CN112473747A - Preparation method and application of gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst - Google Patents
Preparation method and application of gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst Download PDFInfo
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- CN112473747A CN112473747A CN202011481971.4A CN202011481971A CN112473747A CN 112473747 A CN112473747 A CN 112473747A CN 202011481971 A CN202011481971 A CN 202011481971A CN 112473747 A CN112473747 A CN 112473747A
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- bismuth vanadate
- metal phthalocyanine
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- heterojunction photocatalyst
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 110
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 85
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 54
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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 title claims abstract description 54
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 33
- 239000010931 gold Substances 0.000 title claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 28
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 35
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 15
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+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 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 claims description 8
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 23
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 19
- 230000001699 photocatalysis Effects 0.000 description 16
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000010757 Reduction Activity Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002915 BiVO4 Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- AJZRPMVVFWWBIW-UHFFFAOYSA-N [Au].[Bi] Chemical compound [Au].[Bi] AJZRPMVVFWWBIW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- B01J35/39—Photocatalytic properties
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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Abstract
A preparation method and application of an ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated and controlled by gold nanoparticles relate to a preparation method and application of a photocatalyst. The method aims to solve the problems that the separation efficiency of the photo-generated carriers of the bismuth vanadate-based heterojunction composite system prepared by the prior art is low and the catalytic activity center is lacked. The method comprises the following steps: firstly, preparing bismuth vanadate nanosheets; secondly, dispersing bismuth vanadate nanosheets in a precursor solution of gold; thirdly, separating, washing and drying; fourthly, dispersing the complex in an alcoholic solution of metal phthalocyanine; fifthly, evaporating the solution in a water bath; and sixthly, drying the reaction product IV to obtain the ultrathin two-dimensional metal phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst. An ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated by gold nanoparticles is used as a photocatalyst to catalytically reduce carbon dioxide or used as a photocatalyst to catalyze water decomposition.
Description
Technical Field
The invention relates to a preparation method and application of a photocatalyst.
Background
The excessive consumption of traditional fossil energy brings about serious environmental pollution and greenhouse effect. Among the various energy conversion modes, the conversion of carbon dioxide into solar fuel using semiconductor photocatalytic technology is a feasible strategy to solve the above problems.
The reasonable design and preparation of the high-efficiency, cheap and stable photocatalyst are of great significance for carbon dioxide reduction. Among the numerous photocatalysts, BiVO4The advantages of abundant sources, stable chemical properties, no toxicity and the like are widely concerned. But BiVO4The separation efficiency of the photon-generated carriers is low due to the positive conduction band energy level position (0 eV NHE); and generally exhibit poor visible photocatalytic carbon dioxide reduction activity due to the lack of surface catalytic active centers. Based on the structure, a Z-type heterojunction composite system can be constructed by compounding another semiconductor with a more negative conduction band energy level, and the charge transfer and separation processes are promoted. In addition, an active center for catalyzing the reduction reaction of carbon dioxide is further introduced, so that the reduction activity of the carbon dioxide is improved.
However, currently, for the design of bismuth vanadate-based Z-type heterojunction photocatalyst, there is usually no reasonable design for inducing directional transfer of photo-generated electrons of bismuth vanadate to an interface, resulting in limited Z-type charge transfer. In addition, the introduction of catalytic activity sites and the expansion of light absorption range are often neglected in the selection of materials for constructing the Z-type heterojunction with bismuth vanadate, so that the photocatalytic carbon dioxide reduction performance is still not ideal.
Disclosure of Invention
The invention provides a preparation method and application of an ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated and controlled by gold nanoparticles, aiming at solving the problems that the separation efficiency of photo-generated carriers of a bismuth vanadate-based heterojunction composite system prepared by the prior art is low and a catalytic active center is lacked.
