CN105749983A - Meso-tetra(4-methoxyphenyl)copper porphyrin/Bi2WO6 compound photocatalyst and preparation method - Google Patents
Meso-tetra(4-methoxyphenyl)copper porphyrin/Bi2WO6 compound photocatalyst and preparation method Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- -1 copper porphyrin Chemical class 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 20
- 150000004032 porphyrins Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 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 description 13
- 229940043267 rhodamine b Drugs 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005297 material degradation process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—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
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention provides a meso-tetra(4-methoxyphenyl)copper porphyrin (CuTCPP)/Bi2WO6 compound photocatalyst. A particle is of a sheet-shaped structure and the maximum linear distance between any two points in the particle is 50nm-100nm; and the mass ratio of CuTCPP to Bi2WO6 is (0.1-1.0) to (99-99.9). The invention further provides a preparation method of the compound photocatalyst. The preparation method comprises the following steps: adding Bi2WO6 powder into ethanol and carrying out ultrasonic treatment to obtain a Bi2WO6 suspension solution; dissolving CuTCPP into the ethanol to obtain a CuTCPP solution; mixing the Bi2WO6 suspension solution and the CuTCPP solution; stirring at a room temperature to volatilize ethanol; and washing and drying the product to obtain the CuTCPP/Bi2WO6 compound photocatalyst with relatively high photocatalytic activity. The preparation method provided by the invention is simple and strong in controllability, and large-scale production is easy to realize.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of photochemical catalyst, specifically a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi2WO6Composite photo-catalyst and preparation method thereof.
Background technology
The environmental pollution brought due to the fast development of industry and energy crisis, the problem solving environmental pollution is extremely urgent, and the research of Photocatalitic Technique of Semiconductor and application are the most of great interest.The key problem of photocatalysis technology is the design of appropriate light catalyst, develops and develops.Current research focuses primarily upon TiO2Base system row photochemical catalyst.But due to TiO2Greater band gap, is only capable of absorbing the ultraviolet light accounting for sunshine gross energy 4%, almost without photoresponse in visible-range, which greatly limits the utilization rate of sunshine.In order to better profit from sunshine, people are devoted to develop novel visible light responsive photocatalyst.Wherein as the Bi of one of simple Aurivillius oxide2WO6, due to have under visible light decomposition water and the photocatalysis performance of degradable organic pollutant and receive much concern.
But, simple Bi2WO6Being only capable of the absorbing wavelength visible ray at below 450nm, the visible ray for long-wave band then can not utilize.In order to increase the utilization rate to sunshine, need to widen further Bi2WO6Spectral response range.Porphyrin is a kind of metallo-organic compound with big conjugation circulus, in porphyrin and derivative compound thereof are widely present in organism and in the relevant important organelle of energy transfer.Porphyrin has 26 pi-electrons, is the system of a height conjugation, therefore has well absorption to sunshine.The modal photosynthesis of such as nature, it is simply that utilize chlorophyll (magnesium porphyrin) to capture sunshine.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper (CuTCPP)/Bi2WO6Composite photo-catalyst and preparation method thereof, described this CuTCPP/Bi2WO6Composite photo-catalyst and preparation method thereof mainly solves the technical problem that the spectral response range of photochemical catalyst of the prior art is narrow, low to the utilization rate of light.
The invention provides a kind of CuTCPP/Bi2WO6Composite photo-catalyst, its particle is laminated structure, and the maximum air line distance of any two point in particle, between 50-100nm, calculates, CuTCPP(meso-tetra-(4-methoxyphenyl) porphyrin copper in mass ratio): Bi2WO6For 0.1-1.0:99-99.9.
Further, calculate in mass ratio, CuTCPP:Bi2WO6For 0.1:99.9.
Further, calculate in mass ratio, CuTCPP:Bi2WO6For 0.4:99.6.
Further, calculate in mass ratio, CuTCPP:Bi2WO6For 0.7:99.3.
Further, calculate in mass ratio, CuTCPP:Bi2WO6For 1.0:99.0.
