CN110586130A - Z-system visible light catalytic material based on crystal face energy level difference and hole trap synergistic effect and preparation method thereof - Google Patents
Z-system visible light catalytic material based on crystal face energy level difference and hole trap synergistic effect and preparation method thereof Download PDFInfo
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- CN110586130A CN110586130A CN201910966666.5A CN201910966666A CN110586130A CN 110586130 A CN110586130 A CN 110586130A CN 201910966666 A CN201910966666 A CN 201910966666A CN 110586130 A CN110586130 A CN 110586130A
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- 239000013078 crystal Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 230000005524 hole trap Effects 0.000 title claims abstract description 20
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 20
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 147
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 104
- 230000001699 photocatalysis Effects 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 45
- 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 38
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 38
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 30
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 23
- 229940043267 rhodamine b Drugs 0.000 claims description 22
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 19
- 229940032753 sodium iodate Drugs 0.000 claims description 19
- 235000015281 sodium iodate Nutrition 0.000 claims description 19
- 239000011697 sodium iodate Substances 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 230000001678 irradiating effect Effects 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 13
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 229910021281 Co3O4In Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 8
- 239000004100 Oxytetracycline Substances 0.000 claims description 7
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims description 7
- 229960000625 oxytetracycline Drugs 0.000 claims description 7
- 235000019366 oxytetracycline Nutrition 0.000 claims description 7
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 239000000969 carrier Substances 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000010893 electron trap Methods 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/16—Reducing
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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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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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
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Abstract
The invention discloses a Z system based on crystal plane energy level difference and hole trap synergistic effectVisible light catalytic material and preparation method thereof, BiVO4Decahedron is used as matrix, and Co is prepared by light deposition and chemical oxidation reaction3Selectively loading O and Ag @ AgBr to BiVO4110 crystal face and 010 crystal face to obtain the Z system photocatalytic material Ag @ AgBr/BiVO4/Co3O4. Because of BiVO4The 110 crystal face and the 010 crystal face have energy level difference and have the space separation effect of photon-generated carriers, so that BiVO (BiVO)4The photoproduction electrons migrate to be enriched to a 010 crystal face and are compounded with photoproduction holes of Ag @ AgBr loaded on the 010 crystal face, and BiVO4The photogenerated holes are migrated to be enriched to the 110 crystal face and are enriched to Co due to the electron trap effect3O4The above. The invention has higher visible light utilization efficiency, photogenerated carrier oxidation reduction capability, photogenerated carrier separation efficiency and good visible light catalytic activity.
Description
Technical Field
The invention belongs to the field of environment functional materials, and relates to a Z-system photocatalytic composite material based on a crystal surface energy level and hole trap synergistic effect and a preparation method thereof.
Background
The visible light catalytic oxidation technology has attracted extensive attention in the field of water pollution treatment because of the advantages of low energy consumption, no secondary pollution and the like. However, in the practical application process, the existing photocatalytic materials have the following defects, which limit the application of the photocatalytic materials in the actual pollutant degradation. (1) Titanium dioxide (TiO)2) As a commonly used photocatalytic material, the high forbidden band width (3.2eV) determines that the material can only be used at the wavelengthHas higher catalytic activity under ultraviolet light, which limits the application of the catalyst under visible light; (2) bismuth vanadate (BiVO)4) Is a stable visible light catalytic material, has strong photocatalytic oxidation capability although being resistant to light corrosion and having a positive valence band (+2.7eV), but researches show that BiVO4The visible light utilization rate is low, the photon-generated carriers are easy to recombine (the recombination rate is higher than (60%)
