CN110215918A - A kind of vanadic acid bismuth thin film that no ligand nanocrystal is compound, preparation method and application - Google Patents
A kind of vanadic acid bismuth thin film that no ligand nanocrystal is compound, preparation method and application Download PDFInfo
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- CN110215918A CN110215918A CN201910542871.9A CN201910542871A CN110215918A CN 110215918 A CN110215918 A CN 110215918A CN 201910542871 A CN201910542871 A CN 201910542871A CN 110215918 A CN110215918 A CN 110215918A
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 72
- 239000003446 ligand Substances 0.000 title claims abstract description 68
- 239000010409 thin film Substances 0.000 title claims abstract description 56
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 54
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 54
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 title claims abstract description 54
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000084 colloidal system Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000006193 liquid solution Substances 0.000 claims abstract description 13
- 239000007769 metal material Substances 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 229910002929 BaSnO3 Inorganic materials 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 67
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229910002915 BiVO4 Inorganic materials 0.000 description 40
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 13
- 238000004528 spin coating Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 10
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000003321 amplification Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007836 KH2PO4 Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a kind of vanadic acid bismuth thin films that no ligand nanocrystal is compound, preparation method and application, comprising the following steps: conductor oxidate or metal material are dispersed in liquid phase medium, obtain mixed liquor；Under ultrasonic wave added, mixed liquor is placed under laser beam and is irradiated, obtains no ligand colloid nanocrystalline liquid solution；It will be mixed without ligand colloid nanocrystalline liquid solution with pucherite precursor solution, and be film-made, be sintered, and obtain the vanadic acid bismuth thin film compound without ligand nanocrystal.In the present invention, the introducing of no ligand nanocrystal improves the carrier concentration of vanadic acid bismuth thin film, and then promote the transmission process of current-carrying daughter, the film photoelectric current density is tested, it was found that for the vanadic acid bismuth thin film of no compound no ligand nanocrystal, density of photocurrent is from 4.01mA cm‑2It is increased to 5mA cm‑2Left and right, incident photon-to-electron conversion efficiency are increased to 80% or so from 55%, and performance is obviously improved.
Description
Technical field
The present invention relates to photocatalysis and photoelectrocatalysimaterial material preparation technical field, and in particular to a kind of no ligand nanocrystal
Compound vanadic acid bismuth thin film, preparation method and application.
Background technique
Pucherite (BiVO4) widely paid close attention to and ground as a kind of very promising oxide semiconductor electrode material
Study carefully.Due to having the characteristics that cheap, nontoxic, N-type characteristic, good visible light-responded and relatively suitable band structure, BiVO4
Film is often used as light anode.But simple BiVO4Photo-anode film is due to having very low carrier mobility
(0.044cm2V-1s-1) and there is a problem of that photo-generated carrier is compound serious on internal and surface, so as to cause resulting
BiVO4Photo-anode film density of photocurrent is well below its theoretical value (7.5mA cm-2), so that its application is received great limit
System.In recent years, a series of material of high conductivity, such as carbon dots, black phosphorus and graphite alkene are used for BiVO4Film surface promotes
Carrier is in the transmission on surface, but poor current-carrying daughter transmittability still restricts BiVO4The development of photo-anode film
And application.
High conductivity material is used for reference to BiVO4The modification of film surface, by carrier transport ability relatively strong/high conductivity
Material introduces the body transmission process for being expected to promote carrier inside film, and then improves BiVO4The performance of film.It is contemplated that
BiVO4How the material of carrier transport ability relatively strong/high conductivity is introduced BiVO by the crystallization process of film4It is inside film
Obtain high-performance BiVO4The difficult point of light anode, this is also exactly the technical problems to be solved by the invention.
Summary of the invention
The present invention is directed to BiVO4The problem that carrier bluk recombination is serious, transmittability is poor provides a kind of based on liquid phase pulse
The BiVO compound without ligand nanocrystal of laser irradiation technology4The preparation method of film, i.e., by carrier transport ability it is relatively strong/
The nanocrystal of high conductivity material introduces BiVO4Inside film, to obtain the BiVO with high photoelectrochemical behaviour4Light anode
Film.