Present invention also offers above-mentioned CuTCPP/Bi2WO6The preparation method of composite photo-catalyst, comprises the following steps:
(1), preparation Bi2WO6The step of powder:
By Bi (NO3)3·5H2O is dissolved in nitric acid, and obtaining concentration is 0.1-2
Bi (the NO of mol/L3)3Solution；
By Na2WO4·2H2O is dissolved in deionized water, and obtaining concentration is 0.05-1
The Na of mol/L2WO4The aqueous solution；
Calculate the most in molar ratio, i.e. Bi (NO3)3Bi in solution3+: Na2WO4WO in the aqueous solution4 2-For the ratio of 2:1, by Bi (NO3)3Solution and Na2WO4The aqueous solution mixes, obtain white suspension solution, then pH value is adjusted to be 1-2 with the NaOH aqueous solution that mass percent concentration is 5%-10%, transferring in water heating kettle, controlling temperature is to react 10 ~ 30 hours at 140 ~ 180 DEG C, the reacting liquid filtering of gained, the product of gained is successively with deionized water and absolute ethanol washing, being then centrifuged for, the precipitation control temperature of gained is 50 ~ 65 DEG C and is dried 5 ~ 15 hours, it is thus achieved that Bi2WO6Powder；
(2), by the Bi of step (1) gained2WO6Powder is dissolved in ethanol and carrying out ultrasonically treated 20 ~ 50 minutes, and control power is 40-100
W, frequency is 20-40 KHz, obtains Bi2WO6Suspension;
(3), CuTCPP is dissolved in ethanol, obtains CuTCPP solution；
(4), then by the Bi of step (2) gained2WO6The CuTCPP solution mixing of step (3) gained of suspension and certain volume, wherein, calculates, CuTCPP:Bi in mass ratio2WO6For 0.1-1.0:99-99.9, then controlling rotating speed is to carry out under 1000-2000 r/min, room temperature reacting 20 ~ 30 hours, and products therefrom is washed with deionized 3-5 time, and then control temperature is 60-80 DEG C and is dried, and obtains CuTCPP/Bi2WO6Composite photo-catalyst.
The present invention utilizes the CuTCPP capture ability to sunshine, has significantly widened Bi2WO6Spectral response range, not only there is higher photocatalytic activity, also there is the highest stability.Composite degradation rate to rhodamine B in 10 minutes reaches 100%, and compound Bi2WO6In the same time, the degradation rate of rhodamine B is only 48.4%.Visible CuTCPP/Bi2WO6Composite photo-catalyst degraded natural conditions under difficult degradation organic pollution in terms of advantageously, there is application prospect.
The present invention compares with prior art, and its technological progress is significant.The present invention is by porphyrin and Bi2WO6Catalysis material is combined, it is possible to utilize the sensibilization of porphyrin significantly to widen Bi2WO6Absorption region to solar spectrum, thus bring being substantially improved of photocatalysis performance, CuTCPP/Bi2WO6The preparation of composite not only has higher scientific value but also have the practical significance that environmental pollution is administered.The preparation method of the present invention is without special installation and harsh conditions, and technique is simple, and controllability is strong, easily accomplishes scale production, has practicality.
Accompanying drawing explanation
Fig. 1 is the CuTCPP/Bi of embodiment 1 gained2WO6The XRD diffraction spectrogram of composite photo-catalyst.
Fig. 2 is the CuTCPP/Bi of embodiment 1 gained2WO6The transmission electron microscope picture of composite photo-catalyst.
Fig. 3 is the CuTCPP/Bi of embodiment 1 gained2WO6Composite photo-catalyst and simple Bi2WO6Diffusing reflection comparison diagram.
Fig. 4 is with the CuTCPP/Bi of embodiment 1 gained2WO6Composite photo-catalyst and simple Bi2WO6Degradation curve comparison diagram to rhodamine B under xenon lamp.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is expanded on further, but it is not limiting as the present invention.
Raw materials used:
Bi(NO3)3·5H2O (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group)
Na2WO4·2H2O (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group)
Nitric acid (is analyzed pure, Chemical Reagent Co., Ltd., Sinopharm Group)
NaOH (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group)
Absolute ethyl alcohol (is analyzed pure, Chemical Reagent Co., Ltd., Sinopharm Group)
CuTCPP (electron level, lark prestige Science and Technology Ltd.)
Embodiment
1
A kind of CuTCPP/Bi2WO6Composite photo-catalyst, described CuTCPP/Bi2WO6Composite photo-catalyst is the laminated structure of size about 50-100nm, calculates in mass ratio, CuTCPP:Bi2WO6For 0.1:99.9.
