CN106964407A - A kind of CuPc/γ bismuth molybdate composite nano fiber catalysis materials and preparation method and application - Google Patents
A kind of CuPc/γ bismuth molybdate composite nano fiber catalysis materials and preparation method and application Download PDFInfo
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- CN106964407A CN106964407A CN201710192170.8A CN201710192170A CN106964407A CN 106964407 A CN106964407 A CN 106964407A CN 201710192170 A CN201710192170 A CN 201710192170A CN 106964407 A CN106964407 A CN 106964407A
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- bismuth molybdate
- bismuth
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 126
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000000463 material Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 19
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 18
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 18
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 18
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000007146 photocatalysis Methods 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 11
- 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 11
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 10
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims 9
- 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 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001523 electrospinning Methods 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 238000002835 absorbance Methods 0.000 description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 17
- 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 16
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- -1 molybdic acid bismuth series Chemical class 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
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Abstract
The present invention provides a kind of CuPc/γ bismuth molybdate composite nano fiber catalysis materials and preparation method and application.Spinnability precursor sol is prepared by primary raw material of ammonium molybdate, five water bismuth nitrates, citric acid, inorganic acid and polyvinylpyrrolidone, above-mentioned precursor sol electrospinning is obtained into γ bismuth molybdate nanofibers into gelatinous fibre through calcination processing using electrostatic spinning technique；Then CuPc is loaded to by γ bismuth molybdate nanofiber surfaces by solvent-thermal method, prepares CuPc/γ bismuth molybdate composite nano fiber catalysis materials.Prepared nanofiber catalysis material has high photocatalytic activity, and recyclable recycling, significantly reduces application cost.
Description
Technical field
The present invention relates to a kind of CuPc/γ-bismuth molybdate composite nano fiber catalysis material and preparation method thereof with answering
With belonging to catalysis material technical field.
Background technology
Bismuth molybdate (Bi2MoO6), it is by [Bi2O2]2+Layer is mixed in MoO4 2-The layering Aurivillius oxidations that interlayer is constituted
Thing, due to its unique energy gap (Eg=2.5-2.8eV), and absorbable visible ray of the wavelength in the range of 400-500nm
And the photochemical catalyst as great application prospect.However, the same with other single semiconductor light-catalysts, bismuth molybdate is because photoproduction
The recombination rate in electronics and hole is higher to cause quantum yield low, and this is still one and chosen for meeting the need for practical application
War.Therefore, Nanoscale, 2013,5:6307-6310, it was recently reported that Bi2MoO6/ RGO photochemical catalysts, prepared semiconductor is different
Matter structure molybdic acid bismuth series photocatalyst is compared with single bismuth molybdate photochemical catalyst, and its photocatalysis effect improves；But should
Invention is to prepare nano lamellar material using hydro-thermal method, and the pattern is unfavorable for the separation of photo-generate electron-hole pair, and made
The standby photochemical catalyst rate of recovery is relatively low, it is more difficult to recycle and reuse.
In addition, being also disclosed on oxide and the patent document of bismuth molybdate composite photo-catalyst preparation method, for example, CN
104096558 A disclose a kind of ZnO/Bi2MoO6Composite photo-catalyst and preparation method thereof, using zinc acetate, bismuth nitrate and molybdenum
Sour sodium is raw material, is stirred, and adjusts pH value, and ZnO/Bi then is made using hydro-thermal reaction2MoO6Composite photo-catalyst.The hair
Bright obtained composite catalyst has preferable absorption in wavelength for 320-580nm ultraviolet-visible light area, has to methyl orange
Photocatalytic degradation effect.For another example, the A of CN 102658121 disclose a kind of light degradation catalytic organism agent Bi2O3/Bi2MoO6, it is
Synthesized by one step hydro thermal method.The catalyst is made up of bismuth oxide and bismuth molybdate mol ratio 20%.Obtained by the invention
Catalyst has preferable photocatalytic degradation organic matter effect, than single bismuth molybdate or bismuth oxide and other ratios
Bi2O3/Bi2MoO6Heterojunction structure catalytic effect is all more preferable.But the non-monodimension nanometer material of composite prepared by the above method, no
Beneficial to the transmission and separation of photo-generated carrier, and it is more difficult recycle and reuse, application cost is higher.
The content of the invention
In order to make up the deficiencies in the prior art, the present invention provides a kind of CuPc/γ-bismuth molybdate composite nano fiber light and urged
Change material, the CuPc/γ-bismuth molybdate composite nano fiber catalysis material under sunshine irradiation there is high catalysis to live
Property, and recoverable, significantly reduce production cost.
The present invention also provide a kind of CuPc/γ-bismuth molybdate composite nano fiber catalysis material preparation method and its
Using.
Term explanation：
Room temperature：Room temperature of the present invention has implication well known in the art, generally refers to 20-25 DEG C.
Technical scheme is as follows：
A kind of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, its microscopic appearance is received in γ-bismuth molybdate
Rice fiber surface is loaded with CuPc particle；A diameter of 100-400nm of the γ-bismuth molybdate nanofiber, length is 10-20
μm, CuPc particle is diameter 50-200nm spheric granules.
According to currently preferred, the γ-bismuth molybdate nanofiber is former for reaction by ammonium molybdate and five water bismuth nitrates
Material prepares spinnability precursor sol, is made through electrostatic spinning；The CuPc particle is by phthalonitrile, copper acetate and molybdenum
Sour ammonium is that reaction raw materials are deposited on the γ-bismuth molybdate nanofiber through solvent thermal reaction, so as to form CuPc/γ-molybdenum
Sour bismuth composite nano fiber catalysis material.