The first purpose of the invention is to provide a kind of vanadic acid bismuth thin films that no ligand nanocrystal is compound, including contain
(040) the vanadic acid bismuth thin film of Solute Content in Grain, and be compounded in the vanadic acid bismuth thin film without ligand nanocrystal, and institute
Stating mole accounting of no ligand nanocrystal in the compound vanadic acid bismuth thin film of the no ligand nanocrystal is 0.1-5%；
Wherein, the no ligand nanocrystal is by conductor oxidate mixed liquor or metal material mixed liquor through laser beam spoke
According to obtaining；The conductor oxidate mixed liquor or metal material mixed liquor are dispersed in liquid by conductor oxidate or metal material
It is obtained in phase medium.
Preferably, the conductor oxidate is La:BaSnO3Or WO3；The metal material is Au or Ag.
Preferably, the liquid phase medium is one in water, ethyl alcohol, ethylene glycol, acetone, isopropanol, ethyl acetate or acetic acid
Kind is a variety of.
A second object of the present invention is to provide a kind of preparation method of vanadic acid bismuth thin film that no ligand nanocrystal is compound,
The following steps are included:
Conductor oxidate is dispersed in liquid phase medium by step 1, obtains mixed liquor；Or metal material is dispersed in
In liquid phase medium, it is subsequently placed under laser beam and irradiates, metal material is taken out after irradiation, obtains mixed liquor；
Wherein, the concentration of the mixed liquor is 0.5-30mg/mL；
Mixed liquor in step 1 is placed under laser beam and irradiates by step 2, obtains no ligand colloid nanocrystalline liquid solution；
Step 3 will be mixed with pucherite precursor solution without ligand colloid nanocrystalline liquid solution in step 2, be film-made, burning
Knot obtains the vanadic acid bismuth thin film compound without ligand nanocrystal；
Wherein, pucherite precursor solution concentration is 0.1-0.3mol/L；
Volume ratio 1:1-4 without ligand colloid nanocrystalline liquid solution Yu pucherite precursor solution.
Preferably, laser uses non-focusing laser in step 1, and the pulse frequency of the non-focusing laser is 10Hz, defeated
Wavelength is 1064nm out, and output facula diameter is 10mm, and laser irradiation energy is 1.08J/cm2, irradiation time 1min.
Preferably, in step 2 laser use non-focusing laser, and the pulse frequency of the non-focusing laser be 10Hz or
30Hz, output wavelength 355nm, 532nm or 1064nm, output facula diameter are 6~10mm, and laser irradiation energy is 200mJ/
cm2~1.5J/cm2, irradiation time is 5~30min.
Preferably, it is less than 10nm without ligand nanocrystal size obtained in step 2.
Preferably, pucherite presoma described in step 3 is molybdenum doping pucherite (Mo:BiVO4)。
Third object of the present invention is to provide the compound vanadic acid bismuth thin films of above-mentioned no ligand nanocrystal in photocatalysis, light
Application in electro-catalysis.
Compared with prior art, the beneficial effects of the present invention are:
1) present invention obtains size the receiving without ligand less than 10nm of more difficult synthesis using liquid-phase pulse laser irradiation technique
Meter Jing Ti, then the vanadic acid bismuth thin film compound without ligand nanocrystal is prepared using metal-organic decomposition method, specifically in forerunner
Spin coating, burning will be carried out after directly pucherite thin film precursor solution will be introduced without ligand colloid nanocrystalline liquid solution in preparation step
Knot, whole preparation process method is simple, mild condition.
2) in the present invention, the introducing of no ligand nanocrystal improves the carrier concentration of vanadic acid bismuth thin film, and then promotes
The transmission process of current-carrying daughter, tests the film photoelectric current density, finds relative to no compound no ligand nanometer
For the vanadic acid bismuth thin film of crystal, density of photocurrent is from 4.01mA cm-2It is increased to 5mA cm-2Left and right, incident photon-to-electron conversion efficiency from
55% is increased to 80% or so, and performance is obviously improved.
Detailed description of the invention
Fig. 1 is the La:BaSnO prepared in embodiment 13The SEM of particle schemes and XRD diagram, wherein figure a is La:BaSnO3?