The Chinese patent with the patent application number of 201710262160.7 discloses a preparation method and application of a nitrogen and iron co-doped bismuth vanadate visible-light-induced photocatalyst, and the preparation method comprises the steps of preparing pure BiVO by a hydrothermal method4Then, a secondary hydrothermal method is adopted to obtain nitrogen and iron double-element doped BiVO4. Nitrogen (nonmetal) and iron (metal) doping synergies though through the addition of BiVO4The impurity energy level is formed in the original forbidden band, the absorption of the photocatalytic material to visible light is improved to a certain extent, but the metal is dopedThe sites may become recombination centers of photogenerated carriers to reduce the efficiency of photocatalytic degradation of organic matters. In addition, the catalytic material disclosed in the patent needs 180min for degrading 100mL of methylene blue (10ppm), which indicates that the recombination of photon-generated carriers is still serious, resulting in lower photocatalytic degradation efficiency; chinese patent with patent application number 201611011642.7 discloses Pd/BiVO4The patent takes bismuth nitrate pentahydrate and ammonium vanadate as raw materials and prepares BiVO by a hydrothermal method4. Then BiVO is added4With PdCl2The mixture is calcined by a muffle furnace to obtain Pd/BiVO4A composite nano photocatalyst. Through loading in BiVO4Surface Pd nano-particles for improving BiVO4The separation efficiency of photogenerated carriers. However, the catalytic material disclosed in this patent does not control BiVO4The high-energy crystal face of the catalyst is exposed, and Pd is non-selectively loaded on BiVO4On different crystal faces, self-combination of photon-generated carriers is more serious, so that the efficiency of degrading organic matters by the catalytic material is still low, and the patent publication data show that 120min is required for degrading 5ppm of phenol (the concentration of the catalyst is 1 g/L); a Chinese patent with the patent application number of 201710175136.X discloses a carbon nitride/(040) crystal face bismuth vanadate heterojunction and a preparation method and application thereof, and the patent firstly adopts a hydrothermal method to prepare BiVO with an exposed (040) crystal face4Then preparing g-C by a calcination method3N4And finally, under the action of ultrasound, the two are mixed to form a heterostructure, so that the separation of photon-generated carriers is promoted. However, calcination gives g-C3N4The block is easy to agglomerate and difficult to reuse, which is not beneficial to practical application. Furthermore, g-C3N4/(040)BiVO4Formation of heterostructures, g-C according to energy level matching3N4Transfer of conduction band electrons to BiVO4On a guide belt, BiVO4Hole transfer to g-C in valence band3N4In valence band, although the separation of the photon-generated carriers is promoted in the process, the oxidation-reduction capability of the photon-generated carriers is fundamentally reduced, and the oxidation-degradation of organic pollutants is not facilitated. Therefore, the modification of bismuth vanadate becomes the research in the field of photocatalytic materialsFind out the hot spot.
Disclosure of Invention
The invention aims to provide a Z-system photocatalytic composite material based on crystal surface energy level and hole trap synergistic effect and a preparation method thereof aiming at the defects of bismuth vanadate photocatalytic materials and the defects of the existing bismuth vanadate photocatalytic materials, and BiVO is accurately regulated and controlled4Crystal structure, cleverly utilizing BiVO4Due to the space separation effect of photo-generated charges among different exposed crystal faces, a Z system is creatively constructed on an electron gathering face {010}, so that a hole trap is formed on the crystal face of the hole gathering face {110}, the redox capability of a photo-generated carrier is remarkably improved while the visible light utilization rate and the photo-generated carrier separation efficiency of the photocatalytic material are effectively improved, the degradation level and the catalytic stability of the catalytic material on organic pollutants are greatly improved, and a new thought is provided for designing and constructing the Z system visible photocatalytic material based on the crystal face level effect and the electron trap synergistic effect.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a Z-system photocatalytic composite material based on a crystal face energy level and hole trap synergistic effect has a chemical formula of Ag @ AgBr/BiVO4/Co3O4BiVO of the compound4As a matrix, Co3Selectively loading O and Ag @ AgBr to BiVO4On the crystal face; wherein, the BiVO4In order to expose the decahedral frustum morphology of {010} and {110} crystal faces, Ag @ AgBr is selectively deposited on the BiVO in the form of a core-shell structure4On the {010} crystal face of (C), Co3O4Nanoparticles are selectively deposited on the BiVO4On the 110 crystal plane. By photo-deposition and chemical oxidation reaction of Co3O4And Ag @ AgBr are selectively loaded to BiVO4To obtain the Z system photocatalytic material Ag @ AgBr/BiVO4/Co3O4. The material is under the irradiation of visible light, due to BiVO4The {110} crystal plane and the {010} crystal plane have energy level difference, so the crystal plane has a photo-generated carrier space separation effect, and BiVO (binary induced vacuum)4Is enriched in the photo-generated electron migration{010} crystal face and photogenerated holes of Ag @ AgBr loaded on {010} crystal face are recombined, and BiVO4The hole of the photo-generated space is transferred to be enriched to the {110} crystal face and enriched to Co due to the electron trap effect3O4The above. Thus, in BiVO4Space separation effect of photo-generated carriers, Ag @ AgBr/BiVO4Z system effect of (1) and Co3O4Under the synergistic effect of the electron trap effect, the visible light-induced conversion efficiency, the photo-generated carrier separation and the photocatalytic oxidation reduction capability are obviously improved.