It is preferred that, the mass ratio of the ammonium molybdate and five water bismuth nitrates is (0.07-0.55)：(0.38-3.23)；The neighbour
The mass ratio of benzene dicarbonitrile, copper acetate and ammonium molybdate is (5-12)：(1-6)：(0.1-0.5)；The γ-bismuth molybdate nanofiber
Mass ratio with copper acetate is (6-31)：(1-6).
According to currently preferred, a diameter of 200-300nm of the γ-bismuth molybdate nanofiber, length is 10-15 μ
M, a diameter of 100-200nm of CuPc particle.
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol
Citric acid is dissolved in deionized water, ammonium molybdate, five water bismuth nitrates and acid solution A is added, is stirred at room temperature molten
Liquid B；Solution B and acid solution C are added in absolute ethyl alcohol, mixed at room temperature uniformly obtains solution D；Polyvinylpyrrolidone is molten
In the above-mentioned solution Ds of Xie Yu, it is stirred at room temperature, produces spinnability precursor sol；
(2) preparation of γ-bismuth molybdate nanofiber
The spinnability precursor sol that step (1) is obtained is 15-35 DEG C in temperature, and 10-30kV voltage, air is relative
Humidity be 18-55% under the conditions of, carry out electrostatic spinning；Through drying, gelatinous fibre is obtained；In under air atmosphere, with 1-10 DEG C/min
Heating rate be warming up to 400-600 DEG C, high-temperature process 0.5-5h produces γ-bismuth molybdate nanofiber；
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material
At room temperature, phthalonitrile, copper acetate and ammonium molybdate are dissolved into ethylene glycol, add step (2) and prepare
γ-bismuth molybdate nanofiber, after being uniformly dispersed, in hydro-thermal reaction 8-24h at 120-220 DEG C；It is scrubbed, dry, produce phthalein
Cyanines copper/γ-bismuth molybdate composite nano fiber catalysis material.
According to currently preferred, citric acid in the step (1), ammonium molybdate, the matter of five water bismuth nitrates and deionized water
Measuring ratio is：(1.0-3.6)：(0.07-0.55)：(0.38-3.23)：(8-40).
It is preferred that, five water bismuth nitrates and the mass ratio of deionized water are in the step (1)：(0.38-3.23)：(8-
20)。
According to currently preferred, the volume ratio of acid solution A and deionized water is in the step (1)：(1-10)：(8-
40)。
It is preferred that, the volume ratio of acid solution A and deionized water is in the step (1)：(1-3)：(8-20).
According to currently preferred, the volume ratio of solution B, acid solution C and absolute ethyl alcohol is (0.5- in the step (1)
4)：(0.5-4)：(4-20).
It is preferred that, the volume ratio of solution B, acid solution C and absolute ethyl alcohol is (0.5-4) in the step (1)：(0.5-4)：
(8-15)。
According to currently preferred, the quality of polyvinylpyrrolidone is dense in step (1) the spinnability precursor sol
Spend for 0.02-0.3g/mL.
According to currently preferred, acid solution A and acid solution C is respectively that nitric acid, acetic acid or hydrochloric acid are molten in the step (1)
One kind in liquid；The mass fraction of the acid solution A and acid solution C are 30-70%；The acid solution A is identical with acid solution C
Or it is different.
According to currently preferred, electrostatic spinning is by colloidal sol with the syringe with stainless steel syringe needle in the step (2)
Spinning solution is sprayed onto on receiver board；The internal diameter of the stainless steel syringe needle is 0.2-2mm, and the ejection speed of colloidal sol spinning solution is 1-4mL/
H, the reception distance between stainless steel syringe needle and receiver board is 10-35cm.
According to currently preferred, drying condition is to dry 10-30h at 40-120 DEG C in the step (2).
According to currently preferred, 400-600 DEG C, height are warming up to 1-5 DEG C/min heating rate in the step (2)
Temperature processing 1-4h.
According to currently preferred, phthalonitrile, copper acetate, the mass ratio of ammonium molybdate are (2.5- in the step (3)
21)：(1-6)：(0.1-0.5)；The quality of the copper acetate and the volume ratio of ethylene glycol are (0.01-0.06)：(8-50)g/mL.
It is preferred that, phthalonitrile, copper acetate, the mass ratio of ammonium molybdate are (5-12) in the step (3)：(1-6)：
(0.1-0.5)；The quality of the copper acetate and the volume ratio of ethylene glycol are (0.01-0.06)：(20-50)g/mL.
According to currently preferred, the mass ratio of γ-bismuth molybdate nanofiber and copper acetate is (6- in the step (3)
31)：(1-6).
It is preferred that, the mass ratio of γ-bismuth molybdate nanofiber and copper acetate is (13-31) in the step (3)：(1-6).
According to currently preferred, in solvent thermal reaction 12-24h at 140-180 DEG C in the step (3).
According to currently preferred, mode of washing is in the step (3)：Alternately washed with deionized water and absolute ethyl alcohol
Wash.
According to currently preferred, drying condition is in the step (3)：20-40h is dried at 40-120 DEG C.
According to currently preferred, a diameter of 0.2-1.5 μm of gelatinous fibre in the step (2), γ-bismuth molybdate nanometer
A diameter of 100-400nm of fiber.
The application of above-mentioned CuPc/γ-bismuth molybdate composite nano fiber catalysis material, for rhodamine B, methylene blue
Or the photocatalytic degradation of methyl orange.