Above-mentioned a kind of CuTCPP/Bi2WO6Composite photo-catalyst preparation method, specifically includes following steps:
(1), Bi2WO6The preparation of powder
By Bi (NO3)3·5H2O is dissolved in 10mL nitric acid, obtains the Bi (NO that concentration is 2 mol/L3)3Solution；
By Na2WO4·2H2O is dissolved in deionized water, and obtaining concentration is 1
The Na of mol/L2WO4The aqueous solution；
Calculate the most in molar ratio, i.e. Bi (NO3)3Bi in solution3+: Na2WO4WO in the aqueous solution4 2-For the ratio of 2:1, by Bi (NO3)3Solution and Na2WO4The aqueous solution mixes, obtain white suspension solution, then pH value is adjusted to be 1-2 with the NaOH aqueous solution that mass percent concentration is 8 %, transferring in water heating kettle, controlling temperature is to react 20 hours at 160 DEG C, the reacting liquid filtering of gained, the product of gained is successively with deionized water and absolute ethanol washing, being then centrifuged for, the precipitation control temperature of gained is 60 DEG C and is dried 12 hours, it is thus achieved that Bi2WO6Powder；
(2), by the Bi of 0.3 g step (1) gained2WO6Powder joins in 15 mL ethanol, and controlling power is 100 W, and frequency is that 40 KHz are carried out ultrasonically treated 30 minutes, obtains the Bi that concentration is 20 g/L2WO6Suspension;
(3), by 0.003
G CuTCPP is dissolved in 30 mL ethanol, and obtaining concentration is 0.1
The CuTCPP solution of g/L；
(4), then by the Bi of 15 mL step (2) gained2WO6The CuTCPP solution of suspension and 3 mL step (3) gained mixes, then controlling rotating speed is to carry out under 10000 r/min, room temperature reacting 24 hours, and products therefrom is washed with deionized 3 times, then control temperature to be 60 DEG C and be dried, obtain CuTCPP/Bi2WO6Composite photo-catalyst.
Use the X-ray diffractometer (D/max2200PC, the Rigaku Co., Ltd.) CuTCPP/Bi to above-mentioned gained2WO6Composite photo-catalyst is measured, and the XRD of gained spectrum is as it is shown in figure 1, from figure 1 it appears that the CuTCPP/Bi of gained2WO6Bi in composite photo-catalyst2WO6Powder is the Bi of the russellite type structure of rhombic system2WO6, because the compound quantity of CuTCPP is less, XRD spectrum does not shows its diffraction maximum.
Use Flied emission transmission electron microscope (FEI
TecnaiG2F30, FEI Co. of the U.S.) CuTCPP/Bi to above-mentioned gained2WO6Composite photo-catalyst carries out pattern and Characterization for Microstructure, and the transmission electron microscope picture of gained is as in figure 2 it is shown, from figure 2 it can be seen that the CuTCPP/Bi of gained2WO6Composite photo-catalyst is flaky nanometer structure, and the size of nanometer sheet is about 50-100 nm.
Accompanying drawing 3 is the CuTCPP/Bi of the present embodiment gained2WO6Composite photo-catalyst and simple Bi2WO6Diffusing reflection comparison diagram.From accompanying drawing 3 it can be seen that CuTCPP/Bi2WO6The response of visible ray is remarkably reinforced by composite photo-catalyst, and CuTCPP/Bi is described2WO6Composite photo-catalyst can more effectively utilize sunshine.
In order to the photocatalysis performance of sample is prepared by research institute, the experiment of rhodamine B degradation under design simulation sunshine.Step is as follows: by 0.05
The CuTCPP/Bi of g embodiment 1 gained2WO6It is 10 that composite photo-catalyst joins 50 mL concentration-5 In the rhodamine B aqueous solution of mol/L, lucifuge stirs 60 minutes, to reach adsorption equilibrium, is subsequently placed under 500 W xenon lamps irradiation, detects the absorbance of rhodamine B and record result；By ultraviolet-visible absorption spectra measurement rhodamine B solution in the absorbance of 552nm, characterize the change of pollutant levels in solution, and then draw degradation rate；
Testing result shows: start first 5 minutes of illumination, CuTCPP/Bi2WO6Rhodamine B color in the suspension of composite photocatalyst material quickly shoals, and the CuTCPP/Bi obtained intuitively is described2WO6Composite photocatalyst material has higher photocatalytic degradation capability.