The invention also discloses a preparation method of the Z system photocatalytic composite material based on the crystal surface energy level and hole trap synergistic effect, which comprises the following steps:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in nitric acid, adjusting pH with ammonia water, and aging to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to perform closed hydrothermal reaction, centrifuging, washing and drying to obtain BiVO (bismuth VO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) BiVO prepared in the step (2)4Placing the mixture into cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating the mixture by visible light to react, and oxidizing the cobalt nitrate into Co by a photoproduction cavity3O4And deposited on BiVO4To obtain Co3O4/BiVO4；
(4) Co prepared in the step (3)3O4/BiVO4Putting the silver nitrate into silver nitrate solution, adding ammonium oxalate, irradiating the solution by visible light for reaction, reducing the silver nitrate into silver simple substance by photoproduction electrons, and depositing the silver simple substance on BiVO4To {010} crystal face to obtain Ag/BiVO4/Co3O4；
(5) The Ag/BiVO prepared in the step (4)4/Co3O4Putting the solution into ferric nitrate solution, adding sodium bromide, fully stirring, centrifuging, washing and drying to obtain the Z system photocatalytic material Ag @ AgBr/BiVO4/Co3O4。
In order to optimize the technical scheme, the specific measures adopted further comprise:
in the step (1), the reaction molar ratio of the bismuth nitrate pentahydrate to the ammonium metavanadate is 1 (0.5-2), the pH of the solution is adjusted to 1-5, and the curing time is 1-5 hours.
In the step (2), the reaction temperature of the closed hydrothermal reaction is 150-250 ℃, and the reaction time is 12-18 h.
In the step (3), the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is (0.008-0.2) to 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (0.02-0.5) to (100); the irradiation time of the visible light is 2-4 h.
In the step (4), the reaction molar ratio of the ammonium oxalate to the silver nitrate is (0.02-0.1): 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4The mass ratio of (2-10) to (100); the irradiation time of the visible light is 2-5 h.
In the step (5), Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1 (0.02-0.1) to 0.02-0.1, and the stirring reaction time is 2-4 h.
The invention further protects the application of the photocatalytic composite material prepared by the preparation method of the Z-system photocatalytic composite material based on the synergistic effect of the crystal plane energy level and the hole trap in the catalytic degradation of organic pollutants, wherein the organic pollutants comprise rhodamine B or oxytetracycline.
Ag @ AgBr/BiVO prepared by the method4/Co3O4The Z system photocatalytic material has the following advantages:
1. the invention is prepared by taking bismuth nitrate pentahydrate, ammonium metavanadate, silver nitrate, cobalt nitrate hexahydrate, ammonium oxalate, sodium iodate, ferric nitrate, sodium bromide and the like as raw materials through hydrothermal reaction, light deposition and chemical precipitation. Using BiVO4Space separation effect of photo-generated carriers with different exposed crystal faces, and Ag @ AgBr is selectively loaded on BiVO through a photo-deposition reaction4{010} upper, Co plane3O4Selectively loaded in BiVO4The {010} crystal plane. In the visible light catalytic reaction process, BiVO4{010} crystal face quickly transfers self photo-generated electrons to Ag0Is combined with the photoproduction holes of AgBr, and simultaneously the photoproduction electrons of AgBr are reduced to O2Is O2 -Participate in the degradation of organic pollutants. In addition, Ag0The material not only serves as an electron mediator of a Z system, but also exhibits SPR effect, and the response of the photocatalytic material to visible light is increased. BiVO, on the other hand4The photogenerated holes on the {110} crystal plane are due to Co3O4Is enriched to oxidize organic contaminants. The process realizes the synergistic effect of the pre-separation of the photon-generated carriers, the Z system and the hole trap effect, thereby obviously improving the utilization efficiency of visible light, the catalytic oxidation capability of the photon-generated carriers and the reaction stability.