The technical characterstic and excellent results of the present invention：
CuPc (C32H16CuN8, CuPc) and it is a kind of blue compound, it is very steady under strong acid, highly basic and hot conditions
It is fixed.The present invention, which surprisingly has found CuPc and γ-bismuth molybdate nanofiber being combined, can make material absorb more visible rays, have
Beneficial to raising photocatalysis efficiency；One-dimensional linear heterojunction structure is formed between CuPc and γ-bismuth molybdate, light induced electron can be promoted
With the separation in hole, so as to ensure that more light induced electrons and hole participate in redox reaction, greatly strengthen photocatalysis efficiency.
Synthesis and the report of photocatalytic activity of the one-dimensional linear CuPc with γ-bismuth molybdate heterojunction structure are not yet related at present.
Beneficial effects of the present invention are as follows：
1st, for catalysis material, microscopic appearance is to influence the key factor of its photocatalysis performance.The phthalein of the present invention
Cyanines copper/γ-bismuth molybdate composite nano fiber catalysis material, nanofiber surface is coated with a large amount of spheric granules, and this shows phthalein
Heterojunction structure is formd between cyanines copper and γ-bismuth molybdate, the separation in light induced electron and hole can be promoted；This one-dimensional linear knot
Structure, compared with the composite of other patterns, is more beneficial for the transmission and transfer of electronics, transmission beneficial to photo-generated carrier and point
From so as to ensure that more light induced electrons and hole participate in redox reaction, greatly strengthening photocatalysis efficiency.
2nd, CuPc/γ-bismuth molybdate composite nano fiber produced by the present invention, the composite nano fiber diameter dimension phase
To uniform, CuPc particle disperses relatively uniform, and achievement solves the technical barrier that CuPc particle is easily reunited.CuPc pair can
There is stronger absorption in Jian Guang areas, material is absorbed more visible rays after being combined with γ-bismuth molybdate nanofiber, are conducive to
Improve photocatalysis efficiency.
3rd, preparation method step of the invention is simple, it is easy to operate, with low cost.And the material of one-dimensional linear pattern is just
Reclaimed in by sedimentation, reusable edible further reduces cost, solve conventional powder phthalocyanine salts heterojunction structure light and urge
The problem of agent hardly possible reclaims and causes secondary pollution.
Brief description of the drawings
Fig. 1 is the SEM image under γ made from the step of embodiment 1 (2)-low multiplication factor of bismuth molybdate nanofiber.
Fig. 2 is the SEM image under γ made from the step of embodiment 1 (2)-bismuth molybdate nanofiber high-amplification-factor.
Fig. 3 is under CuPc/γ-low multiplication factor of bismuth molybdate composite nano fiber catalysis material made from embodiment 1
SEM image.
Fig. 4 is under CuPc/γ made from embodiment 1-bismuth molybdate composite nano fiber catalysis material high-amplification-factor
SEM image.
Fig. 5 is the X-ray diffractogram of CuPc/γ-bismuth molybdate composite nano fiber catalysis material made from embodiment 2
Spectrum.
Fig. 6 is CuPc/γ-bismuth molybdate composite nano fiber catalysis material made from embodiment 3 and CuPc, implementation
The UV-vis DRS contrast spectrum of γ-bismuth molybdate nanofiber made from the step of example 3 (2).
Fig. 7 is CuPc/γ-bismuth molybdate composite nano fiber catalysis material in application examples 1 in simulated solar light irradiation
The absorbance curve of lower photocatalytic degradation methylene blue.
Fig. 8 is CuPc/γ-bismuth molybdate composite nano fiber catalysis material and γ-bismuth molybdate Nanowire in application examples 1
The A of dimensiont/A0With the change curve comparison diagram of light application time.
Fig. 9 is being simulated too for CuPc/γ-bismuth molybdate composite photocatalyst material that comparative example 1 in application examples 1 is prepared
The absorbance curve of the lower photocatalytic degradation methylene blue of sunlight irradiation.
Figure 10 is the CuPc catalysis material for preparing of comparative example 2 light under simulated solar light irradiation in application examples 1
The absorbance curve of catalytic degradation methylene blue.
CuPc/γ-bismuth molybdate composite photocatalyst material and contrast that Figure 11 prepares for comparative example 1 in application examples 1
The A for the CuPc catalysis material that example 2 is preparedt/A0With the change curve comparison diagram of light application time.
Figure 12 is CuPc/γ-bismuth molybdate nanofiber catalysis material weight under simulated solar light irradiation in application examples 1
Four degradation rate curves to methylene blue are recycled again.
Figure 13 is CuPc/γ-bismuth molybdate nanofiber catalysis material light under simulated solar light irradiation in application examples 2
The absorbance curve of catalytic degradation rhodamine B solution.
Figure 14 is A in application examples 2t/A0With the change curve comparison diagram of light application time.
Figure 15 is CuPc/γ-bismuth molybdate nanofiber catalysis material weight under simulated solar light irradiation in application examples 2
Four degradation rate curves to rhodamine B solution are recycled again.
Embodiment
With reference to specific embodiment, the present invention is described further, but not limited to this.
Experimental method described in following embodiments, is conventional method unless otherwise specified simultaneously；The reagent and material
Material, unless otherwise specified, is commercially obtained；Device therefor is conventional equipment.