A preparation method of an ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated by gold nanoparticles comprises the following steps:
firstly, preparing a bismuth vanadate nanosheet:
firstly, adding a bismuth source and a surfactant into an alcohol solvent, stirring until the bismuth source and the surfactant are completely dissolved, adding sodium metavanadate, and continuously stirring for 20-30 min to obtain a suspension;
secondly, transferring the suspension into a high-pressure reaction kettle, reacting for 10-12 h at 120-130 ℃, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, centrifuging the reaction product I, and removing supernatant to obtain a precipitate I; washing the precipitate I with deionized water, drying, and calcining to obtain bismuth vanadate nanosheets;
dispersing bismuth vanadate nanosheets in a precursor solution of gold:
mixing the chloroauric acid solution and the citric acid solution at the temperature of 25-30 ℃, stirring for 10-20 min, then adding the sodium borohydride solution, continuing to stir for 10-20 min, finally adding the bismuth vanadate nanosheet, and stirring for 30-60 min to obtain a reaction product II;
thirdly, separating, washing and drying:
carrying out suction filtration separation on the reaction product II to obtain a precipitate substance II; centrifugally cleaning the sediment substance II by using deionized water as a cleaning agent, and finally drying to obtain a complex;
fourthly, dispersing the complex in an alcoholic solution of metal phthalocyanine:
firstly, dispersing metal phthalocyanine into absolute ethyl alcohol, and then performing ultrasonic dispersion to obtain an alcoholic solution of the metal phthalocyanine;
dispersing the complex in an alcohol solution of metal phthalocyanine, and stirring to obtain a reaction product III;
fifthly, evaporating the solution in a water bath:
placing the reaction product III in a water bath kettle, and evaporating the solution to dryness at the temperature of 60-80 ℃ to obtain a reaction product IV;
and sixthly, drying the reaction product IV to obtain the ultrathin two-dimensional metal phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst.
The invention has the advantages that:
compared with the existing bismuth vanadate-based Z-type photocatalytic material, the gold nanoparticle-regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst prepared by the invention has the advantages that the regulation of the interface by the gold nanoparticles is favorable for the directional transfer and separation of photogenerated electrons;
secondly, the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst prepared by the method has rich surface catalytic active centers, and a cocatalyst is not required to be introduced to catalyze the carbon dioxide reduction reaction;
the prepared gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst is suitable for being used as a photocatalytic carbon dioxide reduction and photocatalytic decomposition water catalyst, and each gram of the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst can be used for photocatalytic reduction of carbon dioxide to generate 12-23 micromolar carbon monoxide and 2-4 micromolar methane.
An ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated by gold nanoparticles is used as a photocatalyst to catalytically reduce carbon dioxide or used as a photocatalyst to catalyze water decomposition.
Drawings
FIG. 1 is an X-ray diffraction pattern of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
FIG. 2 is a transmission electron microscope image of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
FIG. 3 is a fluorescence spectrum of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
FIG. 4 is a graph of the photocatalytic carbon dioxide reduction activity of a prepared ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst tested;
FIG. 5 is a graph showing the photocatalytic water splitting activity of a prepared ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst;
FIG. 6 is a surface photovoltage spectrum of the ultra-thin cobalt-bis-phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in experiment two;
FIG. 7 is a UV-VISIBLE Diffuse reflectance plot of ultra-thin cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in experiment two;
fig. 8 is a bar graph of carbon dioxide reduction by the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the first test, the ultra-thin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the second test, and the ultra-thin two-dimensional nickel phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the third test.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst in the embodiment is completed according to the following steps:
firstly, preparing a bismuth vanadate nanosheet:
firstly, adding a bismuth source and a surfactant into an alcohol solvent, stirring until the bismuth source and the surfactant are completely dissolved, adding sodium metavanadate, and continuously stirring for 20-30 min to obtain a suspension;
secondly, transferring the suspension into a high-pressure reaction kettle, reacting for 10-12 h at 120-130 ℃, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, centrifuging the reaction product I, and removing supernatant to obtain a precipitate I; washing the precipitate I with deionized water, drying, and calcining to obtain bismuth vanadate nanosheets;
dispersing bismuth vanadate nanosheets in a precursor solution of gold:
mixing the chloroauric acid solution and the citric acid solution at the temperature of 25-30 ℃, stirring for 10-20 min, then adding the sodium borohydride solution, continuing to stir for 10-20 min, finally adding the bismuth vanadate nanosheet, and stirring for 30-60 min to obtain a reaction product II;
thirdly, separating, washing and drying:
carrying out suction filtration separation on the reaction product II to obtain a precipitate substance II; centrifugally cleaning the sediment substance II by using deionized water as a cleaning agent, and finally drying to obtain a complex;
fourthly, dispersing the complex in an alcoholic solution of metal phthalocyanine:
firstly, dispersing metal phthalocyanine into absolute ethyl alcohol, and then performing ultrasonic dispersion to obtain an alcoholic solution of the metal phthalocyanine;
dispersing the complex in an alcohol solution of metal phthalocyanine, and stirring to obtain a reaction product III;
fifthly, evaporating the solution in a water bath:
placing the reaction product III in a water bath kettle, and evaporating the solution to dryness at the temperature of 60-80 ℃ to obtain a reaction product IV;
and sixthly, drying the reaction product IV to obtain the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the bismuth source in the first step is bismuth chloride; the alcohol solvent in the first step is glycol; the surfactant in the first step is cetyl trimethyl ammonium bromide. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the volume ratio of the mass of the bismuth source to the alcohol solvent in the first step is (2.21 g-11.05 g): 60 mL-300 mL; the volume ratio of the mass of the surfactant to the volume of the alcohol solvent in the first step is (1.05-5.25 g): 30-60 mL; the volume ratio of the mass of the sodium metavanadate to the alcohol solvent in the first step is (2.8 g-14 g) to (60 mL-300 mL); the stirring speed in the first step is 300 r/min-500 r/min. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the step one, the drying temperature is 60-80 ℃, the drying time is 12-24 h, the calcining temperature is 400-450 ℃, and the calcining time is 8-12 min. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the concentration of the chloroauric acid solution in the step two is 2 g/L-4 g/L; the concentration of the citric acid solution is 0.6 g/L-0.8 g/L; the concentration of the sodium borohydride solution is 0.01-0.02 mol/L; the stirring speed is 100 r/min-300 r/min. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the volume ratio of the mass of the bismuth vanadate nanosheet to the volume of the chloroauric acid solution in the second step is (0.1-0.2 g): 0.5-1 mL; the volume ratio of the mass of the bismuth vanadate nanosheet to the volume of the citric acid solution is (0.1-0.2 g): 10-20 mL); the volume ratio of the mass of the bismuth vanadate nanosheet to the volume of the sodium borohydride solution is (0.1-0.2 g) to (0.2-0.5 mL). The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the speed of the centrifugal cleaning in the third step is 3000 r/min-4000 r/min, the times of the centrifugal cleaning are 3-6 times, and the time of each centrifugal cleaning is 5-10 min; the drying temperature in the third step is 60-70 ℃, and the drying time is 12-24 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the volume ratio of the mass of the metal phthalocyanine to the absolute ethyl alcohol in the fourth step is (0.001-0.003 g): 20-30 mL; the metal phthalocyanine in the fourth step is copper phthalocyanine, cobalt phthalocyanine or nickel phthalocyanine; the power of ultrasonic dispersion in the step IV is 100W-300W, and the ultrasonic dispersion time is 30 min-40 min; the volume ratio of the mass of the complex to the alcoholic solution of the metal phthalocyanine in the fourth step is (0.1 g-0.2 g): 30 mL-40 mL; and fourthly, the stirring speed is 100r/min to 300r/min, and the stirring time is 30min to 60 min. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and the drying temperature in the sixth step is 60-70 ℃, and the drying time is 12-24 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst is used as a photocatalyst to catalyze and reduce carbon dioxide or used as a photocatalyst to catalyze water decomposition.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Test one: a preparation method of an ultrathin two-dimensional copper phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated by gold nanoparticles comprises the following steps:
