness, no toxicity, low cost and the like. When the nano zinc oxide is excited by light, photo-generated electrons and holes can be quickly generated, but the larger forbidden bandwidth means that the nano zinc oxide can only absorb less than 5% of ultraviolet light in sunlight and is difficult to utilize visible light accounting for about 46% of the sunlight (the wavelength range of the ultraviolet light is 10-400nm, and the wavelength range of the visible light is 400-780 nm); meanwhile, the nanometer zinc oxide has the defects of high recombination rate of photon-generated carriers, photo-corrosion, difficulty in separation and recovery and the like, and the defects limit the application of the zinc oxide in the field of photocatalysis to a great extent.
The compounding of nano zinc oxide with semiconductors, metals or nano carbon materials is one of the common methods for modifying zinc oxide, and is also a hotspot in the field of semiconductor photocatalyst research in recent years. In a nano zinc oxide composite material system, the components can generate mutual coupling effect, and can show a plurality of novel physicochemical characteristics while influencing the respective characteristics of the material, thereby breaking through the limitation of the performance of a single component material. Such as: 1. the zinc oxide semiconductor is compounded with a nano carbon material (activated carbon, carbon nano tube, graphene, carbon quantum dot and the like) to improve the dispersibility and stability of the zinc oxide semiconductor, widen the photoresponse range and improve the photocatalytic activity (Angew. chem. int. Ed,2014,53, 7305-7309). 2. The zinc oxide semiconductor modified by metal can improve the conductivity of nano zinc oxide, accelerate the transmission of electrons, effectively inhibit the recombination and the photo-corrosion of photo-generated electron-hole pairs, and improve the photocatalytic efficiency to a certain extent. Common metal-modified zinc oxide semiconductor composite catalysts are mainly modified by noble metals, such as Pt, Pd, Au, Ag and the like (J.Am.chem.Soc.2011,133, 5660-5663). At present, in the preparation processes of the two composite materials, common preparation methods comprise an impregnation method, a template method, a hydrothermal (solvent) method, a chemical vapor deposition method and the like, and the methods have the defects of complex preparation process, multiple reagents, low product crystallinity, low purity, poor dispersibility, high raw material price, difficult material recovery and the like.
Layered Double Hydroxides (LDHs) are multifunctional Layered materials with a supermolecular structure, are composed of Layered metal cations and Layered anions which are dispersed at an atomic level, have good chemical stability, have the characteristics that the types and the proportions of the Layered metal cations and the Layered anions can be adjusted, and have wide application prospects in the fields of catalysis, magnetism, photoelectric conversion, construction of functional materials and the like. The layered double hydroxide is used as a single precursor to be applied to the preparation of the zinc oxide nano composite photocatalyst, and the problems of low visible light catalytic activity, difficult recovery and the like of nano zinc oxide are hopefully solved.
Disclosure of Invention
The invention aims to provide a metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst, a preparation method thereof and application thereof in catalytic degradation of organic pollutants. The ternary Fe/ZnO/C nano composite visible light catalyst designed by the invention has a multi-component structure which can play a synergistic effect among components, so that photo-generated electron holes respectively participate in redox reactions on different surfaces, and the problems of narrow zinc oxide photoresponse range, easy recombination of photo-generated electron-hole pairs, easy agglomeration of metal iron nano particles, difficult catalyst recovery and the like are solved.
The size of the metallic iron nano particles in the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst is 5-10nm, the size of the zinc oxide nano particles is 10-40nm, and the metallic iron and the zinc oxide nano particles are uniformly dispersed in a graphitized carbon matrix.
The preparation method of the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst comprises the following steps: the salicylic acid radical intercalated layered zinc-iron hydroxide is used as a precursor and is prepared by one-step solid pyrolysis reaction in nitrogen or inert atmosphere.
The preparation method of the salicylic acid radical intercalated layered zinc-iron hydroxide precursor comprises the following steps: the concentration is 0.12-0.50mol ·L-1The zinc salt solution and the concentration of the zinc salt solution are 0.02-0.20 mol.L-1The ferric salt solution is mixed evenly, and then the concentration is 0.15-0.30 mol.L-1The salicylate solution is dropwise added into the mixed solution of zinc salt and iron salt, wherein the molar ratio of the zinc salt to the iron salt is 5-2:1, and the molar ratio of the sum of the molar numbers of the zinc salt and the iron salt to the salicylate is 2-1: 1; and (3) adjusting the pH value of the mixed solution to 7-8 by using a sodium hydroxide solution, reacting for 6-48h at 40-100 ℃, and centrifuging, washing and drying to obtain the salicylic acid radical intercalated layered zinc-iron hydroxide precursor.