2. The photocatalytic material prepared by the method can show good catalytic activity and stability in rhodamine B and oxytetracycline.
Drawings
FIG. 1 shows Ag @ AgBr/BiVO prepared by the present invention4/Co3O4Schematic structural diagram of (1).
FIG. 2 is a diagram showing the preparation of Ag @ AgBr/BiVO4/Co3O4Is a schematic flow diagram.
FIG. 3 is the Ag @ AgBr/BiVO prepared in example 14/Co3O4SEM image of (d).
FIG. 4 is the Ag @ AgBr/BiVO prepared in example 14/Co3O4EDS map of (a).
FIG. 5 is the Ag @ AgBr/BiVO prepared in example 24/Co3O4Electron energy spectrum of (1).
FIG. 6 is the 1d orbital electron energy spectrum of O in FIG. 5.
The 2p3 orbital electron energy spectrum of Co in fig. 5 in fig. 7.
FIG. 8 is the 3d orbital electron energy spectrum of Ag in FIG. 5.
FIG. 9 is Ag @ AgBr/BiVO prepared in example 34/Co3O4UV-Vis profile of (1).
FIG. 10 is the Ag @ AgBr/BiVO prepared in example 44/Co3O4Electricity (D) fromChemical characterization pattern.
FIG. 11 is the Ag @ AgBr/BiVO prepared in examples 1-64/Co3O4A schematic diagram of the degradation effect of the rhodamine B with the initial concentration of 10 ppm.
FIG. 12 is Ag @ AgBr/BiVO prepared in example 74/Co3O4The effect of multi-batch degradation on oxytetracycline with the initial concentration of 10ppm is shown schematically.
FIG. 13 is Ag @ AgBr/BiVO prepared in example 74/Co3O4XPS comparison of materials before and after medium reaction.
FIG. 14 is Ag @ AgBr/BiVO prepared in example 74/Co3O4XRD contrast of the materials before and after the reaction in (1).
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples.
Example 1
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:1, adjusting the pH to 2 by using ammonia water, and curing for 2h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 150 ℃ for 15h, centrifuging, washing and drying to obtain BiVO (bismuth VO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 2 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4To obtain Co on the {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.008:1, and the prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (A) to (B) is 0.02: 100;
(4) the step (3) is to prepareObtained Co3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4To obtain Ag/BiVO on the {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of ammonium oxalate to silver nitrate is 0.1:1, and the prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of ferric nitrate to sodium bromide is 1:0.1:0.1, and Ag/BiVO4/Co3O4Ag @ AgBr and BiVO in powder4In a mass ratio of 10: 100; the stirring time was 4 h.
The products prepared in each step are subjected to SEM and EDS characterization, see figures 1 and 3, and BiVO can be obviously seen in scanning electron micrographs4Has decahedral morphology with crystal faces of {010} and {110} exposed simultaneously, and Ag @ AgBr is selectively deposited on the BiVO in the form of a core-shell structure4{010} crystal face of (C), Co3O4Nanoparticles are selectively deposited on the BiVO4{110} crystal plane; referring to fig. 4, the characterization data of EDS shows that the prepared material contains elements of Bi, V, O, etc.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.02 wt%) and pre-adsorbing in dark for 30min, using 350W xenon lamp to simulate sunlight, sampling every 8min to determine rhodamine B concentration, the degradation effect is shown in FIG. 11, and it can be seen from the figure that Co3O4When the load is 0.02 wt%, Ag @ AgBr/BiVO is subjected to 32min of photocatalytic degradation reaction4/Co3O4(0.02 wt%) had a RhB degradation rate of 88%, indicating that the voids were due to Co3O4"cavity")The trap' acts to enrich and effectively remove RhB.