The SEM figure of grain, figure b are La:BaSnO3The XRD diagram of particle；
Fig. 2 is La:BaSnO in embodiment 13The XRD diagram and TEM of nanocrystal are schemed, wherein figure a is La:BaSnO3Nanometer
The XRD diagram of crystal, figure b are La:BaSnO3The TEM of nanocrystal schemes；
Fig. 3 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4The SEM and TEM of film
Figure, wherein figure a and b is the Mo:BiVO of comparative example 14SEM figure, c and d of the film under different amplification are different times magnifications
TEM figure under several；Scheme the La:BaSnO that e and f is embodiment 13-Mo:BiVO4Film under different amplification SEM figure, g and
H is the TEM figure under different amplification；
Fig. 4 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4The volt-ampere curve of film
Figure and photoelectric conversion efficiency curve graph, wherein figure a is volt-ampere curve figure, schemes b photoelectric conversion efficiency curve graph；
Fig. 5 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4The impedance curve of film
Figure and MS curve graph；
Fig. 6 is WO before non-focusing laser beam treatment in embodiment 33The SEM of particle schemes and WO3The TEM of nanocrystal schemes,
Wherein, figure a is WO before non-focusing laser beam treatment3The SEM of particle schemes, and figure b is WO3The TEM of nanocrystal schemes；
Fig. 7 is Mo:BiVO in comparative example 14WO in film and embodiment 33-Mo:BiVO4The volt-ampere curve figure of film；
Fig. 8 is the TEM figure of Au nanocrystal in embodiment 5；
Fig. 9 is Mo:BiVO in comparative example 14Au-Mo:BiVO in film and embodiment 54The volt-ampere curve figure of film.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific
The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
In the present invention, WO3From Sigma Aldrich, the purchase of Au piece is scientific and technological from middle promise green wood (Beijing) for particle purchase
Co., Ltd, ultrasonic power is 300W, frequency 40kHz in each embodiment；Experimental method described in following each embodiments for example without
Specified otherwise is conventional method；The reagent and material can be commercially available on the market unless otherwise specified.
Embodiment 1
A kind of La:BaSnO3Without the compound vanadic acid bismuth thin film of ligand nanocrystal, including contain (040) Solute Content in Grain
Vanadic acid bismuth thin film and the La:BaSnO that is compounded in vanadic acid bismuth thin film3Without ligand nanocrystal, La:BaSnO3No ligand is received
Meter Jing Ti is in La:BaSnO3Mole accounting in the compound vanadic acid bismuth thin film of no ligand nanocrystal is 0.3%.
Specific preparation method the following steps are included:
Step 1, La:BaSnO is prepared3Particle: by the BaCl of 1mmol2, 0.95mmol SnCl2With the La of 0.05mmol
(NO3)3It is dissolved in the H that 35ml mass concentration is 30%2O2In aqueous solution, with ammonia spirit regulation system pH to 10, then at 50 DEG C
Lower reaction 30min is filtered after completion of the reaction, is dried, and product is finally sintered to 1h at 500 DEG C to get La:BaSnO is arrived3?
Grain；
Step 2, by the La:BaSnO of 1mg3Particle is dispersed in be made of 0.75ml ethylene glycol, 0.25ml water and 1ml acetic acid
In the mixed solvent, obtain mixed liquor；
Step 3, by mixed liquor, first ultrasound pre-processes 30min, then mixed liquor is placed in irradiation reaction under non-focusing laser beam,
Ultrasonic wave added is used in reaction process, react fully progress；Wherein the pulse frequency of non-focusing laser is 10Hz, output wavelength
For 355nm, output facula diameter is 10mm, single pulse energy 200mJ/cm2, clear, colorless colloid is obtained after irradiating 10min
Particle solution, as La:BaSnO3Colloidal solution, the La:BaSnO3La:BaSnO in colloidal solution3The size of nanocrystal is small
In 10nm；
Step 4, La:BaSnO is prepared using spin-coating method3The compound Mo:BiVO of nanocrystal4Film: first by Bi (NO3)3·
5H2O and MoO2(acac)2It is dissolved in the mixed solution being made of 1.125ml ethylene glycol, 1.5ml acetic acid and 0.375ml water, mixes
VO (acac) is added after closing uniformly2, obtain mixture；It is equal that 0.35g block copolymer F-108 mixing is added into mixture
It is even, obtain the Mo:BiVO that concentration is 0.15mol/L4Precursor solution；Wherein, Bi (NO in mixture3)3·5H2The concentration of O is
0.15mol/L, MoO2(acac)2Mass concentration is 2%, VO (acac)2Concentration be 0.3mol/L；
La:BaSnO made from 1ml step 3 is taken again3Colloid nanocrystalline liquid solution is added to the above-mentioned Mo:BiVO of 4ml4Presoma
It in solution, is uniformly mixed, obtains mixed solution, mixed solution is spun on FTO glass, every spin coating is once hot at 350 DEG C
10min is handled, spin coating 3 times repeatedly are finally heat-treated the La:BaSnO that 1h is about 250nm to get film thickness in 500 DEG C3-
Mo:BiVO4Film.