The solid state pyrolysis reaction conditions are as follows: the layered zinc-iron hydroxide precursor of the salicylate intercalation is placed in a porcelain boat, the temperature is raised to 600-800 ℃ at the temperature rise rate of 2-5 ℃/min, and the temperature is kept for 0-4 h.
The zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate; the ferric salt is one or more of ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate; the salicylate is sodium salicylate or potassium salicylate.
The inert atmosphere is one or two of argon and helium.
The prepared metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst is applied to catalytic degradation of organic pollutants.
The steps for catalytically degrading organic pollutants are as follows:
1) adjusting the concentration of organic pollutants to 5-30mg/L and the pH value to 5-8;
2) adding metal iron/zinc oxide/carbon ternary nano composite visible light catalyst with the dosage of 0.1-1 g/L;
3) firstly, carrying out dark treatment for 30-60min under the condition of no illumination to ensure that a reaction system reaches absorption and desorption balance, then carrying out catalytic degradation reaction by using visible light source irradiation, wherein the light power is 100-350W, and the system temperature is kept at 25-30 ℃.
In order to improve the visible light catalytic activity of zinc oxide, the invention introduces a transition metal Fe cocatalyst, and disperses the transition metal Fe cocatalyst on the surface of a zinc oxide main catalyst, because the Fermi level of the transition metal cocatalyst is generally lower than that of a semiconductor photocatalyst, generated photoproduction electrons are captured by the cocatalyst when transferred to the surface of the catalyst, and photoproduction holes are remained on the main catalyst and transferred to the surface, and the separation of the photoproduction electrons and the holes is realized by changing the energy band structure of the semiconductor zinc oxide. However, the metallic zero-valent iron nanoparticles are easily agglomerated, oxidized and passivated, resulting in low reactivity. Therefore, in the present invention, the reaction is strictly controlled to be carried out under an inert atmosphere, and the solid state pyrolysis temperature is controlled to be 600-800 ℃, and if the temperature is lower than or higher than the range, the metallic zero-valent iron nanoparticles cannot be formed. And secondly, the graphite carbon has conductivity and can improve the adsorption of the catalyst to organic pollutants, and the separation of photoproduction electrons and holes can be promoted by introducing a graphite carbon substrate, so that the electron transmission is accelerated, and the photocatalytic reaction activity is improved.
The invention has the beneficial effects that: 1. the preparation method comprises the following steps of firstly adopting a simple one-step solid pyrolysis reaction, modulating and controlling the reaction conditions (temperature and time) of a precursor and a solid phase to prepare the metallic iron/zinc oxide/carbon three-element nano composite material, wherein no reducing agent, template agent and additional carbon source are needed to be added in the whole preparation process, the hydroxide precursor loses interlayer adsorption water and laminate hydroxyl groups to be converted into mixed metal oxide in the roasting process, interlayer salicylate is pyrolyzed to generate graphitized carbon in situ and release reducing gas, and high-valence iron in the laminate is reduced into metallic zero-valent iron; 2. the preparation method is simple, economic, green and controllable, does not need expensive equipment, and is favorable for large-scale industrial production; 3. the prepared photocatalyst has uniform size distribution, high purity, high graphitization degree, high crystallinity, high activity, high stability and high dispersibility, is applied to the field of photocatalysis, has 18 times of degradation efficiency of methylene blue under visible light as compared with commercial zinc oxide, still keeps the degradation efficiency at about 90 percent after 5 times of recycling, has high saturation magnetization intensity, is easy to magnetically recover, and has high practical value and application prospect.
Drawings
FIG. 1a is an X-ray crystal diffraction pattern (XRD) of the salicylate intercalated layered zinc iron hydroxide precursor prepared in example 1; b is the X-ray crystal diffraction pattern (XRD) of the metallic iron/zinc oxide/carbon three-element nano composite visible-light-driven photocatalyst prepared in the examples 1, 2 and 3; c is the Raman spectrum (Raman) of the metallic iron/zinc oxide/carbon three-element nano composite visible-light-driven photocatalyst prepared in the examples 1, 2 and 3.
FIG. 2a is a Scanning Electron Microscope (SEM) photograph of the salicylate intercalated layered zinc iron hydroxide precursor prepared in example 1; b is a Scanning Electron Microscope (SEM) photograph of the metallic iron/zinc oxide/carbon three-element nanocomposite visible light catalyst prepared in example 1.