Embodiment 1
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol：At room temperature, 1.0g citric acids are dissolved into 8ml deionized water,
Stirring is extremely dissolved；0.177g ammonium molybdates and the water bismuth nitrates of 0.970g five are added in above-mentioned solution again, 1.6ml mass is added
Fraction is 68% concentrated nitric acid, is stirred at room temperature after 2h and obtains clear transparent solutions B；It is by 3ml solution Bs and 1.5ml mass fractions
68% concentrated nitric acid is added in 15ml absolute ethyl alcohols, and mixed at room temperature is uniform to obtain solution D；By 1.2g polyvinylpyrrolidones (PVP,
K-90) it is dissolved in above-mentioned solution D, is stirred at room temperature after 15h and produces spinnability precursor sol.
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is transferred to 20ml
In the plastic injector for connecting stainless pin；Internal diameter is connected for 1mm stainless pin with 16kV power supply；In 25 DEG C, air phase
To humidity be 25% under the conditions of, carry out electrostatic spinning；The ejection speed of the colloidal sol spinning solution is 3.40ml/h, stainless steel syringe needle
It is 18cm with the distance between receiver board；Obtained fiber is collected, is placed in 70 DEG C of drying box and dries 10h, obtain gelatinous fibre；
Then, under air atmosphere, 500 DEG C are warming up to 1 DEG C/min heating rate, and is incubated 1h, γ-bismuth molybdate Nanowire is produced
Dimension.
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by the adjacent benzene two of 0.115g
Formonitrile HCN, 0.045g copper acetates and 0.003g ammonium molybdates are dissolved into 20ml ethylene glycol, are sufficiently stirred for；Added into above-mentioned solution
The γ that 0.135g steps (2) are prepared-bismuth molybdate nanofiber, after being uniformly dispersed, is transferred to 50ml polytetrafluoroethyllining linings
Stainless steel cauldron in, and 140 DEG C be incubated 18h；Then reactor is taken out and is cooled to room temperature, through deionized water and nothing
24h is dried in water-ethanol alternating washing three times, 70 DEG C of drying boxes, CuPc/γ-bismuth molybdate composite nano fiber photocatalysis is produced
Material.
Fig. 1 is the SEM image for γ-low multiplication factor of bismuth molybdate nanofiber that the present embodiment is prepared；Fig. 2 be γ-
The SEM image of bismuth molybdate nanofiber high-amplification-factor；Fig. 3 is that CuPc/γ-bismuth molybdate that the present embodiment is prepared is combined
The SEM image of the low multiplication factor of nanofiber catalysis material；Fig. 4 is CuPc/γ-bismuth molybdate composite nano fiber photocatalysis
The SEM image of material high-amplification-factor.From Fig. 1,2, the γ that the present embodiment step (2) is obtained-bismuth molybdate nanofiber
Diameter is in 200-300nm or so, and diameter is relatively uniform, there is 12-15 μm long；From Fig. 3,4, prepared CuPc/γ-
Bismuth molybdate composite nano fiber diameter is about in 200-300nm, and Surface coating has a large amount of spheric granules, and spherical particle diameters size is about
For 100-200nm, illustrate to have carried out between CuPc and γ-bismuth molybdate to be combined well, and form heterojunction structure.
Embodiment 2
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol：At room temperature, 2.5g citric acids are dissolved into 20ml deionized water
In, stirring to dissolving；0.442g ammonium molybdates and the water bismuth nitrates of 2.425g five are added in above-mentioned solution again, 3ml matter is added
The concentrated hydrochloric acid that fraction is 37% is measured, is stirred at room temperature after 1h and obtains clear transparent solutions B.By 2ml solution Bs and 1.0ml mass fractions
It is added to for 37% concentrated hydrochloric acid in 10ml absolute ethyl alcohols, mixed at room temperature is uniform to obtain solution D；By 0.75g polyvinylpyrrolidones
(PVP, K-90) is dissolved in above-mentioned solution D, is stirred at room temperature after 12h and is produced spinnability precursor sol.
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is transferred to 20ml
In the plastic injector for connecting stainless pin；Internal diameter is connected for 1mm stainless pin with 20kV power supply；In 25 DEG C, air phase
It is about under the conditions of 30%, to carry out electrostatic spinning to humidity；The ejection speed of the colloidal sol spinning solution is 2.27ml/h, stainless steel
The distance between syringe needle and receiver board are 15cm；Obtained fiber is collected, is placed in 50 DEG C of drying box and dries 15h, obtain gel
Fiber；Then, under air atmosphere, 450 DEG C are warming up to 2 DEG C/min heating rate, and is incubated 2h, γ-bismuth molybdate is produced
Nanofiber.
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by the adjacent benzene two of 0.077g
Formonitrile HCN, 0.030g copper acetates and 0.005g ammonium molybdates are dissolved into 50ml ethylene glycol, are sufficiently stirred for；Added into above-mentioned solution
The γ that 0.305g steps (2) are prepared-bismuth molybdate nanofiber, after being uniformly dispersed, is transferred to 50ml polytetrafluoroethyllining linings
Stainless steel cauldron in, and 180 DEG C be incubated 12h；Then reactor is taken out and is cooled to room temperature, through deionized water and nothing
24h is dried in water-ethanol alternating washing three times, 50 DEG C of drying boxes, CuPc/γ-bismuth molybdate composite nano fiber photocatalysis is produced
Material.
The diameter of the γ that the present embodiment step (2) is obtained-bismuth molybdate nanofiber is in 200-300nm or so, and diameter is equal
It is even, it is about 12-15 μm.The diameter for CuPc/γ-bismuth molybdate composite nano fiber that the present embodiment is prepared is about in 200-
300nm, surface is coated by a large amount of spheric granules, and spherical particle diameters size is about 100-200nm, illustrate CuPc and γ-
Carry out being combined well between bismuth molybdate, and formd heterojunction structure.