firstly, preparing a bismuth vanadate nanosheet:
firstly, adding 2.21g of bismuth chloride and 1.05g of hexadecyl trimethyl ammonium bromide into 60mL of ethylene glycol, stirring until the bismuth chloride and the hexadecyl trimethyl ammonium bromide are completely dissolved, then adding 2.8g of sodium metavanadate, and continuously stirring for 30min to obtain a suspension;
the stirring speed in the first step is 300 r/min;
secondly, transferring the suspension into a high-pressure reaction kettle, reacting for 12 hours at 120 ℃, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, centrifuging the reaction product I, and removing supernatant to obtain a precipitate I; washing the precipitate I with deionized water, drying, and calcining to obtain bismuth vanadate nanosheets;
the drying temperature in the third step is 60 ℃, the drying time is 12 hours, the calcining temperature is 400 ℃, and the calcining time is 8 min;
dispersing bismuth vanadate nanosheets in a precursor solution of gold:
mixing 1mL of chloroauric acid solution and 20mL of citric acid solution at the temperature of 30 ℃, stirring for 20min, then adding 0.5mL of sodium borohydride solution, continuing to stir for 20min, finally adding 0.2g of bismuth vanadate nanosheet, and stirring for 60min to obtain a reaction product II;
the concentration of the chloroauric acid solution in the step two is 4 g/L;
the concentration of the citric acid solution in the second step is 0.73 g/L;
the concentration of the sodium borohydride solution in the step two is 0.01 mol/L;
the stirring speed in the step two is 300 r/min;
thirdly, separating, washing and drying:
carrying out suction filtration separation on the reaction product II to obtain a precipitate substance II; centrifugally cleaning the sediment substance II by using deionized water as a cleaning agent, and finally drying to obtain a complex;
the speed of the centrifugal cleaning in the third step is 4000r/min, the times of the centrifugal cleaning are 5 times, and the time of each centrifugal cleaning is 5 min; the drying temperature in the third step is 60 ℃, and the drying time is 12 hours;
fourthly, dispersing the complex in an alcoholic solution of metal phthalocyanine:
dispersing 0.003g of metal phthalocyanine into 30mL of absolute ethyl alcohol, and then performing ultrasonic dispersion for 30min at the ultrasonic dispersion power of 300W to obtain an alcohol solution of the metal phthalocyanine;
the metal phthalocyanine in the step IV is copper phthalocyanine;
secondly, dispersing 0.1g of the complex in 30mL of alcoholic solution of metal phthalocyanine, and stirring for 60min at the stirring speed of 300r/min to obtain a reaction product III;
fifthly, evaporating the solution in a water bath:
placing the reaction product III in a water bath kettle, and evaporating the solution to dryness at the temperature of 60 ℃ to obtain a reaction product IV;
sixthly, drying the reaction product IV at 60 ℃ for 12 hours to obtain the ultrathin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst.
FIG. 1 is an X-ray diffraction pattern of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
as can be seen from FIG. 1, the introduction of copper phthalocyanine and gold nanoparticles did not change the crystal phase and degree of crystallization of bismuth vanadate.
FIG. 2 is a transmission electron microscope image of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
as can be seen from fig. 2, the ultrathin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the experiment has an ultrathin two-dimensional lamellar structure, and is beneficial to rapid charge transfer and separation.
FIG. 3 is a fluorescence spectrum of an ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by experiment one;
as can be seen from FIG. 3, the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the experiment is beneficial to transferring and separating photogenerated charges.
0.1g of the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in test one was added to 5mL of a photocatalyst containing saturated CO2The gas in distilled water was transferred to a 50mL quartz glass reactor using a visible light intensity of 400mW/cm2Irradiating the quartz glass reaction kettle with visible light for 4 hours, then extracting gas in the quartz glass reaction kettle, and finally detecting by using a chromatograph, wherein the detection result is shown in figure 4;
FIG. 4 is a graph of the photocatalytic carbon dioxide reduction activity of a prepared ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst tested;
as can be seen from FIG. 4, the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the experiment is beneficial to photocatalytic carbon dioxide reduction.