Fig. 3 is the transmission electron microscope (a) and high resolution transmission electron microscope (b) photographs of the metallic iron/zinc oxide/carbon ternary nanocomposite visible light catalyst prepared in example 1.
FIG. 4a is a graph of the ultraviolet-visible Diffuse Reflectance Spectrum (DRS) of the metallic iron/zinc oxide/carbon three-component nanocomposite visible light catalyst prepared in examples 1, 2 and 3 and commercial zinc oxide; b is a comparative graph of experiments of the metal iron/zinc oxide/carbon three-component nano composite visible-light-induced photocatalyst prepared in examples 1, 2 and 3 for catalytically degrading Methylene Blue (MB) solution (comprising a methylene blue blank control, commercial zinc oxide, titanium oxide (P25) and the metal iron/zinc oxide/carbon three-component nano composite light-induced photocatalyst prepared at different temperatures).
Fig. 5 is a summary table of the first order kinetics fitting curve and chemical reaction kinetics constants of the metallic iron/zinc oxide/carbon three-element nano composite visible light catalyst prepared in examples 1, 2 and 3.
FIG. 6 is a magnetization curve of the metallic iron/zinc oxide/carbon ternary nanocomposite visible light catalyst prepared in example 1 (lower left in the inset: low field magnified view; upper right: digital photograph of magnetic separation with applied magnetic field).
Fig. 7 is a histogram of the recycling property of the metallic iron/zinc oxide/carbon three-element nano composite visible light catalyst prepared in example 1 for catalytically degrading methylene blue dye.
Detailed Description
The metallic iron/zinc oxide/carbon three-element nanocomposite visible light catalyst and the preparation method thereof according to the present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
(1) 4.455g of zinc nitrate hexahydrate, 2.02g of ferric nitrate nonahydrate and 6.4044g of sodium salicylate are weighed and dissolved in 50mL of deionized water at room temperature respectively by ultrasonic wave; firstly, pouring zinc salt and iron salt solution into a four-neck flask, and dropwise adding salicylic acid sodium salt solution into zinc-iron mixed salt solution by using a constant-pressure separating funnel under the action of continuous stirring.
(2) Weighing 6g of sodium hydroxide, dissolving in 100ml of deionized water to prepare an alkali liquor, slowly dropwise adding the alkali liquor into the mixed salt solution in the step (1) under the stirring action, adjusting the pH value of the system to be 7.5, raising the temperature of a water bath to 95 ℃ after the pH value is stabilized, reacting for 24 hours at the temperature, centrifuging and washing the obtained mixture to be neutral, and drying at 60 ℃ for 12 hours to obtain the reddish brown salicylic acid radical intercalated layered zinc-iron hydroxide precursor.
(3) Placing the salicylate intercalation layered zinc-iron hydroxide precursor prepared in the step (2) into a porcelain boat, roasting in nitrogen atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, and controlling the gas flow rate to be 55mL/cm2And min, obtaining the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst.
In order to verify the structure and performance of the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst, the performance evaluation of photocatalytic degradation of methylene blue dye was performed on the sample prepared in example 1.
The photocatalytic reaction is specifically operated as follows: dispersing 30mg of photocatalyst in 100mL of methylene blue solution with the concentration of 20ppm (20 mg/L); firstly, carrying out dark treatment for 30min under the condition of no illumination to ensure that a reaction system achieves absorption and desorption balance, then turning on a visible light source (a 300W xenon lamp, lambda is more than or equal to 420nm) and introducing circulating water into a reaction container to keep the reaction system at a constant temperature of 28 ℃; after the reaction was started, 3mL of the reaction solution was taken out every 30min and filtered with a 0.22 μm aqueous filter, immediately after which the photocatalytic degradation effect was tested with an ultraviolet-visible spectrophotometer.
The specific operation of the cycling stability experiment was as follows: and separating the reacted metal iron/zinc oxide/carbon nano composite visible light catalyst by using a magnet, washing the separated catalyst for a plurality of times by using deionized water and alcohol, and drying for later use. The process is carefully carried out to minimize catalyst loss.
As can be seen from fig. 1a, the main diffraction peak positions 2 θ of the salicylate intercalated zinc-iron hydroxide are 5.380 °, 11.036 °, 16.618 ° and 22.154 °, which are in good fold relationship, and are characteristic diffraction peaks of the (00l) series of layered hydroxides, indicating that the synthesized precursor has a layered structure. The powder sample was reddish brown.
As can be seen from FIG. 1b, the product components at different firing temperatures are ZnO in the hexagonal phase (PDF #36-1451) and α -Fe in the cubic phase (PDF #06-0696), and due to the high dispersibility of carbon and the low crystallinity relative to iron and zinc oxide, a weak diffraction peak appears at about 26 deg.