Fig. 5 is the X-ray diffraction of CuPc/γ-bismuth molybdate composite nano fiber catalysis material made from the present embodiment
Collection of illustrative plates.As shown in Figure 5, bismuth molybdate is low-temperature phase γ-bismuth molybdate, and occurs in that the diffraction maximum of CuPc, is not found other
Impurity peaks, it is CuPc/γ-bismuth molybdate composite nano fiber to illustrate prepared nanofiber, and forms heterojunction structure.
Embodiment 3
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol：At room temperature, 2g citric acids are dissolved into 16ml deionized water,
Stirring is extremely dissolved；0.353g ammonium molybdates and the water bismuth nitrates of 1.94g five are added in above-mentioned solution again, 2ml mass point is added
Number is 37% concentrated hydrochloric acid, is stirred at room temperature after 4h and obtains clear transparent solutions B.It is by 2ml solution Bs and 2.0ml mass fractions
37% concentrated hydrochloric acid is added in 8ml absolute ethyl alcohols, and mixed at room temperature is uniform to obtain solution D；By 1g polyvinylpyrrolidones (PVP, K-
90) it is dissolved in above-mentioned solution D, is stirred at room temperature after 24h and produces spinnability precursor sol.
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is transferred to 20ml
In the plastic injector for connecting stainless pin；Internal diameter is connected for 0.8mm stainless pin with 10kV power supply；In 25 DEG C, air
Relative humidity is about under the conditions of 40%, to carry out electrostatic spinning；The ejection speed of the colloidal sol spinning solution is 1.18ml/h, stainless
The distance between draw point head and receiver board are 25cm；Obtained fiber is collected, is placed in 80 DEG C of drying box and dries 20h, obtain solidifying
Glue fiber；Then, under air atmosphere, 550 DEG C are warming up to 4 DEG C/min heating rate, and is incubated 3.5h, γ-molybdenum is produced
Sour bismuth nanofiber.
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by the adjacent benzene of 0.0513g
Dimethoxy nitrile, 0.0199g copper acetates and 0.004g ammonium molybdates are dissolved into 36ml ethylene glycol, are sufficiently stirred for；Add into above-mentioned solution
Enter γ-bismuth molybdate nanofiber that 0.139g steps (2) are prepared, after being uniformly dispersed, be transferred in 50ml polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, and 24h is incubated at 160 DEG C；Then reactor is taken out and is cooled to room temperature, through deionized water and
24h is dried in absolute ethyl alcohol alternating washing three times, 90 DEG C of drying boxes, CuPc/γ-bismuth molybdate composite nano fiber light is produced and urges
Change material.
Fig. 6 is the CuPc/γ-bismuth molybdate composite nano fiber catalysis material and CuPc that the present embodiment is prepared
The UV-vis DRS pair of γ-bismuth molybdate nanofiber prepared by (preparation method is shown in comparative example 2), the present embodiment step (2)
Compare spectrum.It will be appreciated from fig. 6 that the obvious red shift of absorption region of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, this
Q band absorptions with CuPc are relevant, illustrate successfully to construct CuPc/γ-bismuth molybdate heterojunction structure.The expansion of light absorption range,
CuPc/γ-bismuth molybdate composite nano fiber catalysis material is absorbed more visible rays, be conducive to improving photocatalysis
Efficiency.
Embodiment 4
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol：At room temperature, 3.5g citric acids are dissolved into 40ml deionized water
In, stirring to dissolving；0.53g ammonium molybdates and the water bismuth nitrates of 2.91g five are added in above-mentioned solution again, 8ml mass is added
Fraction is 68% concentrated nitric acid, is stirred at room temperature after 2h and obtains clear transparent solutions B.It is by 4ml solution Bs and 4ml mass fractions
68% concentrated nitric acid is added in 20ml absolute ethyl alcohols, and mixed at room temperature is uniform to obtain solution D；By 5g polyvinylpyrrolidones (PVP, K-
90) it is dissolved in above-mentioned solution D, is stirred at room temperature after 15h and produces spinnability precursor sol.
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is transferred to 20ml
In the plastic injector for connecting stainless pin；Internal diameter is connected for 2mm stainless pin with 30kV power supply；In 25 DEG C, air phase
To humidity be 25% under the conditions of, carry out electrostatic spinning；The ejection speed of the colloidal sol spinning solution be 4ml/h, stainless steel syringe needle and
The distance between receiver board is 35cm；Obtained fiber is collected, is placed in 70 DEG C of drying box and dries 10h, obtain gelatinous fibre；So
Afterwards, under air atmosphere, 500 DEG C are warming up to 1 DEG C/min heating rate, and is incubated 0.5h, γ-bismuth molybdate Nanowire is produced
Dimension.
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by the adjacent benzene two of 0.154g
Formonitrile HCN, 0.06g copper acetates and 0.005g ammonium molybdates are dissolved into 20ml ethylene glycol, are sufficiently stirred for；Added into above-mentioned solution
The γ that 0.2g steps (2) are prepared-bismuth molybdate nanofiber, after being uniformly dispersed, is transferred to 50ml polytetrafluoroethyllining linings
In stainless steel cauldron, and 8h is incubated at 220 DEG C；Then reactor is taken out and is cooled to room temperature, through deionized water and anhydrous
24h is dried in ethanol alternating washing three times, 70 DEG C of drying boxes, CuPc/γ-bismuth molybdate composite nano fiber photocatalysis material is produced
Material.