Example 2
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:0.5, adjusting the pH to 1 with ammonia water, and curing for 1h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 250 ℃ for 18h, centrifuging, washing and drying to obtain BiVO (bismuth VO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 4 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.02: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (A) to (B) is 0.05: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4The mass ratio of (A) to (B) is 2: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1:0.02:0.02,the stirring time was 2 h.
XPS characterization of the product prepared in each step revealed that the peak at 779.5eV of the electron binding energy of Co2p3 is Co2p3 as shown in FIGS. 5 to 83O4Characteristic peak of (a); peaks at the electron binding energy 531eV and 529eV of O1s belong to characteristic peaks of V-O and C-O, respectively; the peaks at 367.2eV and 373.4eV of the electron binding energy of Ag 3d belong to Ag in AgBr+The peaks at 368.0eV and 374.2eV belong to Ag @ AgBr/BiVO4Middle Ag0Characteristic peak of (2). As can be seen from the above, Ag @ AgBr and Co3O4Are all successfully loaded in BiVO4On the corresponding crystal plane.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.05 wt%) and pre-adsorbing in dark for 30min, using 350W xenon lamp to simulate sunlight, sampling every 8min to determine rhodamine B concentration, the degradation effect is shown in FIG. 11, and it can be seen from the graph that when Co is adsorbed in dark for 30min3O4When the load of the catalyst is 0.05 wt%, Ag @ AgBr/BiVO4/Co3O4(0.05 wt%) has better degradation effect on RhB, and the degradation rate in 32min is more than 90%.
Example 3
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:2, adjusting the pH to 5 by using ammonia water, and curing for 5 hours to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours, centrifuging, washing and drying to obtain BiVO (BiVO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 3 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein, the sodium iodate and the hexahydrateThe reaction molar ratio of the cobalt nitrate to the cobalt nitrate is 0.04: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (A) to (B) is 0.1: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1:0.1:0.1, and the stirring time is 4 hours.
Characterization of UV-Vis was performed on the product prepared in each step above, as can be seen in FIG. 9, Ag @ AgBr and Co3O4The response of the catalytic material to visible light is greatly enhanced.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.1 wt%) and pre-adsorbing in dark for 30min, using a 350W xenon lamp to simulate sunlight, sampling every 8min to determine the concentration of rhodamine B, wherein the degradation effect is shown in figure 11, and Ag @ AgBr/BiVO is obtained by 32min of photocatalytic reaction4/Co3O4(0.1 wt%) has a degradation rate of 92% for RhB, indicating that Ag @ AgBr/BiVO4/Co3O4Efficiency of RhB degradation with Co3O4The amount of load increases.
Example 4
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:1, adjusting the pH to 2 by using ammonia water, and curing for 2h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours, centrifuging, washing and drying to obtain BiVO (BiVO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 3 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.08: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (A) to (B) is 0.2: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1:0.1:0.1, and the stirring time is 4 hours.
Electrochemical characterization of the products prepared in each step is shown in FIG. 10, where BiVO is observed4A Z system is formed by selectively loading Ag @ AgBr on a {010} crystal face at a {110Lattice face selective loading Co3O4And a hole trap is formed, so that the separation efficiency of the photo-generated carriers of the catalytic material is improved.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.2 wt%) and pre-adsorbing in dark for 30min, using a 350W xenon lamp to simulate sunlight, sampling every 8min to determine the concentration of rhodamine B, wherein the degradation effect is shown in figure 11, 93% of rhodamine B is removed through 32min photocatalytic reaction, and pure BiVO is contained4Under the same condition, the removal rate of rhodamine B is only 6 percent, and Ag @ AgBr/BiVO4The removal rate of (2) was only 83%. This is fully illustrated in BiVO4Z system constructed by Ag @ AgBr selectively loaded on {010} crystal face and BiVO4Co selectively loaded by {010} crystal face3O4The synergistic effect of the hole trap is formed, and the efficiency of the catalytic material for degrading organic pollutants is improved.