By La:BaSnO3-Mo:BiVO4Film is in KH2PO4With Na2SO3Mixed solution in testing photoelectronic current density,
In, KH in mixed solution2PO4Concentration be 1mol/L, Na2SO3Concentration be 0.1mol/L.
Embodiment 2
A kind of La:BaSnO3Without the compound vanadic acid bismuth thin film of ligand nanocrystal, including contain (040) Solute Content in Grain
Vanadic acid bismuth thin film and the La:BaSnO that is compounded in vanadic acid bismuth thin film3Without ligand nanocrystal, La:BaSnO3No ligand is received
Meter Jing Ti is in La:BaSnO3Mole accounting in the compound vanadic acid bismuth thin film of no ligand nanocrystal is 0.3%.
Specific preparation method is identical with embodiment 1, the difference is that, the La of 1mg in the step 2 of embodiment 2:
BaSnO3Particle is dispersed in 2ml water, obtains mixed liquor.
Embodiment 3
A kind of WO3Without the compound vanadic acid bismuth thin film of ligand nanocrystal, the vanadic acid including containing (040) Solute Content in Grain
Bismuth thin film and the WO being compounded in vanadic acid bismuth thin film3Without ligand nanocrystal, WO3Without ligand nanocrystal in WO3No ligand is received
Mole accounting in meter Jing Ti compound vanadic acid bismuth thin film is 1.5%.
Specific preparation method the following steps are included:
Step 1, by the WO of 2mg3Particle be dispersed in by 0.75ml acetone, 0.25ml water and 1ml ethyl alcohol at mixed solvent
In, obtain mixed liquor；
Step 2, by mixed liquor, first ultrasound pre-processes 30min, then sample is placed in irradiation reaction under non-focusing laser beam, instead
Ultrasonic wave added should be used in the process, and react fully progress；Wherein non-focusing laser pulse frequency is 30Hz, and output wavelength is
355nm, output facula diameter are 8mm, single pulse energy 446mJ/cm2, it is molten that irradiation 10min has obtained transparent blue colloid
Liquid, as size are less than the WO of 10nm3Colloid nanocrystalline liquid solution；
Step 3, WO is prepared using spin-coating method3The compound Mo:BiVO of nanocrystal4Film:
Mo:BiVO4The preparation method is the same as that of Example 1 for precursor solution, wherein Bi (NO in mixture3)3·5H2O's is dense
Degree is 0.1mol/L, MoO2(acac)2Mass concentration is 2%, VO (acac)2Concentration be 0.2mol/L；Mo:BiVO4Presoma
Solution concentration is 0.1mol/L；
Take WO made from 1ml step 23Colloid nanocrystalline liquid solution is added to Mo:BiVO made from 2ml step 34Presoma
It is uniformly mixed after solution, obtains mixed solution, mixed solution is spun on FTO glass, every spin coating is once at 350 DEG C at heat
10min is managed, spin coating 3 times repeatedly are finally heat-treated the WO that 1h is about 250nm to get film thickness in 500 DEG C3-Mo:BiVO4It is thin
Film.
By the WO3-Mo:BiVO4Film is in KH2PO4With Na2SO3Mixed solution in testing photoelectronic current density, wherein it is mixed
Close KH in solution2PO4Concentration be 1mol/L, Na2SO3Concentration be 0.1mol/L.
Embodiment 4
A kind of WO3Without the compound vanadic acid bismuth thin film of ligand nanocrystal, the vanadic acid including containing (040) Solute Content in Grain
Bismuth thin film and the WO being compounded in vanadic acid bismuth thin film3Without ligand nanocrystal, WO3Without ligand nanocrystal in WO3No ligand is received
Mole accounting in meter Jing Ti compound vanadic acid bismuth thin film is 1.5%.
Specific preparation method is identical with embodiment 3, the difference is that, by the WO of 2mg in embodiment 43Particle point
Be dispersed in by 1ml water and 1ml isopropanol in the mixed solvent, obtain mixed liquor.