Embodiment 5
A kind of preparation method of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, including step are as follows：
(1) preparation of spinnability precursor sol：At room temperature, 1.5g citric acids are dissolved into 20ml deionized water
In, stirring to dissolving；0.07g ammonium molybdates and the water bismuth nitrates of 0.388g five are added in above-mentioned solution again, 1ml mass is added
Fraction is 68% concentrated nitric acid, is stirred at room temperature after 2h and obtains clear transparent solutions B.By 0.5ml solution Bs and 0.5ml mass fractions
It is added to for 68% concentrated nitric acid in 4ml absolute ethyl alcohols, mixed at room temperature is uniform to obtain solution D；By 0.1g polyvinylpyrrolidones (PVP,
K-90) it is dissolved in above-mentioned solution D, is stirred at room temperature after 15h and produces spinnability precursor sol.
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is transferred to 20ml
In the plastic injector for connecting stainless pin；Internal diameter is connected for 2mm stainless pin with 30kV power supply；In 25 DEG C, air phase
To humidity be 25% under the conditions of, carry out electrostatic spinning；The ejection speed of the colloidal sol spinning solution be 1ml/h, stainless steel syringe needle and
The distance between receiver board is 10cm；Obtained fiber is collected, is placed in 70 DEG C of drying box and dries 10h, obtain gelatinous fibre；So
Afterwards, under air atmosphere, 400 DEG C are warming up to 10 DEG C/min heating rate, and is incubated 5h, γ-bismuth molybdate Nanowire is produced
Dimension.
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by the adjacent benzene of 0.0257g
Dimethoxy nitrile, 0.01g copper acetates and 0.001g ammonium molybdates are dissolved into 8ml ethylene glycol, are sufficiently stirred for；Added into above-mentioned solution
The γ that 0.06g steps (2) are prepared-bismuth molybdate nanofiber, after being uniformly dispersed, is transferred to 50ml polytetrafluoroethyllining linings
In stainless steel cauldron, and 24h is incubated at 120 DEG C；Then reactor is taken out and is cooled to room temperature, through deionized water and anhydrous
24h is dried in ethanol alternating washing three times, 70 DEG C of drying boxes, CuPc/γ-bismuth molybdate composite nano fiber photocatalysis material is produced
Material.
Comparative example 1
A kind of preparation method of CuPc/γ-bismuth molybdate composite photocatalyst material, including step are as follows：
(1) preparation of γ-bismuth molybdate nano material
The water bismuth nitrates of 0.971g five, 0.1766g ammonium molybdates are dissolved into 20ml ethylene glycol respectively, room temperature is sufficiently stirred for
Mixed after 30min；In the stainless steel cauldron for being transferred to 50ml polytetrafluoroethyllining linings, and 24h is incubated at 160 DEG C；Then will
Reactor takes out and is cooled to room temperature, through drying 12h in deionized water and absolute ethyl alcohol alternating washing three times, 50 DEG C of drying boxes,
Produce γ-bismuth molybdate nano material.
(2) preparation of CuPc/γ-bismuth molybdate composite
0.06g phthalonitriles, 0.01g copper acetates and 0.001g ammonium molybdates are dissolved into 12ml ethylene glycol respectively, room
Temperature is sufficiently stirred for and mixed；γ-bismuth molybdate that 0.06g steps (1) are prepared is added into above-mentioned solution, after being uniformly dispersed,
In the stainless steel cauldron for being transferred to 50ml polytetrafluoroethyllining linings, and 24h is incubated at 120 DEG C；Then reactor is taken out simultaneously
Be cooled to room temperature, through drying 18h in deionized water and absolute ethyl alcohol alternately washing three times, 80 DEG C of drying boxes, produce CuPc/
γ-bismuth molybdate composite photocatalyst material.
Comparative example 2
A kind of preparation method of CuPc catalysis material, including step are as follows：
0.115g phthalonitriles, 0.045g copper acetates and 0.003g ammonium molybdates are dissolved into 20ml ethylene glycol respectively,
It is sufficiently stirred for；In the stainless steel cauldron for being transferred to 50ml polytetrafluoroethyllining linings, and 18h is incubated at 140 DEG C；Then will reaction
Kettle takes out and is cooled to room temperature, through drying 24h in deionized water and absolute ethyl alcohol alternating washing three times, 70 DEG C of drying boxes, produces
CuPc catalysis material.
Application examples 1
The photocatalytic degradation of methylene blue
CuPc/γ that embodiment 1 is prepared-bismuth molybdate composite nano fiber catalysis material, the step of embodiment 1
(2) catalysis material prepared by the γ prepared-bismuth molybdate nanofiber and comparative example 1,2 is respectively applied to methylene blue
(MB) photocatalytic oxidation degradation, the xenon lamp that analog light source used is 500W, the concentration of methylene blue solution is 20mg/L, tool
Body step is as follows：
First, at room temperature, 0.06g testing samples are added in 50ml methylene blue solution, are then put in camera bellows
Middle magnetic agitation 90min, during which, every 30min, takes out 4ml solution；Then, analog light source is opened, takes 4ml molten every 30min
Liquid；The solution centrifugal taken out every time separation is taken into supernatant liquor, supernatant is tested in highest with UV-2550 spectrophotometers respectively
The absorbance of (664nm) at peak；And sample is reclaimed, test the rate of recovery.