The CuTCPP/Bi that accompanying drawing 4 obtains for the present embodiment2WO6Composite photocatalyst material and simple Bi2WO6Nano material correlation curve figure to rhodamine B degradation rate under xenon lamp.From accompanying drawing 4: the CuTCPP/Bi obtained2WO6Composite photocatalyst material degradation rate to rhodamine B in 10 minutes reaches 100%, and simple Bi2WO6Under similarity condition, the degradation rate to rhodamine B only reaches 48.4%, and CuTCPP/Bi is described2WO6Composite photocatalyst material has significant photocatalytic activity.
Embodiment
2
The present embodiment the difference is that only with embodiment 1: CuTCPP and Bi2WO6Mass ratio be 0.4:99.6, remaining content is all identical with described in embodiment 1.Analyze after testing and learn: the CuTCPP/Bi that the present embodiment is obtained2WO6Composite photocatalyst material degradation rate to rhodamine B under the composite the same terms obtained with embodiment 1 is 62.0%, and the composite property obtained than embodiment 1 has declined.
Embodiment
3
The present embodiment the difference is that only with embodiment 1: CuTCPP and Bi2WO6Mass ratio be 0.7:99.3, remaining content is all identical with described in embodiment 1.Analyze after testing and learn: the CuTCPP/Bi that the present embodiment is obtained2WO6Composite photocatalyst material degradation rate to rhodamine B under the composite the same terms obtained with embodiment 1 is 35.1%, and the composite property obtained than embodiment 1 has declined.
Embodiment
4
The present embodiment the difference is that only with embodiment 1: CuTCPP and Bi2WO6Mass ratio be 1.0:99.0, remaining content is all identical with described in embodiment 1.Analyze after testing and learn: the CuTCPP/Bi that the present embodiment is obtained2WO6Composite photocatalyst material degradation rate to rhodamine B under the composite the same terms obtained with embodiment 1 is 30.2%, and photocatalysis performance is poor.
In sum, a kind of CuTCPP/Bi that the present invention provides2WO6Composite photo-catalyst, it is possible to absorb sunshine well, has higher photocatalytic activity, can be used for the dyestuff being difficult to degrade under degraded natural conditions, has application prospect；And described preparation method is simple, controllability is strong, easily accomplishes scale production.
The present invention is not limited by above-mentioned embodiment, the change made, modifies, substitutes, combines, simplifies under other any Spirit Essence without departing from the present invention and principle, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (6)
1. Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi2WO6Composite photo-catalyst, it is characterised in that: its particle is laminated structure, and the maximum air line distance of any two point in particle, between 50-100nm, calculates, CuTCPP:Bi in mass ratio2WO6For 0.1-1.0:99-99.9.
2. a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi as claimed in claim 12WO6Composite photo-catalyst, it is characterised in that: calculate in mass ratio, CuTCPP:Bi2WO6For 0.1:99.9.
3. a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi as claimed in claim 12WO6Composite photo-catalyst, it is characterised in that: calculate in mass ratio, CuTCPP:Bi2WO6For 0.4:99.6.
4. a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi as claimed in claim 12WO6Composite photo-catalyst, it is characterised in that: calculate in mass ratio, CuTCPP:Bi2WO6For 0.7:99.3.
5. a kind of Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi as claimed in claim 12WO6Composite photo-catalyst, it is characterised in that: calculate in mass ratio, CuTCPP:Bi2WO6For 1.0:99.0.