Embodiment 5
A kind of vanadic acid bismuth thin film that Au is compound without ligand nanocrystal, the vanadic acid including containing (040) Solute Content in Grain
Bismuth thin film and the Au being compounded in vanadic acid bismuth thin film are without ligand nanocrystal, and Au is without ligand nanocrystal in Au without ligand nanometer
Mole accounting in the compound vanadic acid bismuth thin film of crystal is 5%.
Specific preparation method the following steps are included:
Step 1, Au piece is placed in the in the mixed solvent being made of 0.75ml ethyl acetate, 0.25ml water and 1ml acetic acid；It will
Mixed solvent containing Au piece, which is placed under non-focusing laser beam, irradiates 1min, and ultrasonic wave added is used in reaction process, fills reaction
Divide and carries out；Non-focusing laser pulse frequency is 10Hz, and output wavelength 1064nm, output facula diameter is about 10mm, pulse
Energy is 1.08J/cm2；Au piece is taken out from the mixed solvent after being disposed, obtains the mixed liquor that concentration is 30mg/ml；
Step 2, continue to use non-focusing laser irradiation mixed liquor 10min, and continue during the reaction using ultrasonic wave added
Reaction, laser pulse frequency 10Hz, output wavelength 1064nm, output facula diameter is about 6mm, and single pulse energy is
1.5J/cm2, obtained transparent powder coloring agent liquid solution, as Au colloid nanocrystalline liquid solution of the size less than 10nm；
Step 3, the compound Mo:BiVO of Au nanocrystal is prepared using spin-coating method4Film: Mo:BiVO4Precursor solution
The preparation method is the same as that of Example 1, wherein Bi (NO in mixture3)3·5H2The concentration of O is 0.3mol/L, MoO2(acac)2Quality is dense
Degree is 2%, VO (acac)2Concentration be 0.6mol/L；Mo:BiVO4The concentration of precursor solution is 0.3mol/L；
Au colloid nanocrystalline liquid solution made from 1ml step 2 is taken to be added to the above-mentioned Mo:BiVO of 1ml4After in precursor solution
Be uniformly mixed, obtain mixed solution, mixed solution is spun on FTO glass, every spin coating once in 350 DEG C of heat treatment 10min,
Spin coating 3 times repeatedly are finally heat-treated the Au-Mo:BiVO that 1h is about 250nm to get film thickness in 500 DEG C4Film.
By the Au-Mo:BiVO4Film is in KH2PO4With Na2SO3Mixed solution in testing photoelectronic current density, wherein mixing
KH in solution2PO4Concentration be 1mol/L, Na2SO3Concentration be 0.1mol/L.
Embodiment 6
A kind of vanadic acid bismuth thin film that Ag is compound without ligand nanocrystal, the vanadic acid including containing (040) Solute Content in Grain
Bismuth thin film and the Ag being compounded in vanadic acid bismuth thin film are without ligand nanocrystal, and Ag is without ligand nanocrystal in Ag without ligand nanometer
Mole accounting in the compound vanadic acid bismuth thin film of crystal is 5%.
Preparation method and embodiment 5 are identical, the difference is that Ag piece is placed in by 0.75ml in the step 1 of embodiment 6
The in the mixed solvent of ethyl acetate, 0.25ml water and 1ml acetic acid composition.
Comparative example 1
Mo:BiVO is prepared using spin-coating method4Film: first by the Bi (NO of 0.15mol/L3)3·5H2O and mass concentration are
2% MoO2(acac)2It is dissolved in the mixed solution being made of 1.5ml ethylene glycol, 2ml acetic acid and 0.5ml water, is uniformly mixed,
Add 0.3mol/L VO (acac)2, the block copolymer F-108 that 0.35g is added after mixing is uniformly mixed, obtain Mo:
BiVO4Precursor solution；
By Mo:BiVO4Precursor solution is spun on FTO glass, and every spin coating is once heat-treated 10min at 350 DEG C, instead
Multiple spin coating 3 times, the Mo:BiVO that 1h is about 250nm to get film thickness is finally heat-treated at 500 DEG C4Film.
By the Mo:BiVO4Film is in KH2PO4With Na2SO3Mixed solution in testing photoelectronic current density, wherein mixing it is molten
KH in liquid2PO4Concentration be 1mol/L, Na2SO3Concentration be 0.1mol/L.