Fig. 7 is CuPc/γ-bismuth molybdate composite nano fiber catalysis material of the preparation of embodiment 1 in simulated solar irradiation
The absorbance curve of the lower photocatalytic degradation methylene blue of irradiation；Wherein, 0.0h is represented to add after catalyst after dark reaction 90min
Absorbance curve (influence for excluding photochemical catalyst absorption), 0.5-4.5h represents the absorbance curve under different light application times.And
Photocatalytic oxidation degradation efficiency of the sample to methylene blue is calculated by public formula (I).
Public formula (I)：η=[(A0-At)/A0] × 100%,
In formula (I), A0The absorbance measured first for solution, AtThe absorbance measured for the t times.
Fig. 8 is the A of CuPc/γ-bismuth molybdate composite nano fiber catalysis material and γ-bismuth molybdate nanofibert/A0
With the change curve comparison diagram of light application time.
Fig. 9 is the obtained CuPc/γ-bismuth molybdate composite photocatalyst material of comparative example 1 light under simulated solar light irradiation
The absorbance curve of catalytic degradation methylene blue；Figure 10 is the obtained CuPc catalysis material of comparative example 2 in simulated solar irradiation
The absorbance curve of the lower photocatalytic degradation methylene blue of irradiation；Figure 11 is CuPc/γ-molybdic acid that comparative example 1,2 is prepared
The A of bismuth composite photocatalyst material and CuPc catalysis materialt/A0With the change curve comparison diagram of light application time.
By Fig. 8,11 it will be clear that prepare compared to the step of embodiment 1 (2) γ-bismuth molybdate nanofiber,
And catalysis material prepared by comparative example 1,2, CuPc/γ-bismuth molybdate nanofiber catalysis material prepared by the present invention
Photocatalysis efficiency is significantly improved, and illustrates one-dimensional phthalocyanine copper/γ-bismuth molybdate heterojunction structure fiber to the degradation effect of methylene blue more
It is excellent.
Figure 12 is that CuPc/γ-bismuth molybdate composite nano fiber catalysis material repeats to follow under simulated solar light irradiation
Ring utilizes four degradation rate curves to methylene blue.As shown in Figure 12, after recycling for four times, the photocatalysis effect of sample is still
It is so very high, illustrate that catalysis material prepared by the present invention has good stability, production cost can be greatly reduced.
Sample recovery rate test is as shown in table 1：
The sample recovery rate of table 1
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Sample recovery rate | 99% | 80% | 78% |
As shown in Table 1, the nanofiber catalysis material rate of recovery that prepared by the present invention is higher, is easier to recycling.
Application examples 2
The photocatalytic degradation of rhodamine B
CuPc/γ that embodiment 1 is prepared-bismuth molybdate composite nano fiber catalysis material, the step of embodiment 1
(2) γ prepared-bismuth molybdate nanofiber is respectively applied to the photocatalytic oxidation degradation of rhodamine B, simulated light used
Source is 350W xenon lamp, and the concentration of rhodamine B solution is 10mg/L, is comprised the following steps that：
First, at room temperature, 0.06g testing samples are added in 50ml rhodamine B solution, be then put in camera bellows
Magnetic agitation 90min, during which, every 30min, takes out 4ml solution；Then, analog light source is opened, takes 4ml molten every 30min
Liquid；The solution centrifugal separation of taking-up is taken into supernatant liquor, supernatant is tested at top with UV-2550 spectrophotometers
The absorbance of (554nm).
Figure 13 is CuPc/γ-bismuth molybdate composite nano fiber catalysis material photocatalysis under simulated solar light irradiation
The absorbance curve of rhodamine B degradation solution；Wherein, 0.0h represents that the extinction added after catalyst after dark reaction 90min is write music
Line (influence for excluding photochemical catalyst absorption), 0.5-4h represents the absorbance curve under different light application times.And based on public formula (I)
Calculate the photocatalytic oxidation degradation efficiency of sample.
Public formula (I)：η=[(A0-At)/A0] × 100%,
In formula (I), A0The absorbance measured first for solution, AtThe absorbance measured for the t times.
Figure 14 is the A of CuPc/γ-bismuth molybdate composite nano fiber catalysis materialt/A0It is bent with the change of light application time
Line comparison diagram, it may be clearly seen that, CuPc/γ-bismuth molybdate composite nano fiber catalysis material photocatalysis efficiency is compared
The γ that the step of embodiment 1 (2) is prepared-bismuth molybdate nanofiber is significantly improved, and illustrates CuPc/γ-bismuth molybdate hetero-junctions
Structure fiber is more excellent to the degradation effect of rhodamine B solution.
Figure 15 is that CuPc/γ-bismuth molybdate composite nano fiber catalysis material repeats to follow under simulated solar light irradiation
Ring utilizes four degradation rate curves to rhodamine B solution.As shown in Figure 15, after recycling for four times, the photocatalysis effect of sample
Fruit is still very high, illustrates that catalysis material prepared by the present invention has good stability, can greatly reduce production cost.
Claims (10)
1. a kind of CuPc/γ-bismuth molybdate composite nano fiber catalysis material, its microscopic appearance is in γ-bismuth molybdate nanometer
Fiber surface is loaded with CuPc particle；A diameter of 100-400nm of the γ-bismuth molybdate nanofiber, length is 10-20 μ
M, CuPc particle is diameter 50-200nm spheric granules.