The method adopts the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the first test to carry out photocatalytic water decomposition, and specifically comprises the following steps:
0.1g of the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the first test is added into 100mL of ultra-pure water, and then the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst is transferred into a 200mL quartz glass reactor, and the visible light intensity is 400mW/cm2The visible light irradiates the quartz glass reactor for 4 hours, and the generated gas is automatically injected into a chromatogram for detection and detectionThe measurement results are shown in FIG. 5;
FIG. 5 is a graph showing the photocatalytic water splitting activity of a prepared ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst;
as can be seen from FIG. 5, the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the experiment is beneficial to photocatalytic water decomposition.
And (2) test II: the difference between this test and test one is: and fourthly, the metal phthalocyanine in the fourth step is cobalt phthalocyanine to obtain the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst. The other steps and parameters were the same as those of experiment one.
The ultra-thin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the test is detected by a surface photovoltage spectrometer, and the detection result is shown in figure 6;
FIG. 6 is a surface photovoltage spectrum of the ultra-thin cobalt-bis-phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in experiment two;
as can be seen from fig. 6, the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the experiment has high charge separation performance, and the two-dimensional complex with the ultrathin structure is proved to be beneficial to photocatalytic carbon dioxide reduction.
Detecting the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared by the test by adopting an ultraviolet visible diffuse reflectance spectrometer, wherein the detection result is shown in figure 7;
FIG. 7 is a UV-VISIBLE Diffuse reflectance plot of ultra-thin cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in experiment two;
as can be seen from fig. 7, the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in test two has a wider visible light response, and it is proved that the two-dimensional complex with the ultrathin structure is beneficial to enhancing visible light absorption.
And (3) test III: the difference between this test and test one is: and fourthly, the metal phthalocyanine is nickel phthalocyanine, and the ultrathin two-dimensional nickel phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst is obtained. The other steps and parameters were the same as those of experiment one.
0.1g of the ultra-thin two-dimensional copper phthalocyanine prepared in test one was separately addedThe gold-bismuth vanadate heterojunction photocatalyst, 0.1g of the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the second experiment and 0.1g of the ultrathin two-dimensional nickel phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the third experiment are respectively added into 5mL of the photocatalyst containing saturated CO2Transferring the gas distilled water into 50mL quartz glass reaction kettles respectively, and respectively using visible light intensity of 400mW/cm2Irradiating the quartz glass reaction kettle with visible light for 4 hours, respectively extracting gas in the quartz glass reaction kettle, and finally respectively detecting by using a chromatograph, wherein the detection result is shown in a figure 8;
fig. 8 is a bar graph of carbon dioxide reduction by the ultra-thin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the first test, the ultra-thin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the second test, and the ultra-thin two-dimensional nickel phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the third test.
As can be seen from fig. 8, the ultrathin two-dimensional copper phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the first test has higher photocatalytic carbon dioxide reduction performance than the ultrathin two-dimensional cobalt phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the second test and the ultrathin two-dimensional nickel phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst prepared in the third test, and the main products are carbon monoxide and methane.