Since the film performance that embodiment 1 and embodiment 2 are prepared is essentially identical, what embodiment 3 and embodiment 4 were prepared
Film performance is essentially identical, and the film performance that embodiment 5 and embodiment 6 are prepared is essentially identical, therefore only to embodiment 1,3,5
It is tested with the density of photocurrent of film obtained in comparative example 1, to illustrate effect of the invention, concrete outcome is shown in Table 1.
1 density of photocurrent of table
| Project | Density of photocurrent (1.23VRHE) |
| Embodiment 1 | 5.15mA cm-2 |
| Embodiment 3 | 4.86mA cm-2 |
| Embodiment 5 | 5.05mA cm-2 |
| Comparative example 1 | 4.01mA cm-2 |
As it can be seen from table 1 the density of photocurrent of film obtained is above the film of comparative example 1 in embodiment 1,3,5
Density of photocurrent.28.75%, 21.5% and has been respectively increased compared with comparative example 1 in the density of photocurrent of embodiment 1,3,5
26.25%.
In order to illustrate effect of the invention, the present invention also to raw material in embodiment 1,3,5 and comparative example 1 and is prepared
The performance of product is tested, and concrete outcome is shown in Fig. 1-9.
Fig. 1 is the La:BaSnO prepared in embodiment 13The SEM of particle schemes and XRD diagram, wherein figure a is La:BaSnO3?
The SEM figure of grain, figure b are La:BaSnO3The XRD diagram of particle can be seen that La:BaSnO from figure a and figure b3Particle is cubic phase tin
Sour barium, particle size are about 40nm.
Fig. 2 is La:BaSnO in embodiment 13The XRD diagram and TEM of nanocrystal are schemed, wherein figure a is La:BaSnO3Nanometer
The XRD diagram of crystal, figure b are La:BaSnO3The TEM of nanocrystal schemes, it can be seen from the figure that nanocrystal is still cubic phase tin
Sour barium, size are less than 10nm.
Fig. 3 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4Film SEM figure and
TEM figure, wherein figure a and b is the Mo:BiVO of comparative example 14SEM figure, c and d of the film under different amplification are TEM figure；
Scheme the La:BaSnO that e and f is embodiment 13-Mo:BiVO4SEM figure, g and h of the film under different amplification are TEM figure；From
Fig. 3 can be seen that La:BaSnO3Introducing so that the partial size of film is become smaller, thickness is constant；This it appears that Mo from TEM figure:
BiVO4Film is relatively smooth, La:BaSnO3-Mo:BiVO4Film is clearly present many small nanocrystals.
Fig. 4 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4The volt-ampere curve of film
Figure and photoelectric conversion efficiency curve graph, wherein figure a is volt-ampere curve figure, and figure b photoelectric conversion efficiency curve graph can be with from figure
Find out, La:BaSnO3La:BaSnO after compound3-Mo:BiVO4The density of photocurrent of film significantly improves, in 1.23VRHEUnder light
Current density improves about 28.4%；Photoelectric conversion efficiency improves about 45.5%.
Fig. 5 is the Mo:BiVO of comparative example 14The La:BaSnO of film and embodiment 13-Mo:BiVO4The impedance curve of film
Figure and MS curve graph, wherein figure a is impedance plot, and figure b is MS curve graph, from fig. 5, it can be seen that La:BaSnO3After compound
La:BaSnO3-Mo:BiVO4The impedance of film is obviously reduced, and carrier concentration significantly increases.
Fig. 6 is WO before non-focusing laser beam treatment in embodiment 33The SEM of particle schemes and WO3The TEM of nanocrystal schemes,
Wherein, figure a is WO before non-focusing laser beam treatment3The SEM of particle schemes, and figure b is WO3The TEM of nanocrystal schemes, can from Fig. 6
Out, particle size is about 100nm before handling, and nanocrystal size is less than 10nm after processing.
Fig. 7 is Mo:BiVO in comparative example 14WO in film and embodiment 33-Mo:BiVO4The volt-ampere curve figure of film, from figure
7 as can be seen that WO3WO after compound3-Mo:BiVO4The density of photocurrent of film significantly improves, in 1.23VRHEUnder photoelectric current it is close
Degree improves about 20.7%.
Fig. 8 is the TEM figure of Au nanocrystal in embodiment 5, from figure 8, it is seen that nanocrystal size is less than 10nm.