Example 5
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:1, adjusting the pH to 2 by using ammonia water, and curing for 2h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours, centrifuging, washing and drying to obtain BiVO (BiVO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 3 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.06: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4In a mass ratio of 0.15: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The molar ratio of the ferric nitrate to the sodium bromide is 1:0.1:0.1, and the stirring time is 4 hours.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.15 wt%) and pre-adsorbing for 30min under dark condition, using 350W xenon lamp to simulate sunlight, sampling every 8min to determine rhodamine B concentration, the degradation effect is shown in figure 11, and after 32min photocatalytic reaction, the removal rate of rhodamine B is increased to 97.56%, which indicates that 0.15 wt% Co is 0.15 wt% and the removal rate of rhodamine B is increased3O4Is the optimum loading amount.
Example 6
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:1, adjusting the pH to 2 by using ammonia water, and curing for 2h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours, centrifuging, washing and drying to obtain BiVO (BiVO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in hexahydrateAdding sodium iodate into cobalt nitrate solution, irradiating with visible light for 3 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.2: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (A) to (B) is 0.5: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1:0.1:0.1, and the stirring time is 4 hours.
(6) Preparing 50ml of 10mg/L rhodamine B solution, pouring the solution into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.5 wt%) and pre-adsorbing for 30min in the dark, using a 350W xenon lamp to simulate sunlight, sampling every 8min to determine the concentration of rhodamine B, wherein the degradation effect is shown in figure 11, and the removal rate of rhodamine B is 90% after 32min photocatalytic reaction, which indicates that Co is used for removing rhodamine B3O4The supported amount is too large and can become a recombination center of an electron hole pair of the catalytic material, so that the photocatalytic efficiency is reduced.
Example 7
The material preparation process is shown in fig. 2, and the specific preparation steps are as follows:
(1) mixing sodium sulfate pentahydrateDissolving bismuth acid and ammonium metavanadate in 60mL of nitric acid according to the mass ratio of 1:1, adjusting the pH to 2 with ammonia water, and curing for 2h to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to carry out closed hydrothermal reaction at the reaction temperature of 200 ℃ for 12 hours, centrifuging, washing and drying to obtain BiVO (BiVO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) 0.1g of BiVO prepared in the step (2)4Placing the powder in cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating with visible light for 3 hr, and oxidizing cobalt nitrate into Co3O4And deposited on BiVO4Obtaining Co on {110} crystal face3O4/BiVO4Powder; wherein the reaction molar ratio of the sodium iodate to the cobalt nitrate hexahydrate is 0.06: 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4In a mass ratio of 0.15: 100;
(4) co prepared in the step (3)3O4/BiVO4Putting the powder into silver nitrate solution, adding ammonium oxalate, irradiating for 2h by visible light, reducing the silver nitrate into silver simple substance and depositing in BiVO4Obtaining Ag/BiVO on {010} crystal face4/Co3O4Powder; wherein the reaction molar ratio of the ammonium oxalate to the silver nitrate is 0.1: 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4In a mass ratio of 10: 100;
(5) the Ag/BiVO prepared in the step (4)4/Co3O4Putting the powder into ferric nitrate solution, adding sodium bromide, fully stirring, and finally centrifuging, washing and drying to obtain the Z-system photocatalytic material Ag @ AgBr/BiVO4/Co3O4(ii) a Wherein, Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1:0.1:0.1, and the stirring time is 4 hours.
(6) Preparing 10mg/L oxytetracycline solution 50ml, pouring into a photoreaction device, and adding 0.5g of Ag @ AgBr/BiVO prepared in the step (5)4/Co3O4(0.15 wt.%) and pre-adsorbed for 30m in the darkin, a 350W xenon lamp is used for simulating the sun, and the photocatalytic reaction is carried out for 22 minutes. The effect graph of photocatalytic degradation of oxytetracycline after recycling is shown in fig. 12, the removal rate of oxytetracycline is still maintained above 90% after 9 times of recycling, and the effect of recycling for 9 times is not obviously reduced.
XPS and XRD characteristics of the materials before and after the reaction are shown in figures 13 and 14, and it can be seen that crystal structures of the materials before and after the reaction are not obviously changed, and Ag0With Ag+The ratio of (A) and (B) is almost unchanged before and after the reaction, which indicates that the material has better stability.