6. Meso-tetra-(4-methoxyphenyl) porphyrin copper/Bi described in claim 12WO6The preparation method of composite photo-catalyst, it is characterised in that comprise the following steps:
(1), a preparation Bi2WO6The step of powder:
By Bi (NO3)3·5H2O is dissolved in nitric acid, obtains the Bi (NO that concentration is 0.1-2 mol/L3)3Solution；
By Na2WO4·2H2O is dissolved in deionized water, obtains the Na that concentration is 0.05-1 mol/L2WO4The aqueous solution；
Calculate the most in molar ratio, i.e. Bi (NO3)3Bi in solution3+: Na2WO4WO in the aqueous solution4 2-For the ratio of 2:1, by Bi (NO3)3Solution and Na2WO4The aqueous solution mixes, obtain white suspension solution, then pH value is adjusted to be 1-2 with the NaOH aqueous solution that mass percent concentration is 5%-10%, transferring in water heating kettle, controlling temperature is to react 10 ~ 30 hours at 140 ~ 180 DEG C, the reacting liquid filtering of gained, the product of gained is successively with deionized water and absolute ethanol washing, being then centrifuged for, the precipitation control temperature of gained is 50 ~ 65 DEG C and is dried 5 ~ 15 hours, it is thus achieved that Bi2WO6Powder；
(2), by the Bi of step (1) gained2WO6Powder is dissolved in ethanol and carrying out ultrasonically treated 20 ~ 50 minutes, and controlling power is 40-100 W, and frequency is 20-40 KHz, obtains Bi2WO6Suspension;
(3), CuTCPP is dissolved in ethanol, obtains CuTCPP solution；
(4), then by the Bi of step (2) gained2WO6The CuTCPP solution mixing of suspension and step (3) gained, wherein, calculates, CuTCPP:Bi in mass ratio2WO6For 0.1-1.0:99-99.9, then controlling rotating speed is to carry out under 1000-2000 r/min, room temperature reacting 20 ~ 30 hours, and products therefrom is washed with deionized 3-5 time, and then control temperature is 60-80 DEG C and is dried, and obtains CuTCPP/Bi2WO6Composite photo-catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610212118.XA CN105749983B (en) | 2016-04-07 | 2016-04-07 | A kind of tetra- (4- methoxyphenyls) porphyrin coppers/Bi of Meso-2WO6Composite photo-catalyst and preparation method |
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|---|---|---|---|
| CN201610212118.XA CN105749983B (en) | 2016-04-07 | 2016-04-07 | A kind of tetra- (4- methoxyphenyls) porphyrin coppers/Bi of Meso-2WO6Composite photo-catalyst and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN105749983A true CN105749983A (en) | 2016-07-13 |
| CN105749983B CN105749983B (en) | 2018-08-28 |
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| CN201610212118.XA Expired - Fee Related CN105749983B (en) | 2016-04-07 | 2016-04-07 | A kind of tetra- (4- methoxyphenyls) porphyrin coppers/Bi of Meso-2WO6Composite photo-catalyst and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159311A (en) * | 2017-04-25 | 2017-09-15 | 西北师范大学 | A kind of flower-shaped bismuth tungstate porphyrin composite and preparation method thereof |
| CN115400798A (en) * | 2022-08-30 | 2022-11-29 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
| CN115999641A (en) * | 2022-08-29 | 2023-04-25 | 山东万博环境治理有限公司 | CeO (CeO) 2 Cu-TCPP composite photocatalyst and preparation method and application thereof |
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| CN104984764A (en) * | 2015-07-08 | 2015-10-21 | 上海应用技术学院 | Poly 3-hexylthiophene-Bi<2>WO<6> composite photocatalyst and preparation method thereof |
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Patent Citations (1)
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| CN104984764A (en) * | 2015-07-08 | 2015-10-21 | 上海应用技术学院 | Poly 3-hexylthiophene-Bi<2>WO<6> composite photocatalyst and preparation method thereof |
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| DAIMEI CHEN ET AL.: ""Visible light photoactivity enhancement via CuTCPP hybridized g-C3N4 nanocomposite"", 《APPLIED CATALYSIS B：ENVIRONMENTAL》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159311A (en) * | 2017-04-25 | 2017-09-15 | 西北师范大学 | A kind of flower-shaped bismuth tungstate porphyrin composite and preparation method thereof |
| CN115999641A (en) * | 2022-08-29 | 2023-04-25 | 山东万博环境治理有限公司 | CeO (CeO) 2 Cu-TCPP composite photocatalyst and preparation method and application thereof |
| CN115999641B (en) * | 2022-08-29 | 2023-08-15 | 山东万博环境治理有限公司 | CeO (CeO) 2 Cu-TCPP composite photocatalyst and preparation method and application thereof |
| CN115400798A (en) * | 2022-08-30 | 2022-11-29 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
| CN115400798B (en) * | 2022-08-30 | 2023-09-26 | 合肥工业大学 | Preparation method and application of bimetallic modified porphyrin-based MOF catalyst |
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