Fig. 9 is Mo:BiVO in comparative example 14Au-Mo:BiVO in film and embodiment 54The volt-ampere curve figure of film, from Fig. 9
As can be seen that Au-Mo:BiVO after Au is compound4The density of photocurrent of film significantly improves, in 1.23VRHEUnder density of photocurrent
Improve about 25.9%.
The present invention describes preferred embodiment and its effect.It is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of vanadic acid bismuth thin film that no ligand nanocrystal is compound, which is characterized in that including containing (040) Solute Content in Grain
Vanadic acid bismuth thin film, and be compounded in the vanadic acid bismuth thin film without ligand nanocrystal, the no ligand nanocrystal exists
Mole accounting in the compound vanadic acid bismuth thin film of the no ligand nanocrystal is 0.1-5%；
Wherein, the no ligand nanocrystal is irradiated by conductor oxidate mixed liquor or metal material mixed liquor through laser beam
It arrives；The conductor oxidate mixed liquor or metal material mixed liquor are dispersed in liquid phase matchmaker by conductor oxidate or metal material
It is obtained in Jie.
2. the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 1, which is characterized in that the semiconductor
Oxide is La:BaSnO3Or WO3, the metal material is Au or Ag.
3. the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 1, which is characterized in that the liquid phase matchmaker
Be situated between is one of water, ethyl alcohol, ethylene glycol, acetone, isopropanol, ethyl acetate or acetic acid or a variety of.
4. a kind of preparation method for the vanadic acid bismuth thin film that no ligand nanocrystal described in claim 1 is compound, which is characterized in that
The following steps are included:
Conductor oxidate is dispersed in liquid phase medium by step 1, obtains mixed liquor；Or metal material is dispersed in liquid phase
In medium, it is subsequently placed under laser beam and irradiates, metal material is taken out after irradiation, obtains mixed liquor；
Wherein, the concentration of the mixed liquor is 0.5-30mg/mL；
Step 2, under ultrasonic wave added, mixed liquor in step 1 is placed under laser beam and is irradiated, no ligand colloidal nanocrystals are obtained
Solution；
Step 3 will be mixed with pucherite precursor solution without ligand colloid nanocrystalline liquid solution in step 2, be film-made, being sintered, and be obtained
Obtain the vanadic acid bismuth thin film compound without ligand nanocrystal；
Wherein, pucherite precursor solution concentration is 0.1-0.3mol/L.
5. the preparation method of the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 4, which is characterized in that
In step 1 laser use non-focusing laser, and the pulse frequency of the non-focusing laser be 10Hz, output wavelength 1064nm,
Output facula diameter is 10mm, and laser irradiation energy is 1.08J/cm2, irradiation time 1min.
6. the preparation method of the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 4, which is characterized in that
Laser uses non-focusing laser in step 2, and the pulse frequency of the non-focusing laser is 10Hz or 30Hz, and output wavelength is
355nm, 532nm or 1064nm, output facula diameter are 6~10mm, and laser irradiation energy is 200mJ/cm2-1.5J/cm2, spoke
It is 5-30min according to the time.
7. the preparation method of the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 4, which is characterized in that
It is less than 10nm without ligand nanocrystal size obtained in step 2.
8. the preparation method of the compound vanadic acid bismuth thin film of no ligand nanocrystal according to claim 4, which is characterized in that
Pucherite presoma described in step 3 is molybdenum doping pucherite.
9. a kind of vanadic acid bismuth thin film that no ligand nanocrystal described in claim 1 is compound is in photocatalysis, photoelectrocatalysis
Using.
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| CN111302650A (en) * | 2020-03-17 | 2020-06-19 | 吉林大学 | Method for preparing bismuth vanadate photoelectric anode by spin coating of nanoparticle solution |
| CN112941548A (en) * | 2021-01-27 | 2021-06-11 | 西北工业大学 | Hydroxyl-functionalized carbon-point-modified bismuth vanadate film, and preparation method and application thereof |
| CN116283287A (en) * | 2023-03-20 | 2023-06-23 | 西北工业大学 | Quantum sheet anchored bismuth vanadate film, preparation method and application |
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| CN116283287A (en) * | 2023-03-20 | 2023-06-23 | 西北工业大学 | Quantum sheet anchored bismuth vanadate film, preparation method and application |
| CN116283287B (en) * | 2023-03-20 | 2024-04-05 | 西北工业大学 | Quantum sheet anchored bismuth vanadate film, preparation method and application |
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