As can be seen from FIG. 1c, the composite photocatalysts prepared by calcination at different temperatures are 1325 cm and 1596cm-1The characteristic diffraction peak D and the characteristic diffraction peak G of the graphite carbon appear, which shows that the prepared product contains the graphitized carbon; according to the literature, if ID/IGA ratio of (a) to (b) of greater than 0.09 is considered to be fully graphitized carbon, thus yielding a high degree of graphitization of the carbon in the prepared catalyst.
As can be seen from FIG. 2a, the prepared salicylate intercalation layered zinc-iron hydroxide is of a two-dimensional nanosheet structure.
As can be seen from fig. 2b, the nano composite catalyst obtained by calcining the layered zinc-iron hydroxide intercalated with salicylate at 800 ℃ for 2 hours is composed of loose and porous nano particles connected with each other, and the metallic iron nano particles and the nano zinc oxide particles are uniformly dispersed in the graphitized carbon matrix.
As can be seen from fig. 3a, the nanoparticles are connected to each other to form a uniform iron/zinc oxide/carbon nanocomposite, in which the zinc oxide has a grain size of about 40nm and the iron nanoparticles have a grain size of 5-10nm, which is almost identical to the grain size calculated by the Debye-Scherrer formula in XRD.
As can be seen from fig. 3b, the metallic iron nanoparticles and the zinc oxide nanoparticles are protected by the carbon layer with the thickness of about 2.6nm, and two lattice stripes with different widths (d ═ 0.252nm and d ═ 0.201nm) are found at the same time, which correspond to the (101) crystal plane of ZnO and the (110) crystal plane of α -Fe, respectively, further proving that the metallic iron/zinc oxide/carbon three-element nanocomposite visible light catalyst is successfully prepared.
As can be seen from fig. 4a, the absorption band edge of commercial zinc oxide is 390nm, which is only responsive to uv light. And the absorption edge of the metallic iron/zinc oxide/carbon ternary nano composite visible light catalytic material extends from an ultraviolet region to a visible region, and the absorption band edge is red-shifted to 570 nm. 400-600nm can be attributed to d electron transition absorption of transition metal iron, and 600-800nm is attributed to absorption of graphitized carbon.
As can be seen from FIG. 4b, the prepared nanocomposite visible light catalyst shows excellent photocatalytic performance relative to commercial zinc oxide and P25, and is degraded by 73% within 60min, and the 120min degradation rate reaches 94%; while commercial zinc oxide and P25 have little visible light photocatalytic activity on methylene blue.
As can be seen from FIG. 5, the prepared nanocomposite visible light catalyst has a relatively large chemical reaction kinetic constant, which is about the value of commercial zinc oxide and P25 (TiO)2) 18 times higher than the original value.
As can be seen from the magnetization curve of fig. 6, the remanence and the coercive force of the composite material prepared at room temperature are both almost zero, and the composite material belongs to a superparamagnetic material; meanwhile, the saturation magnetization was 52 emu/g. The prepared ternary nano composite visible light catalyst is easy to recycle due to high saturation magnetization and small remanence and coercive force, saves cost and is green and economic.
As can be seen from FIG. 7, the prepared metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst has high stability, and the degradation efficiency of the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst on methylene blue is still about 90% after 5 times of circulation.
Example 2
(1) Weighing 5.1g of zinc chloride, 2.485g of ferrous chloride tetrahydrate and 6.4044g of sodium salicylate, and respectively dissolving the zinc chloride, the ferrous chloride tetrahydrate and the 6.4044g of sodium salicylate in 50mL of deionized water at room temperature by ultrasonic wave to dissolve the zinc chloride, the ferrous chloride and the sodium salicylate; firstly, pouring zinc salt and iron salt solution into a four-neck flask, and dropwise adding salicylic acid sodium salt solution into zinc-iron mixed salt solution by using a constant-pressure separating funnel under the action of continuous stirring.
(2) Weighing 4g of sodium hydroxide, dissolving in 100ml of deionized water to prepare an alkali liquor, slowly dropwise adding the alkali liquor into the mixed salt solution in the step (1) under the stirring action, adjusting the pH value of the system to be 8.0, raising the temperature of a water bath to 95 ℃ after the pH value is stabilized, reacting for 24 hours at the temperature, centrifuging and washing the obtained mixture to be neutral, and drying at 60 ℃ for 12 hours to obtain the reddish brown salicylic acid radical intercalated layered zinc-iron hydroxide precursor.