2. CuPc/γ according to claim 1-bismuth molybdate composite nano fiber catalysis material, it is characterised in that institute
It by ammonium molybdate and five water bismuth nitrates is that reaction raw materials prepare spinnability precursor sol to state γ-bismuth molybdate nanofiber to be, through quiet
Electrospun is made；The CuPc particle be by phthalonitrile, copper acetate and ammonium molybdate be reaction raw materials through solvent thermal reaction
It is deposited on the γ-bismuth molybdate nanofiber, so as to form CuPc/γ-bismuth molybdate composite nano fiber catalysis material；
The mass ratio of the ammonium molybdate and five water bismuth nitrates is (0.07-0.55)：(0.38-3.23)；The phthalonitrile, vinegar
The mass ratio of sour copper and ammonium molybdate is (5-12)：(1-6)：(0.1-0.5)；The γ-bismuth molybdate nanofiber and copper acetate
Mass ratio is (6-31)：(1-6)；
It is preferred that, a diameter of 200-300nm of the γ-bismuth molybdate nanofiber, length is 10-15 μm, CuPc particle
A diameter of 100-200nm.
3. the preparation method of CuPc/γ as claimed in claim 1 or 2-bismuth molybdate composite nano fiber catalysis material, bag
Include step as follows：
(1) preparation of spinnability precursor sol：Citric acid is dissolved in deionized water, ammonium molybdate, five water bismuth nitrates are added
With acid solution A, solution B is stirred at room temperature to obtain；Solution B and acid solution C are added in absolute ethyl alcohol, mixed at room temperature uniformly obtains molten
Liquid D；Polyvinylpyrrolidone is dissolved in above-mentioned solution D, is stirred at room temperature, spinnability precursor sol is produced；
The acid solution A and acid solution C are respectively one kind in nitric acid, acetic acid or hydrochloric acid solution；The acid solution A and acid solution
C mass fraction is 30-70%；The acid solution A and acid solution C are identical or different；
(2) preparation of γ-bismuth molybdate nanofiber：The spinnability precursor sol that step (1) is obtained is 15-35 in temperature
DEG C, 10-30kV voltage, relative air humidity be 18-55% under the conditions of, carry out electrostatic spinning；Through drying, gelatinous fibre is obtained；
In under air atmosphere, 400-600 DEG C is warming up to 1-10 DEG C/min heating rate, high-temperature process 0.5-5h produces γ-molybdic acid
Bismuth nanofiber；
(3) preparation of CuPc/γ-bismuth molybdate composite nano fiber catalysis material：At room temperature, by phthalonitrile, acetic acid
Copper and ammonium molybdate are dissolved into ethylene glycol, add γ-bismuth molybdate nanofiber that step (2) is prepared, after being uniformly dispersed, in
Hydro-thermal reaction 8-24h at 120-220 DEG C；It is scrubbed, dry, produce CuPc/γ-bismuth molybdate composite nano fiber photocatalysis material
Material.
4. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, citric acid in the step (1), ammonium molybdate, the mass ratio of five water bismuth nitrates and deionized water are：(1.0-3.6):
(0.07-0.55)：(0.38-3.23)：(8-40)；The volume ratio of acid solution A and deionized water is：(1-10)：(8-40)；
It is preferred that, five water bismuth nitrates and the mass ratio of deionized water are in the step (1)：(0.38-3.23)：(8-20)；Institute
The volume ratio for stating acid solution A and deionized water is：(1-3)：(8-20).
5. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, the volume ratio of solution B, acid solution C and absolute ethyl alcohol is (0.5-4) in the step (1)：(0.5-4)：(4-
20)；
It is preferred that, the volume ratio of solution B, acid solution C and absolute ethyl alcohol is (0.5-4) in the step (1)：(0.5-4)：(8-
15)。
6. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, the mass concentration of polyvinylpyrrolidone is 0.02-0.3g/mL in step (1) the spinnability precursor sol.
7. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, electrostatic spinning is that colloidal sol spinning solution is sprayed onto into receiver board with the syringe with stainless steel syringe needle in the step (2)
On；The internal diameter of the stainless steel syringe needle is 0.2-2mm, and the ejection speed of colloidal sol spinning solution is 1-4mL/h, stainless steel syringe needle and is connect
The reception distance received between plate is 10-35cm；
It is preferred that, 400-600 DEG C, high-temperature process 1-4h are warming up to 1-5 DEG C/min heating rate in the step (2).
8. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, phthalonitrile, copper acetate, the mass ratio of ammonium molybdate are (2.5-21) in the step (3)：(1-6)：(0.1-
0.5)；The quality of the copper acetate and the volume ratio of ethylene glycol are (0.01-0.06)：(8-50)g/mL；
It is preferred that, phthalonitrile, copper acetate, the mass ratio of ammonium molybdate are (5-12) in the step (3)：(1-6)：(0.1-
0.5)；The quality of the copper acetate and the volume ratio of ethylene glycol are (0.01-0.06)：(20-50)g/mL.
9. the preparation method of CuPc/γ according to claim 3-bismuth molybdate composite nano fiber catalysis material, its
It is characterised by, the mass ratio of γ-bismuth molybdate nanofiber and copper acetate is (6-31) in the step (3)：(1-6)；
It is preferred that, the mass ratio of γ-bismuth molybdate nanofiber and copper acetate is (13-31) in the step (3)：(1-6)；
It is preferred that, in hydro-thermal reaction 12-24h at 140-180 DEG C in the step (3).
10. the application of CuPc/γ as claimed in claim 1 or 2-bismuth molybdate composite nano fiber catalysis material, is used for
The photocatalytic degradation of rhodamine B, methylene blue or methyl orange.
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