Claims (10)
1. A preparation method of an ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst regulated and controlled by gold nanoparticles is characterized by comprising the following steps:
firstly, preparing a bismuth vanadate nanosheet:
firstly, adding a bismuth source and a surfactant into an alcohol solvent, stirring until the bismuth source and the surfactant are completely dissolved, adding sodium metavanadate, and continuously stirring for 20-30 min to obtain a suspension;
secondly, transferring the suspension into a high-pressure reaction kettle, reacting for 10-12 h at 120-130 ℃, and naturally cooling to room temperature to obtain a reaction product I;
thirdly, centrifuging the reaction product I, and removing supernatant to obtain a precipitate I; washing the precipitate I with deionized water, drying, and calcining to obtain bismuth vanadate nanosheets;
dispersing bismuth vanadate nanosheets in a precursor solution of gold:
mixing the chloroauric acid solution and the citric acid solution at the temperature of 25-30 ℃, stirring for 10-20 min, then adding the sodium borohydride solution, continuing to stir for 10-20 min, finally adding the bismuth vanadate nanosheet, and stirring for 30-60 min to obtain a reaction product II;
thirdly, separating, washing and drying:
carrying out suction filtration separation on the reaction product II to obtain a precipitate substance II; centrifugally cleaning the sediment substance II by using deionized water as a cleaning agent, and finally drying to obtain a complex;
fourthly, dispersing the complex in an alcoholic solution of metal phthalocyanine:
firstly, dispersing metal phthalocyanine into absolute ethyl alcohol, and then performing ultrasonic dispersion to obtain an alcoholic solution of the metal phthalocyanine;
dispersing the complex in an alcohol solution of metal phthalocyanine, and stirring to obtain a reaction product III;
fifthly, evaporating the solution in a water bath:
placing the reaction product III in a water bath kettle, and evaporating the solution to dryness at the temperature of 60-80 ℃ to obtain a reaction product IV;
and sixthly, drying the reaction product IV to obtain the ultrathin two-dimensional metal phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst.
2. The preparation method of the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the bismuth source in the first step is bismuth chloride; the alcohol solvent in the first step is glycol; the surfactant in the first step is cetyl trimethyl ammonium bromide.
3. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the ratio of the mass of the bismuth source to the volume of the alcohol solvent in the first step (i) is (2.21 g-11.05 g) to (60 mL-300 mL); the volume ratio of the mass of the surfactant to the volume of the alcohol solvent in the first step is (1.05-5.25 g): 30-60 mL; the volume ratio of the mass of the sodium metavanadate to the alcohol solvent in the first step is (2.8 g-14 g) to (60 mL-300 mL); the stirring speed in the first step is 300 r/min-500 r/min.
4. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst according to claim 1, characterized in that the drying temperature in the first step is 60-80 ℃, the drying time is 12-24 h, the calcining temperature is 400-450 ℃, and the calcining time is 8-12 min.
5. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the concentration of the chloroauric acid solution in the step two is 2 g/L-4 g/L; the concentration of the citric acid solution is 0.6 g/L-0.8 g/L; the concentration of the sodium borohydride solution is 0.01-0.02 mol/L; the stirring speed is 100 r/min-300 r/min.
6. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the ratio of the mass of the bismuth vanadate nanosheet to the volume of the chloroauric acid solution in the second step is (0.1 g-0.2 g): (0.5 mL-1 mL); the volume ratio of the mass of the bismuth vanadate nanosheet to the volume of the citric acid solution is (0.1-0.2 g): 10-20 mL); the volume ratio of the mass of the bismuth vanadate nanosheet to the volume of the sodium borohydride solution is (0.1-0.2 g) to (0.2-0.5 mL).
7. The preparation method of the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the speed of centrifugal cleaning in the third step is 3000r/min to 4000r/min, the number of centrifugal cleaning is 3 to 6, and the time of each centrifugal cleaning is 5 to 10 min; the drying temperature in the third step is 60-70 ℃, and the drying time is 12-24 h.
8. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst as claimed in claim 1, wherein the volume ratio of the mass of the metal phthalocyanine to the absolute ethyl alcohol in the fourth step is (0.001-0.003 g): 20-30 mL; the metal phthalocyanine in the fourth step is copper phthalocyanine, cobalt phthalocyanine or nickel phthalocyanine; the power of ultrasonic dispersion in the step IV is 100W-300W, and the ultrasonic dispersion time is 30 min-40 min; the volume ratio of the mass of the complex to the alcoholic solution of the metal phthalocyanine in the fourth step is (0.1 g-0.2 g): 30 mL-40 mL; and fourthly, the stirring speed is 100r/min to 300r/min, and the stirring time is 30min to 60 min.