(3) Roasting the salicylate intercalation layered zinc-iron hydroxide precursor prepared in the step (2) in a nitrogen atmosphere, heating to 700 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h, and controlling the gas flow rate to be 40mL/cm2And min, obtaining the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst.
Example 3
(1) Weighing 4.752g of zinc nitrate hexahydrate, 1.616g of ferric nitrate nonahydrate and 12.8088g of sodium salicylate, and respectively dissolving in 50mL of deionized water at room temperature to dissolve by ultrasonic waves; firstly, pouring zinc salt and iron salt solution into a four-neck flask, and dropwise adding salicylic acid sodium salt solution into zinc-iron mixed salt solution by using a constant-pressure separating funnel under the action of continuous stirring.
(2) Weighing 6g of sodium hydroxide, dissolving in 100ml of deionized water to prepare an alkali liquor, slowly dropwise adding the alkali liquor into the mixed salt solution in the step (1) under the stirring action, adjusting the pH value of the system to be 7.2, raising the temperature of a water bath to 95 ℃ after the pH value is stabilized, reacting for 24 hours at the temperature, centrifuging and washing the obtained mixture to be neutral, and drying at 60 ℃ for 12 hours to obtain the reddish brown salicylic acid radical intercalated layered zinc-iron hydroxide precursor.
(3) Roasting the salicylate intercalation layered zinc-iron hydroxide precursor prepared in the step (2) in a nitrogen atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, and controlling the gas flow rate to be 60mL/cm2And min, obtaining the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst.
Claims (8)
1. The metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst is characterized in that the size of metallic iron nano particles of the catalyst is 5-10nm, the size of zinc oxide nano particles is 10-40nm, and the metallic iron and the zinc oxide nano particles are uniformly dispersed in a graphitized carbon matrix.
2. A preparation method of metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst is characterized in that the method takes layered zinc-iron hydroxide of salicylate intercalation as a precursor, and the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst is prepared by one-step solid state pyrolysis reaction in nitrogen or inert atmosphere.
3. The preparation method of the metallic iron/zinc oxide/carbon three-element nano composite visible light catalyst according to claim 2, wherein the preparation method of the salicylate intercalation layered zinc-iron hydroxide precursor comprises the following steps: the concentration is 0.12-0.50 mol.L-1The zinc salt solution and the concentration of the zinc salt solution are 0.02-0.20 mol.L-1The ferric salt solution is mixed evenly, and then the concentration is 0.15-0.30 mol.L-1The salicylate solution is dropwise added into the mixed solution of zinc salt and iron salt, wherein the molar ratio of the zinc salt to the iron salt is 5-2:1, and the molar ratio of the sum of the molar numbers of the zinc salt and the iron salt to the salicylate is 2-1: 1; and (3) adjusting the pH value of the mixed solution to 7-8 by using a sodium hydroxide solution, reacting for 6-48h at 40-100 ℃, and centrifuging, washing and drying to obtain the salicylic acid radical intercalated layered zinc-iron hydroxide precursor.
4. The preparation method of the metallic iron/zinc oxide/carbon ternary nanocomposite visible light catalyst according to claim 2, wherein the solid state pyrolysis reaction conditions are as follows: the layered zinc-iron hydroxide precursor of the salicylate intercalation is placed in a porcelain boat, the temperature is raised to 600-800 ℃ at the temperature rise rate of 2-5 ℃/min, and the temperature is kept for 0-4 h.
5. The preparation method of the metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst according to claim 2, wherein the zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate; the ferric salt is one or more of ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate; the salicylate is sodium salicylate or potassium salicylate.
6. The method for preparing metallic iron/zinc oxide/carbon ternary nanocomposite visible light catalyst according to claim 2, wherein the inert atmosphere is one or both of argon and helium.
7. The application of the metallic iron/zinc oxide/carbon three-element nano composite visible light catalyst prepared by the method according to any one of claims 2 to 6 in catalytic degradation of organic pollutants.
8. Use according to claim 7, characterized in that the step of catalytically degrading organic pollutants is:
1) adjusting the concentration of organic pollutants to 5-30mg/L and the pH value to 5-8;
2) adding metal iron/zinc oxide/carbon ternary nano composite visible light catalyst with the dosage of 0.1-1 g/L;
3) firstly, carrying out dark treatment for 30-60min under the condition of no illumination to ensure that a reaction system reaches absorption and desorption balance, then carrying out catalytic degradation reaction by using visible light source irradiation, wherein the light power is 100-350W, and the system temperature is kept at 25-30 ℃.
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