In conclusion, the photocatalytic material prepared by the invention and the traditional BiVO4Compared with a base photocatalytic material, the material has higher visible light utilization efficiency, photocarrier redox capability and photocarrier separation efficiency, the removal rates of rhodamine B and terramycin respectively reach 97.56% (32min) and 97.26% (22min), the effect is not obviously reduced after 9 times of cyclic use, and the material has good catalytic activity and stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (8)
1. A Z system photocatalytic composite material based on crystal surface energy level and hole trap synergistic effect is characterized in that: the chemical formula of the photocatalytic composite material is Ag @ AgBr/BiVO4/Co3O4BiVO of the compound4As a matrix, Co3Selectively loading O and Ag @ AgBr to BiVO4On the crystal face; wherein, the BiVO4In order to expose the decahedral frustum morphology of {010} and {110} crystal faces, Ag @ AgBr is selectively deposited on the BiVO in the form of a core-shell structure4On the {010} crystal face of (C), Co3O4Nanoparticles are selectively deposited on the BiVO4On the 110 crystal plane.
2. The preparation method of the Z system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect as claimed in claim 1, characterized by comprising the following steps:
(1) dissolving bismuth nitrate pentahydrate and ammonium metavanadate in nitric acid, adjusting pH with ammonia water, and aging to obtain BiVO4A precursor solution;
(2) BiVO (bismuth oxide) is added4Placing the precursor solution in a polytetrafluoroethylene reaction kettle to perform closed hydrothermal reaction, centrifuging, washing and drying to obtain BiVO (bismuth VO) with crystal faces of {010} and {110} exposed simultaneously4Powder;
(3) BiVO prepared in the step (2)4Placing the mixture into cobalt nitrate hexahydrate solution, adding sodium iodate, irradiating the mixture by visible light to react, and oxidizing the cobalt nitrate into Co by a photoproduction cavity3O4And deposited on BiVO4To obtain Co3O4/BiVO4；
(4) Co prepared in the step (3)3O4/BiVO4Putting the silver nitrate into silver nitrate solution, adding ammonium oxalate, irradiating the solution by visible light for reaction, reducing the silver nitrate into silver simple substance by photoproduction electrons, and depositing the silver simple substance on BiVO4To {010} crystal face to obtain Ag/BiVO4/Co3O4；
(5) The Ag/BiVO prepared in the step (4)4/Co3O4Putting the solution into ferric nitrate solution, adding sodium bromide, fully stirring, centrifuging, washing and drying to obtain the Z system photocatalytic material Ag @ AgBr/BiVO4/Co3O4。
3. The preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect is characterized in that in the step (1), the reaction molar ratio of bismuth nitrate pentahydrate to ammonium metavanadate is 1 (0.5-2), the pH value of a solution is adjusted to 1-5, and the curing time is 1-5 hours.
4. The preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect according to claim 2, characterized in that in the step (2), the reaction temperature of the closed hydrothermal reaction is 150-250 ℃, and the reaction time is 12-18 h.
5. The preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect is characterized in that in the step (3), the reaction molar ratio of sodium iodate to cobalt nitrate hexahydrate is (0.008-0.2): 1; prepared Co3O4/BiVO4In, Co3O4And BiVO4The mass ratio of (0.02-0.5) to (100); the irradiation time of the visible light is 2-4 h.
6. The preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect is characterized in that in the step (4), the reaction molar ratio of ammonium oxalate to silver nitrate is (0.02-0.1) to 1; prepared Ag/BiVO4/Co3O4In, Ag and BiVO4The mass ratio of (2-10) to (100); the irradiation time of the visible light is 2-5 h.
7. The preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect as claimed in claim 2, characterized in that in the step (5), Ag/BiVO4/Co3O4The reaction molar ratio of the ferric nitrate to the sodium bromide is 1 (0.02-0.1) to 0.02-0.1, and the stirring reaction time is 2-4 h.
8. The application of the photocatalytic composite material prepared by the preparation method of the Z-system photocatalytic composite material based on the crystal plane energy level and hole trap synergistic effect as claimed in claim 2 in catalytic degradation of organic pollutants, wherein the organic pollutants comprise rhodamine B or oxytetracycline.
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