9. The method for preparing gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst according to claim 1, characterized in that the drying temperature in the sixth step is 60-70 ℃ and the drying time is 12-24 h.
10. The application of the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst prepared by the preparation method according to claim 1, wherein the gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst is used as a photocatalyst for catalytically reducing carbon dioxide or used as a photocatalyst for catalyzing water decomposition.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786023A (en) * | 2010-02-12 | 2010-07-28 | 湖州师范学院 | Ultrasonic chemical in-situ preparation method for phthalocyanine-sensitized vanadate nano-powder |
| PT104692A (en) * | 2009-07-29 | 2011-01-31 | Univ Do Minho | PHOTOCATALITICAL COATING FOR CONTROLLED RELEASE OF VOLATILE AGENTS |
| CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
| CN107761127A (en) * | 2017-10-20 | 2018-03-06 | 东北师范大学 | A kind of preparation method for the nanoporous pucherite analysis oxygen electrode that polyacid and phthalocyanine are modified jointly |
| WO2018197715A1 (en) * | 2017-04-28 | 2018-11-01 | Cambridge Enterprise Limited | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN109939744A (en) * | 2019-04-16 | 2019-06-28 | 黑龙江大学 | A kind of preparation method and application of ultra-thin two-dimension metal phthalocyanine/composite bismuth vanadium photocatalyst |
-
2020
- 2020-12-15 CN CN202011481971.4A patent/CN112473747B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT104692A (en) * | 2009-07-29 | 2011-01-31 | Univ Do Minho | PHOTOCATALITICAL COATING FOR CONTROLLED RELEASE OF VOLATILE AGENTS |
| CN101786023A (en) * | 2010-02-12 | 2010-07-28 | 湖州师范学院 | Ultrasonic chemical in-situ preparation method for phthalocyanine-sensitized vanadate nano-powder |
| CN105536770A (en) * | 2016-01-27 | 2016-05-04 | 厦门大学 | Pucherite-based photocatalyst and preparation method and application thereof |
| WO2018197715A1 (en) * | 2017-04-28 | 2018-11-01 | Cambridge Enterprise Limited | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN107761127A (en) * | 2017-10-20 | 2018-03-06 | 东北师范大学 | A kind of preparation method for the nanoporous pucherite analysis oxygen electrode that polyacid and phthalocyanine are modified jointly |
| CN109939744A (en) * | 2019-04-16 | 2019-06-28 | 黑龙江大学 | A kind of preparation method and application of ultra-thin two-dimension metal phthalocyanine/composite bismuth vanadium photocatalyst |
Non-Patent Citations (7)
| Title |
|---|
| JI BIAN ET AL.: "Au-Modulated Z‑Scheme CuPc/BiVO4 Nanosheet Heterojunctions toward Efficient CO2 Conversion under Wide-Visible-Light Irradiation", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| LIU, GS ET AL.: "BiVO4/cobalt phthalocyanine (CoPc) nanofiber heterostructures: synthesis, characterization and application in photodegradation of methylene blue", 《RSC ADVANCES》 * |
| SONG, CL ET AL.: "Enhanced photocatalytic performance of bismuth vanadate assisted by polyoxometalates and phthalocyanine", 《NEW JOURNAL OF CHEMISTRY》 * |
| 刘翀等: "高光催化活性的磷氧桥连TiO2/g-C3N4纳米复合体的合成", 《催化学报》 * |
| 宋美婷: "钒酸铋及其复合半导体纳米催化剂的设计、制备与催化性能研究", 《中国优秀硕士学位论文全文数据库》 * |
| 李厚芬: "异质结光催化剂界面电子迁移的调控方法及光催化特性", 《中国博士学位论文全文数据库》 * |
| 马伟倩: "BiVO4新型光催化剂的制备及性能研究", 《中国优秀硕士学位论文全文数据库》 * |
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